WO2021132578A1

WO2021132578A1 - Curable resin composition, cured film, layered product, method for producing cured film, and semiconductor device

Info

Publication number: WO2021132578A1
Application number: PCT/JP2020/048779
Authority: WO
Inventors: 和臣井上
Original assignee: 富士フイルム株式会社
Priority date: 2019-12-27
Filing date: 2020-12-25
Publication date: 2021-07-01
Also published as: TW202130705A; JPWO2021132578A1; CN114981360A; KR20220107008A; JP7334268B2

Abstract

Provided are: a curable resin composition having a pH lower than 7.0 and containing a solvent, a compound having a triazole structure, and at least one resin selected from the group consisting of polyimides, polybenzoxazoles, and precursors thereof; a cured film obtained by curing the curable resin composition; a layered product including the cured film; a method for producing the cured film; and a semiconductor device including the cured film or the layered product.

Description

Curable resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device

The present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.

Resins such as polyimide and polybenzoxazole are applied to various applications because they have excellent heat resistance and insulating properties. The above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.

For example, in the above-mentioned applications, resins such as polyimide and polybenzoxazole are used in the form of a curable resin composition containing these resins themselves or a curable resin composition containing a precursor of these resins. A cured resin can be formed on the base material by applying such a curable resin composition to the base material by, for example, coating, and then exposing, developing, heating, etc., if necessary. .. Since the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it has excellent adaptability. In addition to the high performance of polyimide, etc., from the viewpoint of excellent manufacturing adaptability, industrial application development of curable resin compositions containing resins such as polyimide and polybenzoxazole or precursors thereof is expanding. It is expected more and more.

For example, Patent Document 1 describes (A) photosensitive resin: 100 parts by mass, (B) photosensitive agent: 1 to 40 parts by mass, (C) copper discoloration inhibitor: 0.05 to 20 parts by mass, and (D). ) A photosensitive resin composition containing a solvent and having a water content of 0.6 to 10% by mass in the photosensitive resin composition is described.

Japanese Unexamined Patent Publication No. 2011-169980

The cured film containing polyimide or polybenzoxazole is used, for example, in the above-mentioned insulating film, encapsulant material, protective film, flexible substrate base film, coverlay, and the like.
In these applications, it is desired to provide a curable resin composition capable of obtaining a cured film excellent in suppressing corrosion of metals such as copper used for wiring and the like.

The present invention relates to a curable resin composition capable of obtaining a cured film excellent in suppressing corrosion of adjacent metals, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film. It is an object of the present invention to provide a method for producing the above and a semiconductor device containing the cured film or the laminate.

Examples of typical embodiments of the present invention are shown below.
<1> At least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
Compounds having a triazole structure, as well as
Contains solvent,
A curable resin composition in which the pH of the composition is less than 7.0.
<2> The curable resin composition according to <1>, wherein the pKa in dimethyl sulfoxide of the compound having a triazole structure is less than 15.
<3> The curable resin composition according to <1> or <2>, wherein the compound having a triazole structure contains a compound having a 1,2,3-triazole structure.
<4> The curable resin composition according to any one of <1> to <3>, wherein the compound having a triazole structure contains a compound having a benzotriazole structure.
<5> A photosensitizer containing 1 to 40 parts by mass, a compound having a triazole structure of 0.05 to 20 parts by mass, and a solvent of 50 to 300 parts by mass with respect to 100 parts by mass of the resin. The curable resin composition according to any one of <4>.
<6> The curable resin composition according to any one of <1> to <5>, which contains a solvent containing no nitrogen atom as the solvent.
<7> The curable resin composition according to any one of <1> to <6>, which comprises a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms as the solvent.
<8> The curable resin composition according to any one of <1> to <7>, which is used for forming an interlayer insulating film for a rewiring layer.
<9> A cured film obtained by curing the curable resin composition according to any one of <1> to <8>.
<10> A laminate containing two or more layers of the cured film according to <9> and containing a metal layer between any of the cured films.
<11> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of <1> to <8> to a substrate to form a film.
<12> The method for producing a cured film according to <11>, which comprises an exposure step of exposing the film and a developing step of developing the film.
<13> The method for producing a cured film according to <11> or <12>, which comprises a heating step of heating the film at 50 to 450 ° C.
<14> A semiconductor device comprising the cured film according to <9> or the laminate according to <10>.

According to the present invention, a curable resin composition capable of obtaining a cured film excellent in suppressing corrosion of adjacent metals, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, the above. A method for producing a cured film and a semiconductor device including the cured film or the laminate are provided.

Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
In the present specification, the term "process" means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacryl", or , Either, and "(meth) acryloyl" means both "acryloyl" and "methacryloyl", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In the present specification, for the weight average molecular weight (Mw) and the number average molecular weight (Mn), for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as "upper". The opposite direction is referred to as "down". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.

(Curable resin composition)
The curable resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) is triazole, at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof. It contains a compound having a structure and a solvent, and the pH of the composition is less than 7.0.
Hereinafter, at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof is also referred to as "specific resin".

According to the curable resin composition of the present invention, a cured film excellent in suppressing corrosion of adjacent metals can be obtained.
The mechanism by which the above effect is obtained is unknown, but it is presumed as follows.

The cured film containing polyimide or polybenzoxazole is used in various devices, for example, as an insulating film, a material for a sealing material, a protective film, a base film for a flexible substrate, a coverlay, and the like.
In such an application, corrosion of the metal at a portion where a metal such as copper used as wiring or the like in a device and a cured film is in contact may become a problem.
The present inventors have found that such metal corrosion is related to the acidity of the composition used for forming the cured film.
When the acidity of the composition is high, the present inventors migrate metal such as copper into the composition as ions, and the components in the cured film or water, oxygen, or water supplied from the outside of the cured film, or It is speculated that it reacts with halogens to form fragile copper compounds and corrosion progresses.

Therefore, as a result of diligent studies by the present inventors, corrosion of metals such as copper is remarkably suppressed by using a composition containing a compound having a triazole structure and having a pH adjusted to less than 7. The present invention has been completed.
In the present invention, when a compound having a triazole structure is dissociated (for example, deprotonated), the adhesion energy with a metal such as copper is improved (J. Phys. Chem. C 2015, 119, 11625-11635). It is presumed that a cured film having an excellent ability to suppress corrosion can be obtained by using a compound having a triazole structure in the composition adjusted to the specific pH.

Here, particularly when the device is used for a long period of time under high humidity or high temperature, corrosion of the metal due to melting of the metal such as copper becomes a problem.
According to the composition of the present invention, it is excellent in the ability to suppress corrosion of a compound having a triazole structure and a metal such as copper even under high temperature and high humidity conditions (for example, conditions such as 150 ° C. and 90% RH relative humidity). ..
Further, according to the composition of the present invention, for example, even when the cured film and the metal are exposed to high temperature conditions, voids (voids) at the interface between the metal and the cured film due to the corrosion suppressing effect of the metal. ) Is considered to be suppressed.

Further, in the composition containing the polyimide precursor or the polybenzoxazole precursor, the cyclization of the polyimide precursor and the polybenzoxazole precursor is suppressed by setting the pH to less than 7, and thus the liquid of the composition. It is considered to have excellent storage stability.
Further, in the composition containing polyimide or polybenzoxazole, when the pH is set to less than 7, main chain breakage (that is, decrease in molecular weight) due to hydrolysis is less likely to occur, and the composition is excellent in liquid storage stability. Conceivable.

Here, Patent Document 1 does not describe or suggest that the pH of the curable resin composition containing the specific resin is within the specific range.
Hereinafter, the curable resin composition of the present invention will be described in detail.

<pH>
The pH of the curable resin composition of the present invention is less than 7.0, preferably 6.8 or less, preferably 6.5 or less, from the viewpoint of metal corrosion inhibition and storage stability of the composition. It is more preferable, it is more preferably 6.2 or less, and it is particularly preferable that it is 6.0 or less.
The lower limit of the pH is not particularly limited, but is preferably 2.0 or higher, more preferably 3.0 or higher, further preferably 4.0 or higher, and preferably 4.5 or higher. It is particularly preferable, and most preferably 5.0 or more.
In the present invention, the pH of the composition is measured by the methods described in (1) to (4) below.
(1) An apparatus (D-71 manufactured by HORIBA) calibrated using standard solutions having pH = 4, 7 and 9 is used.
(2) The electrode of the above device is immersed in a 3.33 mmol / L potassium chloride (KCl) solution.
(3) The composition is diluted with the solvent contained in the composition, and the pH is measured. The above measurement is performed at least at three points where the dilution ratio is changed.
(4) Using the above apparatus, the pH of the measurement solution is measured, and the pH of the composition is calculated from the amount ^{of H + before dilution in consideration of the dilution ratio.}
_{Specifically, when x = log 10} (dilution ratio) and y = pH of the solution after each dilution with respect to the measured values of 3 points or more in which the dilution ratio was changed, which was measured in (3) above. A linear regression (y = ax + b) is performed and the section b is used as the pH of the composition before dilution.
The linear regression is performed by the method of least squares.

Hereinafter, the pH calculation method in Example 1 described later will be described.
_{In Table 1, in the curable resin composition used in Example 1, log 10} (dilution ratio) of the dilution ratio when the dilution ratio (mass ratio) is 3, 30, and 300 times, and each dilution. The pH (measured value) of the subsequent solution is described.

As a result of performing linear regression (y = ax + b) by the least squares method when x = log ₁₀ (dilution ratio) and y = pH of the solution after each dilution, y = 0.22x + 6.0044 is obtained. That is, the pH of the composition described in Example 1 is 6.0.

The pH of the composition is determined by, for example, selection of a solvent, use of an acidic resin (for example, polyimide having an acid group, polybenzoxazole having an acid group, or a precursor thereof and a resin having an acid group). It is adjusted by using a pH adjuster, adjusting the content of a compound having a triazole structure, or a combination of these methods.

<Compound with triazole structure>
The curable resin composition of the present invention contains a compound having a triazole structure.
Hereinafter, a compound having a triazole structure is also referred to as a “specific compound”.
The number of triazole structures in the specific compound may be 1 or more, preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and preferably 1. Especially preferable.
In the present invention, the triazole structure is an aromatic 5-membered ring structure containing three nitrogen atoms, and may be a 1,2,3-triazole structure or a 1,2,4-triazole structure. However, from the viewpoint of suppressing metal corrosion, a 1,2,3-triazole structure is preferable.
There are two types of tautomers in the 1,2,3-triazole structure, 1H-1,2,3 triazole structure and 2H-1,2,3 triazole structure, and any of these may be used. However, it may be a mixture of these.
The 1H-1,2,3 triazole structure has a structure represented by the following formula (T-1), and the 2H-1,2,3 triazole structure has a structure represented by the following formula (T-2). Examples of the 1,2,4 triazole structure include structures represented by the following formula (T-3).

In the above formulas (T-1) to (T-3), # and * each represent a binding site with a hydrogen atom or another structure.
As the triazole structure in the specific compound, a structure represented by any of the formula (T-1), the formula (T-2) and the formula (T-3) is preferable, and from the viewpoint of suppressing metal corrosion, the above formula is described below. The structure represented by either (T-1) or (T-2) is more preferable.

[PKa]
From the viewpoint of suppressing metal corrosion, the pKa in dimethyl sulfoxide (DMSO) of the specific compound is preferably less than 15, more preferably 8 or more and less than 15, and further preferably 10 or more and less than 15. It is particularly preferably 10 or more and 14 or less.
Here, pKa represents the logarithm of the reciprocal of the first dissociation constant of acid, and the Determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, DH, Hafliger, O., Nachod, FC; compilation: Braude). , EA, Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (author: Dawson, RMCet al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula using ACD / pKa (manufactured by ACD / Labs) software is used as pKa.

[Equation (T1-1) to Equation (T1-3)]
The specific compound preferably contains a compound represented by any of the following formulas (T1-1) to (T1-3) or a salt thereof, and is preferably represented by the formula (T1-1) or the formula (T1-2). It is more preferable to contain the compounds represented or salts thereof.

In formulas (T1-1) to (T1-3), R ¹¹ and R ¹² independently represent a hydrogen atom or a monovalent substituent, and R ²¹ and R ²² independently represent a hydrogen atom or 1 respectively. R ³¹ and R ³² each independently represent a valent substituent, and ^{RN 1} , RN ² ^{and RN 3} each represent a hydrogen atom or a monovalent substituent, R ¹¹ . R ^12, may form at least two members ring structure of ^{R ^N1,} may be formed at least two bonded ring structure of ^{^{R 21, R 22, R N2}} , R 31, At ^{least two of R 32} and ^{RN 3} may be combined to form a ring structure.

In the formula (T1-1), R ¹¹ and R ¹² are preferably hydrogen atoms or hydrocarbon groups, respectively, and more preferably hydrocarbon groups.
The hydrocarbon group is not particularly limited, but an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable, and an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable. More preferred.
Wherein ^{(T1-1), R N1} represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom.
Examples of the monovalent substituent described above include the same groups as the hydrocarbon groups represented by R ^11, preferable embodiments thereof are also the same.
Further, in the formula (T1-1), when ^{at least two of R 11} , R ¹² , ^{and RN 1} are bonded to form a ^{ring structure, it is preferable that R 11} and R ¹² are bonded to form a ring structure. ..
The ring structure may be any of an aliphatic hydrocarbon ring structure, an aromatic hydrocarbon ring structure, an aliphatic heterocyclic structure, and an aromatic heterocyclic structure, and the pKa in the DMSO of the specific compound is described above. From the viewpoint of the range, the aromatic hydrocarbon ring structure is preferable.
Examples of the aliphatic hydrocarbon ring structure include an aliphatic hydrocarbon ring structure having 4 to 20 carbon atoms.
Examples of the aromatic hydrocarbon ring structure include an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, and a benzene ring structure is preferable.
Examples of the aliphatic heterocyclic structure include an aliphatic heterocyclic structure having 5 to 20 ring members. Examples of the complex atom in the above aliphatic heterocyclic structure include a nitrogen atom, an oxygen atom, a sulfur atom and the like.
Examples of the aromatic heterocyclic structure include an aromatic heterocyclic structure having 5 to 20 ring members. Examples of the complex atom in the above aliphatic heterocyclic structure include a nitrogen atom, an oxygen atom, a sulfur atom and the like.

Wherein ^(T1-2), each R ^{21, R 22} and ^{R N2,} have the same meaning as ^R ^{11, R 12} and ^{R N1} in the formula (T1-1), preferable embodiments thereof are also the same.
Wherein ^(T1-3), each R ^{31, R 32} and ^{R N3,} have the same meaning as ^R ^{11, R 12} and ^{R N1} in the formula (T1-1), preferable embodiments thereof are also the same.
Examples of the salt of the compound represented by any of the formulas (T1-1) to (T1-3) include known inorganic salts such as sodium salt, potassium salt and magnesium salt, or tetrabutylphosphonium salt and the like. Known organic salts of.

[Benzotriazole structure]
From the viewpoint of keeping pKa in DMSO of the specific compound within the above range, the specific compound preferably contains a compound having a benzotriazole structure.
The benzotriazole structure refers to a structure in which the above-mentioned triazole structure and a benzene ring structure form a condensed ring.
When the specific compound has a benzotriazole structure, the number of benzotriazole structures in the specific compound may be 1 or more, preferably 1 to 10, more preferably 1 to 4, and 1 or 2. It is more preferably present, and particularly preferably 1. When the specific compound has a benzotriazole structure, it may have only a benzotriazole structure as a triazole structure, or may have a benzotriazole structure and a triazole structure other than the benzotriazole structure.
There are two types of tautomers of the 1H-benzotriazole structure and the 2H-benzotriazole structure in the benzotriazole structure, and any of these tautomers may be used, or a mixture thereof may be used.
Examples of the 1H-benzotriazole structure include a structure represented by the following formula (T-4), and examples of the 2H-benzotriazole structure include a structure represented by the following formula (T-5).

In the above formulas (T-4) and (T-5), # and * represent a binding site with a hydrogen atom or another structure, respectively.

[Equation (T1-4) and Equation (T1-5)]
When the specific compound is a compound having a benzotriazole structure, the specific compound preferably contains a compound represented by any of the following formulas (T1-4) and (T1-5) or a salt thereof.

In formulas (T1-4) and (T1-5), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁵¹ , R ⁵² , R ^53. and ^{R 54} each independently represent a hydrogen atom or a monovalent ^substituent, each ^{R N4} and ^{R N5} represent a hydrogen atom or a monovalent ^{^{^{substituent, R 41, R 42, R}}} 43, R 44 and , R ^N4 may be combined to form a ring structure, or at least two of R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ and ^{RN 5} may be combined to form a ring structure. Good.

In the formula (T1-4), R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and the hydrogen atom or the number of carbon atoms. Alkyl groups of 1 to 10 are more preferable, alkyl groups having a hydrogen atom or 1 to 4 carbon atoms are particularly preferable, and hydrogen atoms or methyl groups are particularly preferable.
From the viewpoint of high temperature stability of the specific compound, it is preferable that at least one of ^{R 41} , R ⁴² , R ⁴³ and R ^{44 is a monovalent substituent.} As the monovalent substituent, a hydrocarbon group is preferable, an alkyl group is more preferable, an alkyl group having 1 to 10 carbon atoms is further preferable, an alkyl group having 1 to 4 carbon atoms is particularly preferable, and a methyl group is most preferable. ..
Wherein ^{(T1-4), R N4} represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom.
Examples of the monovalent substituent include the same group as ^{the hydrocarbon group in R 11} in the above formula (T1-1), and the preferred embodiment is also the same.
In formula (T1-4), ^{at least two of R 41} , R ⁴² , R ⁴³ , R ^44, and ^{RN 4} may be bonded to form a ring structure, but it is preferable not to form a ring structure.
In formula (T1-4), when ^{at least two of R 41} , R ⁴² , R ⁴³ , R ⁴⁴ and ^{RN 4} are combined to form a ring structure, of R ⁴¹ , R ⁴² , R ⁴³ and R ⁴⁴ . It is preferable that at least two of them are combined to form a ring structure.
As the ring structure, similar to the ring structure and the ring structure at least two are formed by bonding ^of ^{R 11,} R ^12, R ^N1 in the above formula (T1-1) and the like, a preferred embodiment also the same Is.

In formula (T1-5), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ and R ^{N 5} ^{are R 41} , R ⁴² , R ⁴³ , R ⁴⁴ and R ^{N 4} in formula (T1-4), respectively. It has the same meaning, and the preferred embodiment is also the same.

〔Concrete example〕
The compound having a triazole structure is not particularly limited, but 1H-benzotriazole, 2H-benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, 7-methyl-1H-benzotriazole, tolyl. Triazole, 5,6-dimethylbenzotriazole, carboxybenzotriazole, 5-chloro-2-methylbenzotriazole, 1-methyl-1H-benzotriazole, 5-nitrobenzotriazole, 1-aminobenzotriazole, 4,5,6 , 7-Tetrabromobenzotriazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1,2,4-triazole, tris (1H-benzotriazole-1-yl) methane, these Examples thereof include benzotriazoles of the above compounds and salts of these compounds.

[Molecular weight]
The molecular weight of the specific compound is preferably 69 to 1,000, more preferably 69 to 500, and even more preferably 69 to 200.

〔Content〕
The content of the specific compound is preferably 0.1 to 30% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, particularly preferably 5% by mass or less, and most preferably 3% by mass or less. As the specific compound, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Resin>
The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
The curable resin composition of the present invention preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide precursor.
Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radically polymerizable group, the curable resin composition preferably contains a photoradical polymerization initiator described later as a photosensitizer, contains a photoradical polymerization initiator described below as a photosensitizer, and is described later. It is more preferable to contain the radical cross-linking agent described above, and it is further preferable to contain the photoradical polymerization initiator described below as the photosensitizer, the radical cross-linking agent described below, and the sensitizer described below. From such a curable resin composition, for example, a negative type photosensitive layer is formed.
Further, the specific resin may have a polarity converting group such as an acid-degradable group.
When the specific resin has an acid-degradable group, the curable resin composition preferably contains a photoacid generator described later as a photosensitizer. From such a curable resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.

[Polyimide precursor]
The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
Equation (2)

In formula (2), A ¹ and A ² independently represent an oxygen atom or NH, R ¹¹¹ represents a divalent organic group, R ¹¹⁵ represents a tetravalent organic group, and R ^113. And R ¹¹⁴ independently represent a hydrogen atom or a monovalent organic group.

^{A 1} and A ² in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
^{R 111} in the formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms. A cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable. As a particularly preferable embodiment of the present invention, a group represented by -Ar-L-Ar- is exemplified. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, −CO−, —S—. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. These preferred ranges are as described above.

R ¹¹¹ is preferably derived from diamine. Examples of the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include:

In the formula, A is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —C (= O) −, —S—, —SO. ₂ -, NHCO-, or is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - C ( = O) -, - S-, or, -SO ₂ -, more preferably a group selected _{from, -CH 2 -, - O -} , - S -, - SO 2 -, - C (CF 3 ) _2- or -C (CH ₃ ) _2- is more preferable.
In the formula, * represents the binding site with other structures.

Specific examples of the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4'-and 3,3'-diaminodiphenylmethane, 4,4'-and 3,3'-diamino Diphenylsulfone, 4,4'-and 3,3'-diaminodiphenylsulfide, 4,4'-or 3,3'-diaminobenzophenone, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2 '-Dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-aminophenyl) ) Hexafluoropropane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis (3-amino) -4-Hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) ) Sulfur, 4,4'-diaminoparaterphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) ) Phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 9,10-bis (4-aminophenyl) anthracene, 3,3'- Dimethyl-4,4'-diaminodiphenylsulfone, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-) Aminophenyl) benzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminooctafluorobiphenyl, 2,2-bis [4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 3,3', 4,4'-tetraaminobiphenyl, 3,3', 4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4, 4'-Diaminobiphenyl, 9,9'-bis (4-aminophenyl) fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3', 5,5'-tetramethyl-4 , 4'-diaminodiphenylmethane, 2,4- and 2,5-diaminocumene, 2,5-dimethyl-p-phenylenediamine, acetguanamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2, , 4,6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis (4-aminophenyl) ethane , Diaminobenzanilide, ester of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminobenzotrifluoride, 1,3-bis (4-aminophenyl) hexafluoropropane, 1,4-bis (4-aminophenyl) octa Fluorobutane, 1,5-bis (4-aminophenyl) decafluoropentane, 1,7-bis (4-aminophenyl) tetradecafluoroheptane, 2,2-bis [4- (3-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (2-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) -3,5-dimethylphenyl] hexafluoropropane, 2,2-Bis [4- (4-aminophenoxy) -3,5-bis (trifluoromethyl) phenyl] hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4, 4'-bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluo) Lomethylphenoxy) Biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2, 2-Bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl] hexafluoropropane, 3,3', 5,5'-tetramethyl-4,4'-diaminobiphenyl, 4,4'- At least one selected from diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2', 5,5', 6,6'-hexafluorotridin and 4,4'-diaminoquaterphenyl. Diamine is mentioned.

Further, the diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/0385898 are also preferable.

Further, a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/0385898 is also preferably used.

R ¹¹¹ is preferably represented by —Ar—L—Ar— from the viewpoint of the flexibility of the obtained organic film. However, Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, −CO−, —S—. , -SO _2- or NHCO-, or a group consisting of a combination of two or more of the above. Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO ₂ - are preferred. The aliphatic hydrocarbon group here is preferably an alkylene group.

Further, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, a divalent organic group represented by the formula (61) is more preferable.
Equation (51)

In formula (51), R ⁵⁰ to R ⁵⁷ are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and ^{at least one of R 50} to R ⁵⁷ is a fluorine atom, methyl group or trifluoro. It is a methyl group.
The ^{monovalent organic group of R 50} to R ⁵⁷ includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.

In formula (61), R ⁵⁸ and R ⁵⁹ are independently fluorine atoms or trifluoromethyl groups, respectively.
Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used.

^{R 115} in the formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
In formula (5) or formula (6), * represents a binding site with another structure.
Equation (5)

In formula (5), R ¹¹² is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —CO−, —S—, —SO. _2- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO More preferably, it is a group selected from-, -S- and SO _2- _{, -CH 2-} , -C (CF ₃ ) _2- , -C (CH ₃ ) _{2-, -O-, -CO.} It is more preferably a divalent group selected from the group consisting of-, -S- and SO _2-.

Equation (6)

Specific examples of R ¹¹⁵ include tetracarboxylic acid residues remaining after removal of the anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
Equation (O)

In formula (O), R ¹¹⁵ represents a tetravalent organic group. A preferred range of R ¹¹⁵ has the same meaning as ^{R 115} in formula (2), and preferred ranges are also the same.

Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-. Diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3' , 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 , 7-naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,5-tetracarboxylic dianhydride, 1,4,5, 6-naphthalenetetracarboxylic dianhydride, 2,2', 3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4 5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthenetetracarboxylic dianhydride, 1,1-bis (2, 3-dicarboxyphenyl) ethanedianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethanedianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and these Examples thereof include alkyl having 1 to 6 carbon atoms and alkoxy derivatives having 1 to 6 carbon atoms.

Further, the tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.

It is also preferable that at least one of R ¹¹¹ and R ^{115 has an OH group.} More specifically, ^{as R 111} , a residue of a bisaminophenol derivative can be mentioned.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group, ^{and it is preferable that at least one of R 113} and R ¹¹⁴ contains a polymerizable group, and both contain a polymerizable group. preferable. The polymerizable group is a group capable of a cross-linking reaction by the action of heat, radicals, etc., and a radical polymerizable group is preferable. Specific examples of the polymerizable group include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a methylol group and an amino. The group is mentioned. As the radically polymerizable group contained in the polyimide precursor or the like, a group having an ethylenically unsaturated bond is preferable.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.

In formula (III), ^R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH _2- or a polyalkyleneoxy group.
Examples of suitable R ²⁰¹ are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH ₂ CH (OH) CH _2- , polyalkyleneoxy group, and ethylene group, propylene group, trimethylene group, -CH ₂ CH (OH) CH _2- , polyalkyleneoxy group are more preferable, and organic film. From the viewpoint of facilitating the filling of the formula (1) or the formula (2), the polyalkyleneoxy group is more preferable.
In the present invention, the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
The carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

R ¹¹³ and R ¹¹⁴ are independently hydrogen atoms or monovalent organic groups. Examples of the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one. Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned. The acidic group is preferably an OH group.
It is also more preferable that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.

From the viewpoint of solubility in an organic solvent, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
The alkyl group preferably has 1 to 30 carbon atoms. The alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group. , Isobutyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) ethoxy ) Ethoxy group is mentioned. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group. Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
Specific examples of the aromatic group include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene. Ring, naphthacene ring, chrysen ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acrydin ring, phenanthrene ring, It is a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferable.

In formula (2), when R ¹¹³ is a hydrogen atom or R ¹¹⁴ is a hydrogen atom, even if the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond. Good. Examples of the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.

At ^{least one of R 113} and R ¹¹⁴ may be a polar converting group such as an acid-degradable group. The acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group. , A tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
Specific examples of the acid-degradable group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl. Examples include a group and a trimethylsilyl ether group. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.

It is also preferable that the polyimide precursor has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

The repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened.
Equation (2-A)

In formula (2-A), A ¹ and A ² represent oxygen atoms, R ¹¹¹ and R ¹¹² each independently represent a divalent organic group, and R ¹¹³ and R ¹¹⁴ each independently. Representing a hydrogen atom or a monovalent organic group ^{, at least one of R 113} and R ¹¹⁴ is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.

^{^{^{A 1, A 2, R 111}}} , R 113 and ^{R 114} each independently have the same meaning as ^{^{^{A 1, A 2, R 111}}} , R 113 and ^{R 114} in formula (2), and preferred ranges are also the same ..
R ¹¹² has the same meaning as ^{R 112} in formula (5), and preferred ranges are also the same.

The polyimide precursor may contain one type of repeating structural unit represented by the formula (2), but may contain two or more types. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).

As one embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more of all repeating units, further 70 mol% or more, particularly 90 mol% or more is a repeating unit represented by the formula (2) is used. Illustrated.

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly defined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.

[Polyimide]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
In the present specification, the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern forming property. A polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable. The upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
Further, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained organic film.
In the present specification, the "main chain" refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain" refers to other binding chains.

-Fluorine atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a fluorine atom.
The fluorine atom is preferably contained in, for example, R ¹³² in the repeating unit represented by the formula (4) described later, or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that it is contained as an alkyl fluoride group ^{in R 132} in the repeating unit represented by 4) ^{or R 131} in the repeating unit represented by the formula (4) described later.
The amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, and more preferably 5 to 30 mol / g.

-Silicon atom-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has a silicon atom.
The silicon atom is ^{preferably contained in R 131} in the repeating unit represented by the formula (4) described later, and is organically modified (poly ^{) in R 131} in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure.
Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
The amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.

-Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained organic film, the polyimide preferably has an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferably provided at the side chain.
The ethylenically unsaturated bond preferably has radical polymerization property.
The ethylenically unsaturated bond is ^{preferably contained in R 132} in the repeating unit represented by the formula (4) described later or R ¹³¹ in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later. ^{It is more preferable that R 132} in the repeating unit represented by (4) ^{or R 131} in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
Of these, ethylenically unsaturated bond, ethylene R ¹³¹ in the repeating unit represented by the preferably contained in R ¹³¹ in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and which is directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group and a (meth) group. Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).

In formula (IV), R ²⁰ represents a hydrogen atom or a methyl group, and a methyl group is preferable.

In formula (IV), R ²¹ is an alkylene group having 2 to 12 carbon atoms, -O-CH ₂ CH (OH) CH _2- , -C (= O) O-, -O (C = O) NH-. , A (poly) alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1 ~ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.

Among these, R ²¹ is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).

In the formulas (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded, and X. Indicates an oxygen atom or a sulfur atom, * represents a bond site with another structure, and ● represents a bond site with an oxygen atom to which ^{R 201 in the formula (III) is bonded.}
In the formulas (R1) to (R3), a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R ²¹ having 2 to 12 carbon atoms. This is the same as the preferred embodiment of 12 alkylene groups or (poly) alkyleneoxy groups having 2 to 30 carbon atoms.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * is synonymous with * in formula (IV), and the preferred embodiment is also the same.
The structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
The structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
The polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance. A group in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.

In formula (IV), * represents a bonding site with another structure, and is preferably a bonding site with the main chain of polyimide.

The amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.

-Crosslinkable groups other than ethylenically unsaturated bonds-
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained ^{in R 131} in the repeating unit represented by the formula (4) described later, for example.
The amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g.
From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.

-Polarity converter-
The polyimide may have a polarity converting group such as an acid-degradable group. The acid-degradable group in the polyimide is the same as the acid-degradable group described in R ¹¹³ and R ¹¹⁴ in the above formula (2), and the preferred embodiment is also the same.

-Acid value-
When the polyimide is subjected to alkaline development, the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving the developability. Is more preferable.
The acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
When the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
The acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
The pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
As such an acid group, the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.

-Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, the polyimide preferably has a phenolic hydroxy group.
The polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
The phenolic hydroxy group is preferably contained ^{in, for example, R 132} in the repeating unit represented by the formula (4) described later, or R ^{131 in the repeating unit represented by the formula (4) described later.}
The amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.

The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). More preferably, it is a compound containing a repeating unit and having a polymerizable group.
Equation (4)

In formula (4), R ¹³¹ represents a divalent organic group and R ¹³² represents a tetravalent organic group.
When having a polymerizable group, the polymerizable group ^{may be located at at least one of R 131} and R ¹³² , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
Equation (4-1)

In formula (4-1), ^R133 is a polymerizable group, and the other groups are synonymous with formula (4).
Equation (4-2)

At ^{least one of R 134} and R ¹³⁵ is a polymerizable group, when it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).

The polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
R ¹³¹ represents a divalent organic group. ^{Examples of the divalent organic group include those similar to R 111} in the formula (2), and the preferred range is also the same.
Further, as R ¹³¹ , a diamine residue remaining after removal of the amino group of the diamine can be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines.
Specific examples include an example of R ^{111 in} the polyimide precursor formula (2).

It is preferable that R ¹³¹ is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule, and more preferably, it is a diamine residue containing no aromatic ring.

Jeffermin® KH-511, ED-600, ED-900, ED-2003, EDR are examples of diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples include, but are not limited to, propoxy) propoxy-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propan-2-amine.

R ¹³² represents a tetravalent organic group. ^{Examples of the tetravalent organic group include those similar to R 115} in the formula (2), and the preferred range is also the same.
For example, ^{four conjugates of a tetravalent organic group exemplified as R 115} combine with four −C (= O) − moieties in the above formula (4) to form a fused ring.

In addition, R ¹³² includes a tetracarboxylic acid residue remaining after removal of an anhydride group from the tetracarboxylic dianhydride. Specific examples include an example of R ^{115 in} the polyimide precursor formula (2). From the viewpoint of the strength of the organic film, R ¹³² is preferably an aromatic diamine residue having 1 to 4 aromatic rings.

It is also preferable that at least one of R ¹³¹ and R ^{132 has an OH group.} More specifically, ^{as R 131} , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above (DA-1) to (DA-18) are preferable examples. As R ¹³² , the above (DAA-1) to (DAA-5) are more preferable examples.

It is also preferable that the polyimide has a fluorine atom in the structural unit. The content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.

Further, for the purpose of improving the adhesion to the substrate, the polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specific examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.

Further, in order to improve the storage stability of the composition, the main chain end of polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound. preferable. Of these, it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfone Acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3- Aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.

-Immidization rate (ring closure rate)-
The imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, the insulating property, etc. of the obtained organic film. More preferably, it is 90% or more.
The upper limit of the imidization rate is not particularly limited, and may be 100% or less.
The imidization rate is measured by, for example, the following method.
The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near ^{1377 cm -1, which is the absorption peak derived from the imide structure.} Next, the polyimide is heat-treated at 350 ° C. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of ^{1377 cm -1.} Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100

The polyimide may contain repeating structural units of the above formula (4), all containing one type of R ¹³¹ or R ^132, and the above formula (4) containing two or more different types of R ¹³¹ or R ^132. May include repeating units of. Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).

Polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature. A method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal capping agent which is a monoactive ester compound), a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then diamine (partly monoamine) is obtained. A method of reacting in the presence of a condensing agent with (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and alcohol, and then the remaining dicarboxylic acid is acid-chlorided to diamine (partly monoamine). A polyimide precursor is obtained by using a method such as a method of reacting with an end-capping agent (replaced with an end-capping agent), and the polyimide precursor is completely imidized by using a known imidization reaction method, or an imide in the middle. Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure, and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Co., Ltd.).

The weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 10,000 to 30,000. More preferred. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.

[Polybenzoxazole precursor]
The polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
Equation (3)

In formula (3), R ¹²¹ represents a divalent organic group, R ¹²² represents a tetravalent organic group, and R ¹²³ and R ¹²⁴ independently represent a hydrogen atom or a monovalent organic group. Represent.

In the formula (3), R ¹²³ and R ¹²⁴ ^{are synonymous with R 113} in the formula (2), respectively, and the preferable range is also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferable. As the aliphatic group, a linear aliphatic group is preferable. R ¹²¹ is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.

As the dicarboxylic acid residue, a dicarboxylic acid containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
As the dicarboxylic acid containing an aliphatic group, a dicarboxylic acid containing a linear or branched (preferably straight chain) aliphatic group is preferable, and a linear or branched (preferably straight chain) aliphatic group and two -COOH are preferable. A dicarboxylic acid composed of is more preferable. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, and 4 to 20. It is more preferably 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group.
Examples of the dicarboxylic acid containing a linear aliphatic group include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-Dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-Dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadiponic acid, 3-methyladiponic acid, pimelli acid, 2,2,6,6-tetramethylpimeric acid, suberin Acid, dodecafluorosveric acid, azelaic acid, sebacic acid, hexadecafluorosevacinic acid, 1,9-nonane diic acid, dodecane diic acid, tridecane diic acid, tetradecane diic acid, pentadecane diic acid, hexadecane diic acid, heptadecane diic acid , Octadecan diic acid, nonadecan diic acid, eikosan diic acid, henei cosan diic acid, docosan diic acid, tricosan diic acid, tetracosan diic acid, pentacosan diic acid, hexacosan diic acid, heptacosan diic acid, octacosan diic acid, nonacosan diic acid, tria Examples thereof include contan diic acid, hentoria contan diic acid, dotria contan diic acid, diglycolic acid, and dicarboxylic acid represented by the following formula.

(In the formula, Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6).

As the dicarboxylic acid containing an aromatic group, a dicarboxylic acid having the following aromatic groups is preferable, and a dicarboxylic acid consisting of only the following aromatic groups and two -COOH is more preferable.

In the formula, A is -CH _2- , _{-O-, -S-, -SO 2-} , -CO-, -NHCO-, -C (CF ₃ ) _2- , and -C (CH ₃ ) _2- Represents a divalent group selected from the group consisting of, and each independently represents a binding site with another structure.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same ^{meaning as R 115} in the above formula (2), and the preferable range is also the same.
R ¹²² is also preferably a group derived from a bisaminophenol derivative, and examples of the group derived from the bisaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'. -Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis- (3-amino-) 4-Hydroxyphenyl) methane, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-Amino-3-hydroxyphenyl) hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3-hydroxyphenyl) propane, 4,4'-Diamino-3,3'-dihydroxybenzophenone,3,3'-diamino-4,4'-dihydroxybenzophenone,4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-dihydroxy-4, Examples thereof include 4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene and 1,3-diamino-4,6-dihydroxybenzene. These bisaminophenols may be used alone or in combination.

Among the bisaminophenol derivatives, bisaminophenol derivatives having the following aromatic groups are preferable.

In the formula, X ₁ represents -O-, -S-, -C (CF ₃ ) _2- , -CH _2- , -SO _2- , -NHCO-, and * and # represent other structures, respectively. Represents the binding site of. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom or an alkyl group. Further, ^{it is also preferable that R 122} has a structure represented by the above formula. When R ¹²² has a structure represented by the above formula, any two of the four * and # in total are the binding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bonded, and} preferably R ¹²² in another 2 Exemplary ethynylphenylbiadamantane derivatives (3) is a binding site to the oxygen atom bonding, two * is a bond sites with an oxygen atom R ¹²² are attached in the formula (3) ^{, And two # are the binding sites with the nitrogen atom to which R 122} in the formula (3) is bound, or two * are the binding sites with the nitrogen atom to which ^{R 122 in the formula (3) is bound.} It is more preferable that the site is a site ^{and the two #s} are the binding sites with the oxygen atom to which R 122 in the formula (3) is bonded, and the two * are the oxygen to which ^{the R 122 in the formula (3) is bonded.} It is more preferable that the binding site is a binding site with an atom and the ^{two #s} are the binding sites with a nitrogen atom to which R 122 in the formula (3) is bonded.

In the formula (As), R ₁ is a hydrogen atom, an alkylene, a substituted alkylene, -O-, -S-, -SO _2- , -CO-, -NHCO-, a single bond, or the following formula (A-). It is an organic group selected from the group of sc). R ₂ is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R ₃ is any of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.

(In the formula (A-sc), * indicates that it binds to the aromatic ring of the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

The formula (A-s) in ortho position of the phenolic hydroxyl groups, i.e., to have also substituent R ₃ is believed to closer the distance of the carbonyl carbon and the hydroxyl group of the amide bond was cured at a low temperature It is particularly preferable in that the effect of increasing the cyclization rate is further enhanced.

Further, in the above formula (As), _{it is said that the fact that R 2} is an alkyl group and R ₃ is an alkyl group has high transparency to i-rays and a high cyclization rate when cured at a low temperature. The effect can be maintained, which is preferable.

Further, in the above formula (As), _{it is more preferable that R 1} is an alkylene or a substituted alkylene. Specific examples of the alkylene and the substituted alkylene according to R ₁ include linear or branched alkylene groups having 1 to 8 carbon atoms, among which -CH _{2- and} -CH (CH _3). )-, -C (CH ₃ ) ₂ -has sufficient solubility in a solvent while maintaining the effects of high transparency to i-rays and high cyclization rate when cured at low temperature. It is more preferable in that a well-balanced polybenzoxazole precursor can be obtained.

As a method for producing the bis-aminophenol derivative represented by the above formula (As), for example, paragraph numbers 0085 to 0094 and Example 1 (paragraph numbers 0189 to 0190) of JP2013-256506A are referred to. These contents can be incorporated herein by reference.

Specific examples of the structure of the bis-aminophenol derivative represented by the above formula (As) include those described in paragraphs 0070 to 0080 of JP2013-256506, and the contents thereof are described in the present specification. Incorporated in. Of course, it goes without saying that it is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (3).
It is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit in that the occurrence of warpage due to ring closure can be suppressed.

In formula (SL), Z has an a structure and a b structure, R ^1s is a hydrogen atom or a hydrocarbon group ^{having 1 to 10 carbon atoms, and R 2s} is a hydrocarbon group having 1 to 10 carbon atoms. ^Yes , at least one of R 3s, R ^4s , R ^5s , and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. The mol% of the Z portion is 5 to 95 mol% for the a structure, 95 to 5 mol% for the b structure, and 100 mol% for a + b.

In the formula (SL), preferred Z includes those in which R ^5s and R ^6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, it is possible to more effectively reduce the elastic modulus of the polybenzoxazole precursor after dehydration ring closure, suppress warpage, and improve solvent solubility.

When a diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, the tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride is used as the repeating structural unit. It is also preferable to include it. Examples of such a tetracarboxylic acid residue include the example of R ¹¹⁵ in the formula (2).

The weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further, when used in the compositions described below. It is preferably 22,000 to 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
The degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the dispersity of the molecular weight of the polybenzoxazole precursor is not particularly determined, but for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. Is more preferable, and 2.2 or less is even more preferable.

[Polybenzoxazole]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X). It is more preferable that the compound has a polymerizable group. As the polymerizable group, a radically polymerizable group is preferable. Further, it may be a compound represented by the following formula (X) and having a polarity converting group such as an acid-degradable group.

In formula (X), R ¹³³ represents a divalent organic group and R ¹³⁴ represents a tetravalent organic group.
When having a polar converting group such as a polymerizable group or an acid-degradable group, the polar converting group such as a polymerizable group or an acid-degradable group ^{may be located at at least one of R 133} and R ¹³⁴ , and may be located at least one of the following. It may be located at the end of the polybenzoxazole as shown in the formula (X-1) or the formula (X-2).
Equation (X-1)

In formula (X-1), ^{at least one of R 135} and R ¹³⁶ is a polar converting group such as a polymerizable group or an acid-degradable group, and is not a polar converting group such as a polymerizable group or an acid-degradable group. It is an organic group, and the other groups are synonymous with the formula (X).
Equation (X-2)

In the formula (X-2), R ¹³⁷ is a polar converting group such as a polymerizable group or an acid-degradable group, the other is a substituent, and the other group is synonymous with the formula (X).

A polar converting group such as a polymerizable group or an acid-degradable group is synonymous with the polymerizable group described in the polymerizable group possessed by the above-mentioned polyimide precursor or the like.

R ¹³³ represents a divalent organic group. Examples of the divalent organic group include an aliphatic or aromatic group. ^{Specific examples include the example of R 121} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 121.}

R ¹³⁴ represents a tetravalent organic group. Examples of the ^{tetravalent organic group include R 122} in the formula (3) of the polybenzoxazole precursor. A preferred example thereof is the same as that ^{of R 122.}
For example, ^{four conjugates of a tetravalent organic group exemplified as R 122} combine with a nitrogen atom and an oxygen atom in the above formula (X) to form a condensed ring. For example, when R ¹³⁴ is the following organic group, it forms the following structure.

Polybenzoxazole preferably has an oxazoleization rate of 85% or more, and more preferably 90% or more. When the oxazoleization rate is 85% or more, the membrane shrinkage due to ring closure that occurs when oxazoled by heating is reduced, and the occurrence of warpage can be suppressed more effectively.

Polybenzoxazole, everything may include repeating structural units of formula (X) comprising one of ^{R 131} or ^{R 132,} 2 or more different types of ^{R 131} or the formula comprising ^{R 132} ( It may include the repeating unit of X). Further, the polybenzoxazole may contain other types of repeating structural units in addition to the repeating unit of the above formula (X).

The resulting polybenzoxazole, for example, a bis-aminophenol derivative, a dicarboxylic acid or the dicarboxylic acid containing R ^133, is reacted with a compound selected from such dicarboxylic acid dichloride and dicarboxylic acid derivatives, the polybenzoxazole precursor , This is obtained by oxazoleization using a known oxazoleization reaction method.
In the case of a dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1,2,3-benzotriazole or the like in advance may be used in order to increase the reaction yield or the like.

The weight average molecular weight (Mw) of polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polybenzoxazole are contained, it is preferable that the weight average molecular weight of at least one kind of polybenzoxazole is in the above range.

[Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent such as thionyl chloride and then reacting it with a diamine.

It is also preferable to synthesize using a non-halogen catalyst without using the above halogenating agent. As the non-halogen catalyst, a known amidation catalyst containing no halogen atom can be used without particular limitation. For example, a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used. Examples include carbodiimide compounds such as salts and urea compounds. Examples of the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide and the like.

In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction.
The organic solvent may be one kind or two or more kinds.
The organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
The polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.

-End sealant-
In order to further improve the storage stability in the production method of the polyimide precursor, etc., the end of the polyimide precursor, etc. is used as an end sealant such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol and the like. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.

-Solid precipitation-
A step of precipitating a solid may be included in the production of the polyimide precursor or the like. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran is dissolved in a soluble solvent to cause solid precipitation.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.

〔Content〕
The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 50% by mass or more. The resin content in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less, based on the total solid content of the composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
The composition of the present invention may contain only one type of the specific resin, or may contain two or more types of the specific resin. When two or more types are included, the total amount is preferably in the above range.

<Other resins>
The resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as “other resin”).
Examples of other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, and acrylic resins.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and a pattern (cured film) having excellent solvent resistance can be obtained.
For example, the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of a pattern (cured film), and the like.

When the resin composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. It is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and further preferably 10% by mass or more. preferable.
The content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. % Or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferable aspect of the resin composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Solvent>
The curable resin composition of the present invention contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, amides, and alcohols.

The curable resin composition of the present invention preferably has a water content of 5% by mass or less based on the total mass of the solvent from the viewpoints of suppressing coating defects during coating and improving storage stability. ..
The content of the water is preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass or less.
Moreover, the content of the said water may be 0 mass%.

Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkylalkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl) Propyl oxypropionate and the like (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate), 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, pyruvin Suitable examples include ethyl acid, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, ethyl hexanoate, ethyl heptate, dimethyl malonate, diethyl malonate and the like. ..

Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.

As the ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.

As the aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene and the like are preferable.

As sulfoxides, for example, dimethyl sulfoxide is preferable.

As amides, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Suitable examples include dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

As ureas, N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.

As alcohols, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.

The solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.

In the present invention, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ- Consists of one solvent selected from butyrolactone, dimethylsulfoxide, ethylcarbitol acetate, butylcarbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, or two or more. The mixed solvent to be used is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. Further, a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferable.

The curable resin composition of the present invention preferably contains a solvent containing no nitrogen atom as the solvent. Since dissociation (deprotonation) of a specific compound is likely to occur in a solvent that does not contain nitrogen atoms, the adhesion energy between the specific compound and the metal when the composition is applied to the substrate is likely to increase, and the corrosion suppressing ability is excellent. It is considered easy.
Examples of the solvent having no nitrogen atom include the above-mentioned esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides. Among these, ethyl lactate, γ-butyrolactone, dimethylsulfoxide, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 3-methoxybutyl acetate (3-MBA), methyl-3- Methoxypropionate (MMP), ethyl pyruvate (ethyl pyruvate, EP), 2-ethoxyethyl acetate (EA), n-butyl acetate (BA), or propylene glycol monopropyl ether (PGP) are preferred. Be done.
When the curable resin composition of the present invention contains a solvent containing no nitrogen atom, the content of the solvent containing no nitrogen atom with respect to the total mass of the solvent contained in the curable resin composition is 10 to 100% by mass. It is preferably 20 to 100% by mass, more preferably 50 to 100% by mass.
Further, the curable resin composition of the present invention may be in an embodiment that does not substantially contain a solvent containing a nitrogen atom such as N-methylpyrrolidone. In the above aspect, the content of the solvent containing a nitrogen atom with respect to the total mass of the solvent contained in the curable resin composition is preferably 5% by mass or less, more preferably 3% by mass or less, and 1 It is more preferably mass% or less, and particularly preferably 0.1 mass% or less. The minimum value of the content may be 0% by mass.

The curable resin composition of the present invention preferably contains as a solvent a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms.
A solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms is a solvent containing only atoms selected from carbon atoms, oxygen atoms and hydrogen atoms as atoms constituting the solvent, and contains only carbon atoms and hydrogen atoms. It may be a solvent, but a solvent containing a carbon atom, an oxygen atom and a hydrogen atom is preferable.
Examples of the solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms include the above-mentioned esters, ethers, ketones and aromatic hydrocarbons. Among these, ethyl lactate, γ-butyrolactone, dimethylsulfoxide, cyclopentanone, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 3-methoxybutyl acetate (3-MBA), methyl-3- Methoxypropionate (MMP), ethyl pyruvate (ethyl pyruvate, EP), 2-ethoxyethyl acetate (EA), n-butyl acetate (BA), or propylene glycol monopropyl ether (PGP) are preferred. Be done.
When the curable resin composition of the present invention contains a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms, only carbon atoms, oxygen atoms and hydrogen atoms with respect to the total mass of the solvent contained in the curable resin composition The content of the solvent composed of is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and further preferably 50 to 100% by mass.
Further, the curable resin composition of the present invention may be in a mode that substantially does not contain a solvent containing atoms other than carbon atoms, oxygen atoms and hydrogen atoms. In the above aspect, the content of the solvent containing atoms other than carbon atom, oxygen atom and hydrogen atom with respect to the total mass of the solvent contained in the curable resin composition is preferably 5% by mass or less, preferably 3% by mass. It is more preferably less than or equal to, more preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. The minimum value of the content may be 0% by mass.

From the viewpoint of coatability, the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass. The solvent content may be adjusted according to the desired thickness and coating method.
The curable resin composition of the present invention may contain only one type of solvent, or may contain two or more types of solvent. When two or more kinds of solvents are contained, the total is preferably in the above range.

<pH adjuster>
The curable resin composition of the present invention may further contain a pH adjuster.
Examples of the pH adjuster include acidic compounds and basic compounds.
When the curable resin composition of the present invention contains at least one selected from the group consisting of an acidic compound and a basic compound, so that an acid or a base enters from the outside of the composition or the cured film. However, it is considered that the buffering action of these compounds makes it easier for the pH of the composition or the cured film to be kept below 7, and makes it easier to improve the metal corrosion inhibitory property and the liquid storage stability of the composition.

[Acid compound]
Examples of the acidic compound include compounds having a carboxy group.
The compound having a carboxy group is not particularly limited, but a silane coupling agent having a carboxy group, which will be described later, or a polyaminocarboxylic acid compound or a salt thereof is preferable.
The polyaminocarboxylic acid compound or a salt thereof is not particularly limited, but ethylenediaminetetraacetic acid, trans-1,cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, or amine salts thereof, ammonium. Examples include salt.

Further, from the viewpoint of obtaining the buffering action, the pKa in DMSO of the carboxy group of the compound having the carboxy group is preferably 4 to 20, more preferably 6 to 18, and 6 to 15 Is more preferable.

The content of the acidic compound with respect to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0. It is more preferably 5 to 6% by mass.
The curable resin composition of the present invention may contain only one type of acidic compound, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

[Basic compound]
The curable resin composition of the present invention preferably contains a basic compound as a pH adjuster.
The basic compound does not include the above-mentioned compound having a triazole structure.
From the viewpoint of metal corrosion inhibitory property and storage stability, the basic compound may be a compound corresponding to a thermal acid generator, a photoacid generator, a migration inhibitor, etc., which will be described later, but it does not correspond to these. It is preferably a compound.
In the present invention, the basic compound is not particularly limited as long as it is a compound exhibiting basicity in the curable resin composition, but the pKa of the conjugate acid in DMSO is preferably 1.0 to 7.0. , 1.5 to 7.0, more preferably 2.0 to 7.0.

Further, as the basic compound, a compound containing at least one structure selected from the group consisting of an aromatic amine structure and an alcoholic hydroxyl group is preferable, and a compound containing an aromatic amine structure and an alcoholic hydroxyl group is more preferable.

In the present specification, the aromatic amine structure means a structure in which an amino group or a substituted amino group is directly bonded to an aromatic ring, and a structure in which a substituted amino group is bonded to an aromatic ring is preferable, and the aromatic ring is disubstituted. It is more preferable that the structure has an amino group bonded thereto. The substituent in the substituted amino group or the disubstituted amino group is not particularly limited, but a hydrocarbon group which may have a substituent is preferable, and a hydrocarbon group which has at least an alcoholic hydroxyl group as a substituent is preferable. As the hydrocarbon group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable. The substituents in the disubstituted amino group may be the same or different.
As the aromatic amine structure, a structure represented by the following formula (A-1) is preferably mentioned.

In formula (A-1), * independently represents a binding site with a hydrogen atom or a substituent, and at least one of * represents a binding site with a substituent.
In the formula (A-1), it is preferable that * represents a binding site with a substituent.
Further, in the formula (A-1), the benzene ring may have a known substituent or condensed ring within the range in which the effect of the present invention can be obtained.

In the present specification, the alcoholic hydroxyl group means a hydroxy group directly bonded to a carbon atom that is not a ring member of an aromatic ring, and is preferably a hydroxy group directly bonded to a carbon atom contained in an aliphatic hydrocarbon group. ..
When the basic compound in the present invention has an alcoholic hydroxyl group, the basic compound is preferably an amine compound having an alcoholic hydroxyl group, and more preferably an aromatic amine compound having a basic compound.
Further, the amine compound is preferably a tertiary amine compound, and more preferably a tertiary aromatic amine compound.

Examples of the compound containing at least one structure selected from the group consisting of an aromatic amine structure and an alcoholic hydroxyl group include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, and 2,5-bis (4'-diethylaminobenzal). ) Cyclopentane, 2,6-bis (4'-diethylaminobenzal) cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-Bis (diethylamino) chalcone, p-dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylamino) Phenylbinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) isonaftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone , 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3 -Methenylcarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4- Morphorinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2-( p-Dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) naphtho (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3 ', 4'-Dimethylacetanilide and the like can be mentioned.
Among these, as the compound containing an aromatic amine structure and an alcoholic hydroxyl group, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, or N-phenylethanolamine is preferable.

The content of the basic compound with respect to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0. It is more preferably .5 to 6% by mass.
The curable resin composition of the present invention may contain only one type of basic compound, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Silane coupling agent>
The curable resin composition of the present invention preferably contains a silane coupling agent.
Further, the curable resin composition of the present invention preferably has a silane coupling agent having a carboxy group as the silane coupling agent.
The silane coupling agent having a carboxy group corresponds to the above-mentioned acidic compound.

[Silane coupling agent having a carboxy group]
The silane coupling agent having a carboxy group is not particularly limited, but a compound having a monoalkoxysilyl group, a dialkoxysilyl group or a trialkoxysilyl group and a carboxy group is preferable, and a dialkoxysilyl group or a trialkoxysilyl group And a compound having a carboxy group is more preferable, and a compound having a trialkoxysilyl group and a carboxy group is further preferable.
The alkoxy group in the monoalkoxysilyl group, the dialkoxysilyl group or the trialkoxysilyl group is not particularly limited, but is preferably an alkoxy group having 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.

The number of carboxy groups in the silane coupling agent having a carboxy group may be 1 or more, but is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
The molar amount (mmol / g) of the carboxy group in the silane coupling agent having 1 g of the carboxy group is preferably 3.12 to 12.5 mmol / g, and is 3.12 to 6.25 mmol / g. Is more preferable.

Specific examples of the silane coupling agent having a carboxy group include, but are not limited to, the following compounds.

In the above formula, R represents a methyl group or an ethyl group.

The content of the silane coupling agent having a carboxy group is preferably 0.1% by mass to 20% by mass, and 0.2% by mass to 10% by mass, based on the total solid content of the curable resin composition. It is preferably 0.5 to 5% by mass, and more preferably 0.5 to 5% by mass.
The content of the silane coupling agent having a carboxy group is preferably 5 to 80% by mass, preferably 10 to 70% by mass, based on the total mass of the basic compound contained in the curable resin composition. Is more preferable.
The curable resin composition of the present invention may contain only one type of silane coupling agent having a carboxy group, or may contain two or more types. When two or more kinds of silane coupling agents having a carboxy group are contained, the total is preferably in the above range.

[Other silane coupling agents]
From the viewpoint of adhesion to the base material and the like, the curable resin composition of the present invention may contain another silane coupling agent having no carboxy group.
Examples of other silane coupling agents include cyclic ether groups such as epoxy group and oxetanyl group, groups having an ethylenically unsaturated bond such as vinyl group, allyl group and methacryloyl group, amino group, hydroxy group and mercapto group. Examples thereof include a silane coupling agent having a nitrogen-containing aromatic heterocyclic group such as an imidazole structure and an alkylamide group.
Further, as other silane coupling agents, the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, and International Publication No. 2011/080992. Compounds described in paragraphs 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/0975994. Among the compounds described in paragraph 0055 of the above, compounds having no carboxy group can be mentioned. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A.

When the curable resin composition of the present invention contains another silane coupling agent, it is preferably 0.1% by mass to 20% by mass, preferably 0.2% by mass, based on the total solid content of the curable resin composition. It is preferably from mass% to 10% by mass, and more preferably from 0.5 to 5% by mass.
The curable resin composition of the present invention may contain only one type of other silane coupling agent, or may contain two or more types. When two or more other silane coupling agents are contained, the total is preferably in the above range.

<Other resins>
In addition to the above-mentioned specific resin, the composition of the present invention may further contain another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
For example, by further adding an acrylic resin, a composition having excellent coatability can be obtained, and an organic film having excellent solvent resistance can be obtained.
For example, the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of an organic film, and the like.

When the composition of the present invention contains another resin, the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more. ..
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass, based on the total solid content of the composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
Further, as a preferable aspect of the composition of the present invention, the content of the other resin may be low. In the above embodiment, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass or more.
The composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.

<Photosensitizer>
The composition of the present invention contains a photosensitizer.
As the photosensitizer, a photopolymerization initiator is preferable.

[Photopolymerization initiator]
The composition of the present invention preferably contains a photopolymerization initiator as the photosensitizer.
The photopolymerization initiator is preferably a photoradical polymerization initiator. The photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.

From the viewpoint of facilitating the satisfaction of at least one formula selected from the group consisting of the above formulas (1) and (2) in the organic film, the composition of the present invention will be described later as a photoradical polymerization initiator. It preferably contains a metal element-containing compound. That is, in the present invention, among the metal element-containing compounds described later, those having a radical polymerization initiatoring ability can be used as a photoradical polymerization initiator.
Here, having the ability to initiate radical polymerization means that free radicals capable of initiating radical polymerization can be generated. For example, with respect to a composition containing a radically polymerizable monomer, a binder polymer, and a metal element-containing compound, a wavelength range in which the metal element-containing compound absorbs light and the radically polymerizable monomer does not absorb light. The presence or absence of the polymerization initiation ability can be confirmed by confirming the presence or absence of the disappearance of the radically polymerizable monomer when irradiated with light. In order to confirm the presence or absence of disappearance, an appropriate method can be selected depending on the type of radical polymerizable monomer or binder polymer, but for example, it can be confirmed by IR measurement (infrared spectroscopy) or HPLC measurement (high performance liquid chromatography). Good.

When the composition of the present invention contains a metal element-containing compound or the like having a radical polymerization initiating ability, it is also preferable that the composition of the present invention does not substantially contain a radical polymerization initiator other than the above-mentioned metal element-containing compound. The fact that the composition of the present invention does not substantially contain a radical polymerization initiator other than the metal element-containing compound means that the content of the radical polymerization initiator other than the metal element-containing compound is the metal element-containing compound. It is said that it is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and further preferably 0.1% by mass, based on the total mass of the above.
Further, when the composition of the present invention contains a metal element-containing compound or the like having a radical polymerization initiation ability, the composition of the present invention may contain the metal element-containing compound and another photoradical polymerization initiator. preferable.
When the composition of the present invention contains a metal element-containing compound and another photoradical polymerization initiator, the content of the metal element-containing compound relative to the total content of the metal element-containing compound and the other photoradical polymerization initiator. The amount is preferably 20 to 80% by mass, more preferably 30 to 70% by mass.
Further, as the above-mentioned other photoradical polymerization initiator, an oxime compound described later is preferable.

The photoradical polymerization initiator contains at least one compound having a molar extinction coefficient ^{of at least about 50 L · mol -1} · cm ^-1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable. The molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).

A known compound can be arbitrarily used as the photoradical polymerization initiator. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine structure, compounds having an oxadiazole structure, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc. Oxim compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned. For details thereof, the description of paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.

Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification. As a commercially available product, KayaCure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.

In one embodiment of the present invention, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, the compound described in JP-A-2009-191179, in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

Examples of the metallocene compound include IRGACURE-784 and IRGACURE-784EG (both manufactured by BASF). The metallocene compound includes a metal element-containing compound described later and having a radical polymerization initiation ability.

The photoradical polymerization initiator is more preferably an oxime compound. By using the oxime compound, the exposure latitude can be improved more effectively. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.

As specific examples of the oxime compound, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.

Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of> C = NOC (= O)-in the molecule.

Commercially available products include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052). A radical polymerization initiator 2) is also preferably used. Further, TR-PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA ARCLUDS NCI-831 and ADEKA ARCULDS NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daito Chemix Co., Ltd.) can be used. Further, an oxime compound having the following structure can also be used.

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.

It is also possible to use an oxime compound having a fluorine atom. Specific examples of such an oxime compound include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.

Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl. Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.

More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds. At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.

The photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone). -2-Dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1 and other aromatic ketones, alkylanthraquinone, etc. It is also possible to use quinones fused to the aromatic ring of the above, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkyl benzoin, and benzyl derivatives such as benzyl dimethyl ketal. Further, a compound represented by the following formula (I) can also be used.

In formula (I), ^RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like. Alkyl group with 1 to 20 carbon atoms, alkoxy group with 1 to 12 carbon atoms, halogen atom, cyclopentyl group, cyclohexyl group, alkenyl group with 2 to 12 carbon atoms, carbon number 2 to 2 interrupted by one or more oxygen atoms 18 alkyl group and at least one substituted phenyl group of the alkyl group having 1 to 4 carbon atoms, or biphenyl, R ^I01 is a group represented by formula (II), the same as R ^I00 It is a group, and R ^I02 to R ^I04 are independently alkyl having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.

In the formula, R ^I05 to R ^I07 are the same as ^{R I 02} to R I ⁰⁴ of the above formula (I).

Further, as the photoradical polymerization initiator, the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.

When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total amount is preferably in the above range.

[Photoacid generator]
Further, the composition of the present invention preferably contains a photoacid generator as a photosensitizer.
By containing the photoacid generator, for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is affected by the developing solution. A positive pattern to be removed can be obtained.
Further, when the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed portion promotes the cross-linking reaction of the polymerizable compound. The exposed portion may be more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime. Examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.

As the quinone diazide compound, a polyhydroxy compound in which quinone diazide sulfonic acid is bonded by an ester, a polyamino compound in which quinone diazide sulfonic acid is conjugated with a sulfonamide bond, and a polyhydroxypolyamino compound in which quinone diazide sulfonic acid is ester-bonded and a sulfonamide bond. The one which is bound by at least one of the above is mentioned. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.

In the present invention, as the quinone diazide, either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.

Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).

Wherein (OS-1), ^{X 3} is an alkyl group, an alkoxyl group, or a halogen atom. If X ³ there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X ³ may have a substituent. The alkyl group in the above X ^3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X ^3, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X ^3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X ³ may be the same or different.
In the formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W. W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.

Wherein (OS-1), m3 is 3, ^{X 3} is a methyl group, the substitution position of ^{X 3} is ^{ortho, R 34} is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound having a 7-dimethyl-2-oxonorbornylmethyl group or a p-tolyl group is particularly preferable.

Specific examples of the oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-209692A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.

In formulas (OS-103) to (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, and R ^{s2, which may be present in a plurality of R s2,} independently represents a hydrogen atom, an alkyl group and an aryl group. ^{R s6} , which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, and Xs represents O or S. Represented, ns represents 1 or 2, ms represents an integer from 0 to 6.
In formulas (OS-103) to (OS-105), ^{an alkyl group represented by R s1} (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.

In formulas (OS-103) to (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable. ^{Of the R s2} that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom. The alkyl group or aryl group represented by ^{R s2 may have a substituent T.}
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formulas (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
In formulas (OS-103) to (OS-105), the ^{alkyl group represented by R s6} (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) are substituents. You may have.
In the formulas (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.

The compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111). The compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.

In formulas (OS-106) to (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, and R ^t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups, R ^t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups, and R ^t2 represents a hydrogen atom or a methyl group.
In formulas (OS-106) to (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.

In formulas (OS-106) to (OS-111), R ^t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, or a phenyl group. Alternatively, it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.

In formulas (OS-106) to (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
R ^t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
Further, in the above-mentioned oxime sulfonate compound, the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A. The compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.

Other preferable embodiments of the oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).

In formula (OS-101) or formula (OS-102), ^Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group. The ^{embodiment in which R u9} is a cyano group or an aryl group is more preferable, and the embodiment in which R ^u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
In formula (OS-101) or formula (OS-102), ^Ru2a represents an alkyl or aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, ^-NH- , -NR u5-, -CH _2- , -CR ^u6 H- or CR ^u6 R ^u7. ^Represents −, and R u5 to R ^u7 independently represent an alkyl group or an aryl group.

In the formula (OS-101) or the formula (OS-102), ^Ru1 to ^Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the ^R ^u1 ~ R ^u4. At this time, the ring may be condensed to form a condensed ring together with the benzene ring. The R ^u1 ~ ^{R u4,} a hydrogen atom, preferably a halogen atom or an alkyl group, ^also aspects to form the at least two aryl groups bonded to each other of R u1 ^{~ R u4} preferred. Above all, it is preferable that all of ^Ru1 to ^{Ru4 are hydrogen atoms.} Any of the above-mentioned substituents may further have a substituent.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the oxime sulfonate compound, the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692 and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference.
Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.

In addition, a commercially available product may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-69 (any of which). Also Fujifilm Wako Pure Chemical Industries, Ltd., Omnicat 250, Omnicat 270 (all manufactured by IGM Resins BV), Irgacure 250, Irgacure 270, Irgacure 290 (all manufactured by BASF), MBZ-101 (all manufactured by BASF) (Made by Midori Chemical Industries, Ltd.) and the like.

Further, a compound represented by the following structural formula is also mentioned as a preferable example.

As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-46-4605, JP-A. 48-36281, JP-A-55-3270, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No. 3), (1970) and the like can be mentioned, and in particular, an oxazole compound substituted with a trihalomethyl group: an S-triazine compound can be mentioned.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example 2,4,6-tris (monochromomethyl)- s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.

As a photoacid generator, an organic borate compound can also be applied. Examples of the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" and the like. Organic borates, organic boron sulfonium complexes or organic boron oxosulfonium complexes described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561 and JP-A-6-175554. Japanese Patent Application Laid-Open No. 6-175553, Organic Boron Iodonium Complex, Japanese Patent Application Laid-Open No. 9-188710, Organic Boron Phosphorium Complex, Japanese Patent Application Laid-Open No. 6-348011, Japanese Patent Application Laid-Open No. 7-128785 Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.

A disulfone compound can also be applied as a photoacid generator. Examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.

Examples of the onium salt compound include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.K. S. The diazonium salt described in Bal et al, Polymer, 21,423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365549, etc., US Pat. No. 4,069, Phosphonium salts described in 055, 4,069,056, European Patents 104, 143, US Patents 339,049, 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent No. 4,933,377, No. 161,811, No. 410,201, No. 339,049, No. 4,760,013, No. 4,734,444, No. 2,833,827, The sulfonium salt described in German Patent Nos. 2,904,626, 3,604,580, and 3,604,581. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. Mol. V. Crivello et al, J. et al. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), selenonium salt, C.I. S. Wen et al, Theh, Proc. Conf. Rad. Examples thereof include onium salts such as the arsonium salt and the pyridinium salt described in Curing ASIA, p478 Tokyo, Oct (1988).

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).

In the formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 carbon atom. ~ 12 alkenyl groups, alkynyl groups with 1 to 12 carbon atoms, aryl groups with 1 to 12 carbon atoms, alkoxy groups with 1 to 12 carbon atoms, allyloxy groups with 1 to 12 carbon atoms, halogen atoms, 1 to 12 carbon atoms Alkylamino group, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, Examples thereof include a thioaryl group having 1 to 12 carbon atoms. Z11 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable. In the formula (RI-II), Ar ₂₁ and Ar ₂₂ each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms. Alkyl group, alkenyl group with 1 to 12 carbon atoms, alkynyl group with 1 to 12 carbon atoms, aryl group with 1 to 12 carbon atoms, alkoxy group with 1 to 12 carbon atoms, aryloxy group with 1 to 12 carbon atoms, halogen atom , Alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 carbon number Examples thereof include a thioalkyl group having up to 12 and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms which may independently have 1 to 6 substituents. , Preferably an aryl group from the viewpoint of reactivity and stability. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Allyloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z31 ^- represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.

Specific examples include the following.

When a photoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.

When the curable resin composition of the present invention contains a photosensitive agent, the curable resin composition of the present invention contains 1 to 40 parts by mass of the photosensitive agent and 0. It is preferable to contain 05 to 20 parts by mass and 50 to 300 parts by mass of the above-mentioned solvent.
The content of the photosensitizer is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the specific resin.
The content of the specific compound is preferably 0.1 to 15 parts by mass, more preferably 0.2 to 10 parts by mass, and 0.5 to 8 parts by mass with respect to 100 parts by mass of the specific resin. Is particularly preferable.
The content of the solvent is preferably 70 to 250 parts by mass, more preferably 80 to 230 parts by mass, and particularly preferably 100 to 200 parts by mass with respect to 100 parts by mass of the specific resin.

<Thermal polymerization initiator>
The composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be allowed to proceed in the heating step described later, so that the solvent resistance can be further improved.

Specific examples of the thermal radical polymerization initiator include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. More preferably, it is 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

<Thermal acid generator>
The composition of the present invention may contain a thermoacid generator.
The thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.

The thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
The thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).

The acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane. Haloalkyl sulfonic acid such as sulfonic acid is preferable. Examples of such a thermoacid generator include those described in paragraph 0055 of JP2013-072935A.

Of these, those that generate alkylsulfonic acid having 1 to 4 carbon atoms or haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid is more preferable, from the viewpoint that there is little residue in the organic film and it is difficult to deteriorate the physical properties of the organic film. (4-Hydroxyphenyl) dimethylsulfonium, methanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl methanesulfonate (4-hydroxyphenyl) methylsulfonium, benzyl methanesulphonate (4-((methoxycarbonyl)) Carbonyl) oxy) phenyl) methylsulfonium, methanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, trifluoromethanesulfonic acid (4-) ((Methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzyl (4-hydroxyphenyl) methylsulfonium trifluoromethanesulfonate, benzyl trifluoromethanesulfonate (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-Hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3-(5-(((propylsulfonyl) oxy) imino) thiophen-2 (5H) -iriden) -2- (o-tolyl) Propanenitrile, 2,2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane is preferred as the thermoacid generator.

Further, the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.

The content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. By containing 0.01 part by mass or more, the cross-linking reaction is promoted, so that the mechanical properties and solvent resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.

<Onium salt>
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it preferably contains an onium salt.
The type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.

The onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. ..
That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
As the cation in the onium salt, an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.

The onium salt used in the present invention may be a thermobase generator described later.
The thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.

[Ammonium salt]
In the present invention, the ammonium salt means a salt of an ammonium cation and an anion.

-Ammonium cation-
As the ammonium cation, a quaternary ammonium cation is preferable.
Further, as the ammonium cation, a cation represented by the following formula (101) is preferable.

In formula (101), R ¹ to R ⁴ each independently represent a hydrogen atom or a hydrocarbon group, and ^{at least two of R 1} to R ⁴ may be bonded to each other to form a ring.

In the formula (101), R ¹ to R ⁴ are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups. R ¹ to R ⁴ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group.
When ^{at least two of R 1} to R ⁴ are bonded to each other to form a ring, the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.

The ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).

In the formula (Y1-1) and ^{(Y1-2), R 101} represents an n-valent organic group, ^{R 1} has the same meaning as ^{R 1} in the formula ^{(101), Ar 101} and ^{Ar 102} are each independently , Represents an aryl group, and n represents an integer of 1 or more.
In the formula (Y1-1), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-1), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-2), Ar ¹⁰¹ and Ar ¹⁰² are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.

-Anion-
As the anion in the ammonium salt, one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfuric acid anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermodegradability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion. According to this aspect, the stability, curability and developability of the curable resin composition can be further improved. In particular, by using a divalent carboxylic acid anion, the stability, curability and developability of the curable resin composition can be further improved.

The carboxylic acid anion is preferably represented by the following formula (X1).

In formula (X1), EWG represents an electron-attracting group.

In the present embodiment, the electron-attracting group means that Hammett's substituent constant σm shows a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642. The electron-attracting group in the present embodiment is not limited to the substituent described in the above document.
Examples of substituents in which σm shows a positive value are CF ₃ groups (σm = 0.43), CF ₃ C (= O) groups (σm = 0.63), and HC≡C groups (σm = 0. 21), CH ₂ = CH group (σm = 0.06), Ac group (σm = 0.38), MeOC (= O) group (σm = 0.37), MeC (= O) CH = CH group ( σm = 0.21), PhC (= O) group (σm = 0.34), H ₂ NC (= O) CH ₂ group (σm = 0.06) and the like. In addition, Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter, the same applies).

The EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).

In the formulas (EWG-1) to (EWG-6), R ^x1 to R ^x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.

In the present invention, the carboxylic acid anion is preferably represented by the following formula (XA).

In the formula ^{(XA), L 10} represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR ^X - represents and divalent connecting group selected from the group consisting a combination thereof, ^{R X} is , Hydrogen atom, alkyl group, alkenyl group or aryl group.

Specific examples of the carboxylic acid anion include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.

The onium salt in the present invention contains an ammonium cation as a cation from the viewpoint that the cyclization of the heterocyclic polymer-containing precursor is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved. As the salt as an anion, it is preferable to contain an anion having a conjugate acid pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
The lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the heterocyclic polymer-containing precursor or the like is improved. The above is more preferable.
The above pKa includes Determination of Organic Structures by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F.C.; See Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.

Specific examples of the ammonium salt include the following compounds, but the present invention is not limited thereto.

[Iminium salt]
In the present invention, the iminium salt means a salt of an iminium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iminium cation-
As the iminium cation, a pyridinium cation is preferable.
Further, as the iminium cation, a cation represented by the following formula (102) is also preferable.

In formula (102), R ⁵ and R ⁶ each independently represent a hydrogen atom or a hydrocarbon group, R ⁷ represents a hydrocarbon group, and ^{at least two of R 5} to R ⁷ are bonded to each other to form a ring. It may be formed.
In the formula (102), R ⁵ and R ⁶ ^{are synonymous with R 1} to R ⁴ in the above formula (101), and the preferred embodiment is also the same.
In formula (102), R ⁷ preferably combines with at least one of R ⁵ and R ^{6 to form a ring.} The ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.

The iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).

In Formula ^{(Y1-3) ~ (Y1-5),} R 101 represents an n-valent organic group, ^{R 5} has the same meaning as ^{R 5} in the formula (102), ^{R 7} is R in the formula (102) ^{Synonymous with 7} , n and m represent integers of 1 or more.
In the formula (Y1-3), R ¹⁰¹ is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
In the formula (Y1-3), n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
In the formula (Y1-5), m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.

Specific examples of the iminium salt include the following compounds, but the present invention is not limited thereto.

[Sulfonium salt]
In the present invention, the sulfonium salt means a salt of a sulfonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Sulfonium cation-
As the sulfonium cation, a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable.
Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.

In formula (103), R ⁸ to R ¹⁰ each independently represent a hydrocarbon group.
R ⁸ to R ¹⁰ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ⁸ to R ¹⁰ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group. Among these, the substituent preferably has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and has a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 1 to carbon atoms. It is more preferable to have 10 alkoxy groups.
R ⁸ to R ¹⁰ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the sulfonium salt include the following compounds, but the present invention is not limited thereto.

[Iodonium salt]
In the present invention, the iodonium salt means a salt of an iodonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Iodonium cation-
As the iodonium cation, a diaryl iodonium cation is preferable.
Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.

In formula (104), R ¹¹ and R ¹² each independently represent a hydrocarbon group.
R ¹¹ and R ¹² are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ¹¹ and R ¹² may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R ¹¹ and R ¹² may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the iodonium salt include the following compounds, but the present invention is not limited thereto.

[Phoenium salt]
In the present invention, the phosphonium salt means a salt of a phosphonium cation and an anion. As the anion, the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.

-Phosnium cation-
As the phosphonium cation, a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation.
Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.

In formula (105), R ¹³ to R ¹⁶ each independently represent a hydrogen atom or a hydrocarbon group.
R ¹³ to R ¹⁶ are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
R ¹³ to R ¹⁶ may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy. Examples thereof include a carbonyl group and an acyloxy group. Among these, it is preferable to have an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have an alkoxy group of.
R ¹³ to R ¹⁶ may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.

Specific examples of the phosphonium salt include the following compounds, but the present invention is not limited thereto.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
As the onium salt, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Thermal base generator>
The curable resin composition of the present invention may further contain a thermosetting agent.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as the specific resin, it is preferable to contain a thermosetting agent.
The other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).

In formulas (B1) and (B2), Rb ¹ , Rb ² and Rb ³ are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb ¹ and Rb ² do not become hydrogen atoms at the same time. Further, ^{none of Rb 1} , Rb ² and Rb ³ has a carboxy group. In the present specification, the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.

In formulas (B1) and (B2), ^{it is preferable that at least one of Rb 1} , Rb ² and Rb ³ contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure. The cyclic structure may be either a monocyclic ring or a condensed ring, and a fused ring in which two monocyclic rings or two monocyclic rings are condensed is preferable. The single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. As the single ring, a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.

More specifically, Rb ¹ and Rb ² are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2 to 18 are more preferred, 3 to 12 are more preferred), aryl groups (6 to 22 carbon atoms are preferred, 6 to 18 are more preferred, 6 to 10 are more preferred), or arylalkyl groups (7 carbon atoms are more preferred). ~ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb ¹ and Rb ² may be coupled to each other to form a ring. As the ring to be formed, a 4- to 7-membered nitrogen-containing heterocycle is preferable. Rb ¹ and Rb ² are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent. A cyclohexyl group which may be used is more preferable.

As Rb ³ , an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6). ~ 10 is more preferable), alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). Preferably, 7 to 12 are more preferable), an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24). 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further preferable). Among them, a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable. Rb ³ may further have a substituent as long as the effect of the present invention is exhibited.

The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).

In the formula, Rb ¹¹ and Rb ¹² , and Rb ³¹ and Rb ³² are the same as ^{Rb 1} and Rb ² in the formula (B1), respectively.
Rb ¹³ has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effect of the present invention is exhibited. Of these, Rb ¹³ is preferably an arylalkyl group.

Rb ³³ and Rb ³⁴ independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), arylalkyl groups (7 to 7 to carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable), and a hydrogen atom is preferable.

Rb ³⁵ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.

As the compound represented by the formula (B1-1), the compound represented by the formula (B1-1a) is also preferable.

Rb ¹¹ and ^{Rb 12} have the same meanings as ^{Rb 11} and ^{Rb 12} in the formula (B1-1).
Rb ¹⁵ and Rb ¹⁶ are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7). ~ 19 is more preferable, and 7 to 11 is more preferable), and a hydrogen atom or a methyl group is preferable.
Rb ¹⁷ is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.

The molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

Among the above-mentioned onium salts, specific examples of compounds that are thermal base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.

The content of the other thermobase generator is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less. As the thermobase generator, one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.

<Crosslinking agent>
The curable resin composition of the present invention preferably contains a cross-linking agent.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.

<Radical cross-linking agent>
The curable resin composition of the present invention preferably further contains a radical cross-linking agent.
The radical cross-linking agent is a compound having a radically polymerizable group. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
Among these, the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.

The radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
The compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As the compound having 3 or more ethylenically unsaturated bonds, a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable. The compound having is more preferable.
The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds. A compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the curable resin composition of the present invention has a compound having two ethylenically unsaturated bonds and three or more ethylenically unsaturated bonds. It is also preferable to include a compound.

The molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.

Specific examples of the radical cross-linking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, which are preferably unsaturated. Esters of saturated carboxylic acid and polyhydric alcohol compound, and amides of unsaturated carboxylic acid and polyvalent amine compound. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines, thiols, and a halogeno group. Substitution reaction products of unsaturated carboxylic acid esters or amides having a desorbing substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable. Further, as another example, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether or the like. As a specific example, the description in paragraphs 0113 to 0122 of JP-A-2016-0273557 can be referred to, and these contents are incorporated in the present specification.

Further, as the radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable. Examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin, trimethylolethane, etc. A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993. Urethane (meth) acrylates, such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable. Further, a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.

Further, as a preferable radical cross-linking agent other than the above, it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. Compounds having two or more groups and cardo resins can also be used.

Further, as other examples, the specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Square Root 01-040337, and Japanese Square Root 01-040336, and Japanese Patent Application Laid-Open No. 02-025493. Vinyl phosphonic acid compounds and the like can also be mentioned. Further, a compound containing a perfluoroalkyl group described in JP-A-61-022048 can also be used. Furthermore, the magazine of the Japan Adhesive Association vol. 20, No. Those introduced as photopolymerizable monomers and oligomers on pages 7, 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of International Publication No. 2015/199219 can also be preferably used, and the contents thereof are described in the present specification. Incorporated into the book.

Further, the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol and then (meth) acrylated is also used. It can be used as a radical cross-linking agent.

Further, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as radical cross-linking agents, and their contents are incorporated in the present specification.

As radical cross-linking agents, dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable. These oligomer types can also be used.

Commercially available products of the radical cross-linking agent include, for example, SR-494, which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer, and SR-209 manufactured by Sartmer, which is a bifunctional methacrylate having four ethyleneoxy chains. 231 and 239, DPCA-60, a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, and urethane oligomer UAS-10. , UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.

Examples of the radical cross-linking agent include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. Urethane compounds having an ethylene oxide-based structure described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable. Further, as the radical cross-linking agent, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. You can also do it.

The radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group. The radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A radical cross-linking agent provided with is more preferable. Particularly preferably, in a radical cross-linking agent in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound. Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

The preferable acid value of the radical cross-linking agent having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good. On the other hand, from the viewpoint of the development speed in the case of alkaline development, the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g. The acid value is measured according to the description of JIS K 0070: 1992.

For the curable resin composition of the present invention, it is preferable to use bifunctional metal acrylate or acrylate from the viewpoint of pattern resolution and film elasticity. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene. Glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives Dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates having urethane bonds can be used. it can. If necessary, two or more of these can be mixed and used. For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
Further, from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured film), a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent. Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. (meth) Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used. As the monofunctional radical cross-linking agent, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.

When a radical cross-linking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.

One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.

<Other cross-linking agents>
The curable resin composition of the present invention preferably contains another cross-linking agent different from the radical cross-linking agent described above.
In the present invention, the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer. It is preferable that the compound has a plurality of groups in the molecule for which the reaction to be formed is promoted, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of an acid or a base. A compound having a plurality of groups promoted by the above in the molecule is preferable.
The acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator, which is a photosensitizer, in an exposure step such as a first region exposure step or a second region exposure step.
As the other cross-linking agent, a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom. A compound having a structure directly bonded to is more preferable.
As another cross-linking agent, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group. Examples thereof include compounds having a substituted structure. The method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
As the above amino group-containing compound, the cross-linking agent using melamine is a melamine-based cross-linking agent, the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent, and the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent. A cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
Among these, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and preferably contains a glycoluril-based cross-linking agent and melamine, which will be described later. It is more preferable to contain at least one compound selected from the group consisting of system cross-linking agents.

Specific examples of the melamine-based cross-linking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like.

Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycoluryl-based cross-linking agent;
Urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea,
Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated ethyleneurea, monoethoxymethylated ethyleneurea, diethoxymethylated ethyleneurea, monopropoxymethylated ethyleneurea, dipropoxymethyl Ethyleneurea-based cross-linking agents such as ethyleneurea, monobutoxymethylated, or dibutoxymethylated ethyleneurea,
Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.

Specific examples of the benzoguanamine-based cross-linking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine. , Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like can be mentioned.

In addition, as a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group, at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring). A compound to which a group is directly bonded is also preferably used.
Specific examples of such compounds include benzenedimethanol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, and hydroxymethylbenzoate hydroxymethylphenyl. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzenephenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Methoxymethyl) -1,1'-biphenyl-4,4'-diol and the like can be mentioned.

Commercially available products may be used as other cross-linking agents, and suitable commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP. , DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, Honshu) Nikalac (registered trademark, the same applies hereinafter) MX-290, Nikarak MX-280, Nikarak MX-270, Nikarak MX-279, Nikarak MW-100LM, Nikarak MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.) ) And so on.

Further, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.

[Epoxy compound (compound having an epoxy group)]
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Since the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower and the dehydration reaction derived from the cross-linking does not occur, film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.

The epoxy compound preferably contains a polyethylene oxide group. As a result, the elastic modulus can be further reduced and warpage can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.

Examples of epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propan triglycidyl ether or the like alkylene glycol type epoxy resin or polyhydric alcohol hydrocarbon type epoxy resin; polypropylene glycol diglycidyl ether or the like polyalkylene glycol type epoxy resin; polymethyl (glycidyloxypropyl) siloxane or the like epoxy group Examples of the contained silicone and the like can be mentioned, but the present invention is not limited to these. Specifically, Epicron® 850-S, Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron® EXA-4816, Epicron® EXA-4822, Epicron® EXA-830LVP, Epicron® EXA-8183, Epicron (Registered Trademark) EXA-8169, Epicron (Registered Trademark) N-660, Epicron (Registered Trademark) N-665-EXP-S, Epicron (Registered Trademark) N-740, Rica Resin (Registered Trademark) BEO-20E Name, manufactured by DIC Co., Ltd., Rikaresin (registered trademark) BEO-60E, Rikaresin (registered trademark) HBE-100, Rikaresin (registered trademark) DME-100, Rikaresin (registered trademark) L-200 (trade name, New Japan) Rika Co., Ltd., EP-4003S, EP-4000S, EP-4088S, EP-3950S (trade name, manufactured by ADEKA Co., Ltd.), Serokiside 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Serviners B0134, B0177 (trade name, manufactured by Daicel Co., Ltd.), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000 -L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201 , BREN-S, BREN-10S (trade name, manufactured by Nippon Kayaku Co., Ltd.) and the like.

[Oxetane compound (compound having an oxetanyl group)]
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and the like. Examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like. As a specific example, the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.

[Benzoxazine compound (compound having a benzoxazolyl group)]
Since the benzoxazine compound is a cross-linking reaction derived from the cycloaddition reaction, degassing does not occur during curing, and the heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.

Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly. Examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.

The content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass. The other cross-linking agent may contain only one type, or may contain two or more types. When two or more other cross-linking agents are contained, the total is preferably in the above range.

<Migration inhibitor>
The curable resin composition of the present invention preferably further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.
In the present invention, the above-mentioned compound having a triazole structure does not correspond to a migration inhibitor.

The migration inhibitor is not particularly limited, but a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc. Pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring, piperazine ring, morpholin ring, 2H-pyran ring and 6H-pyran ring, triazine ring) compounds, thioureas and sulfanyl groups, hindered phenol compounds , Salicylic acid derivative compound, hydrazide derivative compound and the like. In particular, tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion trap agent that traps anions such as halogen ions can also be used.

Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656. The compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.

Specific examples of the migration inhibitor include the following compounds.

When the curable resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.

The migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.

<Polymerization inhibitor>
The curable resin composition of the present invention preferably contains a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p-benzoquinone. , 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine , N-nitroso diphenylamine, N-phenylnaphthylamine, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol , 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitrosophenyl hydroxyamine first cerium salt, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4) -Hydroxy-3,5-tert-butyl) phenylmethane, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 4-hydroxy-2,2,6,6-tetramethylpiperidin 1-oxyl free radical, phenothiazine, 1,1-diphenyl-2-picrylhydrazyl, Dibutyldithiocarbanate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt and the like are preferably used. Further, the polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and the compound described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

In addition, the following compounds can be used (Me is a methyl group).

When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is 0.01 to 20.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass.

The polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.

<Metal adhesion improver>
The curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like. Examples of the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds and the like. And so on.

Examples of the silane coupling agent include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992. Compounds described in 0063 to 0071, compounds described in paragraphs 0060 to 0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594. Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent. In the following formula, Et represents an ethyl group.

Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanure, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuppropyl Examples thereof include triethoxysilane and 3-trimethoxysilylpropyl succinate anhydride. These can be used individually by 1 type or in combination of 2 or more types.

[Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.

As the metal adhesiveness improving agent, the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is improved, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are improved. The metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.

<Other additives>
The curable resin composition of the present invention contains various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, and inorganic particles, if necessary, as long as the effects of the present invention can be obtained. , Curing agent, curing catalyst, filler, antioxidant, ultraviolet absorber, anti-aggregation agent and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.

[Sensitizer]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electron-excited state. The sensitizer in the electronically excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684. As the chain transfer agent, for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals. In particular, a thiol compound can be preferably used.

Further, as the chain transfer agent, the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention. Preferably, 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable. The chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.

[Surfactant]
Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability. As the surfactant, various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used. The following surfactants are also preferable. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.

Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving property, and has good solubility in the composition.

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.

Examples of the hydrocarbon-based surfactant include Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin. D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (all manufactured by Takemoto Oil & Fat Co., Ltd.) and the like can be mentioned.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solspers 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orphine E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

Specifically, as a cationic surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like can be mentioned.

Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

When the curable resin composition of the present invention has a surfactant, the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. The surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.

[Higher fatty acid derivative]
The curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.

Further, as the higher fatty acid derivative, the compound described in paragraph 0155 of International Publication No. 2015/199219 can also be used.

When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is 0.1 to 10% by mass based on the total solid content of the curable resin composition of the present invention. Is preferable. The higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.

[Thermal polymerization initiator]
The resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator. A thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. Since the polymerization reaction of the resin and the polymerizable compound can be allowed to proceed by adding the thermal radical polymerization initiator, the solvent resistance can be further improved.

When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.

[Inorganic particles]
The resin composition of the present invention may contain inorganic particles. Specific examples of the inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing a large amount of the average particle size of the inorganic particles, the mechanical properties of the cured film may deteriorate. Further, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

[UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxy-4-octoxybenzophenone and the like can be mentioned. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.

Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like. Furthermore, examples of triazine-based ultraviolet absorbers include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl) -4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2) , 4-Dimethylphenyl) -1,3,5-triazine and other bis (hydroxyphenyl) triazine compounds; 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) )-1,3,5-Triazine, 2,4,6-Tris (2-Hydroxy-4-octyloxyphenyl) -1,3,5-Triazine, 2,4,6-Tris [2-Hydroxy-4 -(3-Butoxy-2-hydroxypropyloxy) phenyl] -1,3,5-Triazine and other tris (hydroxyphenyl) triazine compounds and the like can be mentioned.

In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

[Organic titanium compound]
The resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.

Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
Specific examples of the organic titanium compound are shown in I) to VII) below:
I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained. Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)). , Titanium diisopropoxyside bis (tetramethylheptandionate), titanium diisopropoxyside bis (ethylacetacetate) and the like.
II) Tetraalkoxytitanium compounds: For example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxyside), titanium tetraisobutoxide, titanium tetraisopropoxyside, titanium tetramethoxide. , Titanium Tetramethoxypropoxyside, Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss Butokiside}] etc.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.

Among them, as the organic titanium compound, at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanosen compound has better chemical resistance. It is preferable from the viewpoint of playing. In particular, titanium diisopropoxyside bis (ethylacetacetate), titanium tetra (n-butoxide), and bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H)). -Pyrrole-1-yl) phenyl) titanium is preferred.

When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the precursor of the cyclized resin. .. When the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.

〔Antioxidant〕
The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. Preferred phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As a phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like. Commercially available products of antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, the composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like. Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).

In the general formula (3), R ⁵ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R ⁶ represents an alkylene group having 2 or more carbon atoms. R ⁷ represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom. k represents an integer of 1 to 4.

The compound represented by the general formula (3) suppresses oxidative deterioration of aliphatic groups and phenolic hydroxyl groups of the resin. In addition, metal oxidation can be suppressed by the rust preventive action on the metal material.

Since it can act on the resin and the metal material at the same time, k is more preferably an integer of 2 to 4. R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-. Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent. Among these, it is preferable to have alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of metal adhesion due to interaction with resin and metal complex formation. preferable.

Examples of the compound represented by the following general formula (3) include the following, but the compound is not limited to the following structure.

The amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. If the amount added is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability and the adhesion to the metal material, and if it is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of lowering the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<Restrictions on other contained substances>
The water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties. Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.

The metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.

Further, as a method for reducing metal impurities unintentionally contained in the curable resin composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention. Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.

Considering the use as a semiconductor material, the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.

A conventionally known storage container can be used as the storage container for the curable resin composition of the present invention. Further, as the storage container, for the purpose of suppressing impurities from being mixed into the raw material and the curable resin composition, a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a layered bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

<Use of curable resin composition>
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.

<Preparation of curable resin composition>
The curable resin composition of the present invention can be prepared by mixing each of the above components. The mixing method is not particularly limited, and a conventionally known method can be used.

Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the curable resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm or less is further preferable. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

(Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.

The cured film of the present invention is obtained by curing the curable resin composition of the present invention. The film thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Further, the upper limit value can be 100 μm or less, and can be 30 μm or less.

The cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable. The first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention. A preferred embodiment is a film obtained by curing the resin composition. The curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. It may be present, or it may be a composition having a different composition. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above. For these applications, for example, Science & Technology Co., Ltd. "High-performance and applied technology of polyimide" April 2008, Masaaki Kakimoto / supervision, CMC technical library "Basics and development of polyimide materials" November 2011 You can refer to "Latest Polyimide Basics and Applications", NTS, August 2010, etc., published by Japan Polyimide / Aromatic Polymer Research Association / ed.

The cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.

The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. Is preferable.
The method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
Further, the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C.
Specifically, it is also preferable to include the following steps (a) to (d).
(A) Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer) (b) Exposure step of exposing the film after the film forming step (c) Exposure Development step for developing the above-mentioned film (d) Heating step for heating the developed above-mentioned film at 50 to 450 ° C. By heating in the above-mentioned heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.

The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention. The method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D). In particular, it is preferable to carry out each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order. By laminating the cured film in this way, a laminated body can be obtained. In the present invention, it is particularly preferable to provide a metal layer on the portion provided with the cured film, between the cured films, or both. In the production of the laminate, it is not necessary to repeat all the steps (a) to (d), and as described above, at least (a), preferably (a) to (c) or (a) to (d). ) Can be performed a plurality of times to obtain a laminated body of the cured film.

<Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).

The type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like.
Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
Further, these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
Further, as the base material, for example, a plate-shaped base material (board) is used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
The size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

When the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.

Coating is preferable as a means for applying the curable resin composition to the base material.

Specifically, the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method. And the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method.
Further, the coating method can be appropriately selected depending on the shape of the base material. For a circular base material such as a wafer, a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is preferable. The method, the inkjet method and the like are preferable. In the case of the spin coating method, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
Further, depending on the viscosity of the photosensitive resin composition and the film thickness to be set, it is preferable to apply the photosensitive resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Further, in order to obtain the uniformity of the film thickness, a plurality of rotation speeds can be combined and applied.
Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like.
Further, a pre-wetting step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.

<Drying process>
The production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent. The preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C. The drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.

<Exposure process>
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer). The amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, ^{it is preferable to irradiate 100 to 10,000 mJ / cm 2 in} terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm ^2.

The exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.

In relation to the light source, the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. The curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
From the viewpoint of handling and productivity, a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.

<Development process>
The production method of the present invention may include a developing step of developing the exposed film (curable resin composition layer) (developing the film). By developing, the unexposed portion (non-exposed portion) is removed. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used. The developing process includes a process in which the developing solution is continuously supplied to the base material, a step in which the developing solution is kept in a substantially stationary state on the base material, a step in which the developing solution is vibrated by ultrasonic waves or the like, and a combination thereof. Processes can be adopted.

Development is carried out using a developing solution. The developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
As the developing solution, a developing solution containing an organic solvent or an alkaline aqueous solution can be used.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.

When the developing solution is a developing solution containing an organic solvent, the organic solvent may be, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate. , Butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), 3-alkyloxypropionate alkyl esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) , 3-Methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg 2-alkyloxypropionate) Methyl, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2) -Ethyl propionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol Dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, propylene glycol mono As propyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons, for example, toluene. , Xylene, anisole, limonene and the like, dimethyl sulfoxide is preferably mentioned as sulfoxides, and a mixture of these organic solvents is also preferably mentioned.

When the developer is a developer containing an organic solvent, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention. When the developing solution contains an organic solvent, one kind or a mixture of two or more kinds of organic solvents can be used.

When the developer is a developer containing an organic solvent, 50% by mass or more of the developer is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is organic. It is more preferably a solvent. Further, the developing solution may be 100% by mass of an organic solvent.

The developer may further contain other components.
Examples of other components include known surfactants and known defoamers.

When the developing solution is an alkaline aqueous solution, examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. .. When TMAH is used, for example, the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developer. Is more preferable.

[Method of supplying developer]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable, and the developer is supplied to the image area. From the viewpoint of permeability, the method of supplying with a spray nozzle is more preferable.
Further, after the developer is continuously supplied by the straight nozzle, the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied by the straight nozzle again, and then the base material is spun to use the developer as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times.
Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.

The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly specified, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.

After the treatment with the developing solution, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted. The rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the curable resin composition.
When the developer is a developer containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA. Further, water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, still more preferably 5 seconds to 1 minute. The temperature of the rinsing liquid at the time of rinsing is not particularly specified, but is preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.

Examples of the organic solvent when the rinsing solution contains an organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkyloxyacetate (eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) Ethyl, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionate (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), etc. Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, 2) -Ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropion) Ethyl propionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (eg, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropionate) Ethyl acid acid, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran , Ethyl glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), Propylene glycol monoethyl ether acetate, propionate Lopyrene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons. For example, toluene, xylene, anisole, limonene, etc., dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols. Preferred examples of glycols and the like and amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.

When the rinsing liquid contains an organic solvent, one type or a mixture of two or more types of organic solvent can be used. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferable, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA and PGME are more preferable, and cyclohexanone and PGMEA are preferable. More preferred.

When the rinsing liquid contains an organic solvent, 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable. Further, the rinse liquid may be 100% by mass of an organic solvent.

The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoamers.

[Supplying method of rinse liquid]
The method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the paddle development on the base material, the method of supplying the rinse liquid to the base material by a shower, and the base material. There is a method of continuously supplying the developing solution by means such as a straight nozzle on the top.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, the method of supplying the rinse liquid with a spray nozzle is more preferable. The type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
Further, as a method of supplying the rinse liquid in the rinsing step, a step of continuously supplying the rinse liquid to the base material, a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material. A process of vibrating with a sound conditioner or the like and a process of combining them can be adopted.

<Heating process>
The production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
The heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, the curable resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but may also cure a radically polymerizable compound other than the precursor which is an unreacted specific resin. It can be advanced in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable. The upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.

The heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the temperature rise rate to 1 ° C./min or more, it is possible to prevent excessive volatilization of amine while ensuring productivity, and by setting the temperature rise rate to 12 ° C./min or less, the cured film can be prevented. Residual stress can be relaxed. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. ℃ / sec is more preferable.

The temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C. The temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started. For example, when the curable resin composition is applied onto a substrate and then dried, the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.

The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.

Particularly when forming a multi-layered laminate, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.

Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547. It is possible to improve the characteristics of the film by such a pretreatment step. The pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.

Further, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.

It is preferable that the heating step is performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
The heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.

<Metal layer forming process>
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).

As the metal layer, existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified. The alloy containing the above is more preferable, and copper is further preferable.

The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm at the thickest portion.

<Laminating process>
The production method of the present invention preferably further includes a laminating step.

The laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated.
Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once. Further, the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.

When the laminating step is further performed after the laminating step, the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step. An example of the surface activation treatment is plasma treatment.

The laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times.
Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.

For example, a configuration in which the resin layer is 2 or more and 20 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and a configuration of 3 or more and 7 or less is more preferable. More preferably, it has 3 or more layers and 5 or less layers.

In the present invention, it is particularly preferable to form a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided. Specifically, a mode in which (a) a film forming step, (b) an exposure step, (c) a developing step, (e) a metal layer forming step, and (d) a heating step are repeated in this order, or (a) film forming. Examples thereof include an embodiment in which (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is collectively provided at the end or in the middle. By alternately performing the laminating step of laminating the curable resin composition layer (resin layer) and the metal layer forming step, the curable resin composition layer (resin layer) and the metal layer can be laminated alternately.

(Surface activation treatment process)
The method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activating treatment step is usually performed after the metal layer forming step, but it is also possible to perform the surface activating treatment step on the photosensitive resin composition layer after the exposure development step and then perform the metal layer forming step. Good.
The surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially. The surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer in which the photosensitive resin composition layer is formed on the surface. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. By performing the surface activating treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment.
Specifically, the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF ₄ / O ₂ , NF ₃ / O ₂ , SF ₆ , NF ₃ , NF ₃ / O ₂ , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable. For corona discharge treatment, the energy is preferably 500 ~ 200,000J / ^{m 2,} more preferably 1000 ~ 100,000J / ^{m 2,} and most preferably 10,000 ~ 50,000J / ^{m 2.}

The present invention also discloses a semiconductor device containing the cured film or laminate of the present invention. As specific examples of the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer, the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.

The present invention will be described in more detail with reference to examples below. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.

<Synthesis Example 1: Synthesis of Polymer A-1>
Place 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) in a 2 liter volume separable flask, add 131.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone, and stir at room temperature. Then, 81.5 g of pyridine was added with stirring to obtain a reaction mixture. After the heat generated by the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.
Next, under ice-cooling, a solution of 206.3 g of dicyclohexylcarbodiimide (DCC) dissolved in 180 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes with stirring, followed by 4,4'-diaminodiphenyl ether (DADPE). A suspension of 93.0 g in 350 ml of γ-butyrolactone was added over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution.
The obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer. The produced crude polymer was filtered off and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to 28 liters of water to precipitate a polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a powdery polymer A-1. When the molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.

<Synthesis Example 2: Synthesis of Polymer B-1>
Synthesis Example 1 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride in Synthesis Example 1. The reaction was carried out in the same manner as described in 1. Polymer B-1 was obtained. When the molecular weight of the polymer B-1 was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 22,000.

<Synthesis Example 3: Synthesis of Polymer A-2>
With 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride (dried at 140 ° C for 12 hours) and 17.12 g (131.58 mmol) of 2-hydroxyethyl methacrylate (HEMA). Was suspended in 50 ml of N-methylpyrrolidone and dried on a molecular sieve. The suspension was heated at 100 ° C. for 3 hours. A clear solution was obtained a few minutes after the start of heating. The reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 ml of N-methylpyrrolidone were added. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCL ₂ was added over 10 minutes while keeping the temperature at −10 ± 4 ° C. Viscosity increased while SOCL _{2 was added.} After diluting with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution prepared by dissolving 11.75 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5000 rpm for 15 minutes. The polyimide precursor was collected by filtration, put into 4 liters of water again, stirred for another 30 minutes, and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain polymer A-2.

<Synthesis Example 4: Synthesis of Polymer B-2>
In Synthesis Example 3, 19.0 g (64.5 mmol) of 3,3'4,4'-biphenyltetra instead of 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic dianhydride The reaction was carried out in the same manner as described in Synthesis Example 3 except that the carboxylic dianhydride was used to obtain polymer B-2.

<Synthesis Example 5: Synthesis of Polymer C>
2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (32.78 g (0.0895 mol)) and 1,3-bis (3-aminopropyl) tetramethyldi under a dry nitrogen stream. Siloxane (1.24 g (0.005 mol)) was dissolved in 100 g of NMP. To this solution, bis (3,4-dicarboxyphenyl) ether dianhydride (31.02 g (0.10 mol)) was added with 30 g of NMP and stirred at 20 ° C. for 1 hour, then at 50 ° C. for 4 hours. Stirred. 3-Aminophenol (1.09 g (0.01 mol)) was added to the stirred solution, and the mixture was stirred at 50 ° C. for 2 hours and then at 180 ° C. for 5 hours to obtain a resin solution. Next, this resin solution was poured into water (3 L) to generate a white precipitate. The white precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 5 hours. As a result, a powder of polymer C, which is a polyimide, was obtained.

<Synthesis Example 6: Synthesis of Polymer D>
In a separable flask, 2,2-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane 183.1 g (0.5 mol), N, N-dimethylacetamide (DMAc) 640.9 g, pyridine 63 .3 g (0.8 mol) was mixed and stirred at room temperature (25 ° C.) to prepare a uniform solution. To this, 118.0 g (0.4 mol) of 4,4'-diphenyl ether dicarbonyl chloride dissolved in 354 g of diethylene glycol dimethyl ether (DMDG) was added dropwise from a dropping funnel. At this time, the separable flask was cooled in a water bath at 15 to 20 ° C. The time required for dropping was 40 minutes, and the reaction liquid temperature was 30 ° C. at the maximum.
After 3 hours from the completion of the dropwise addition, 30.8 g (0.2 mol) of 1,2-cyclohexyldicarboxylic acid anhydride was added to the reaction solution, and the mixture was left to stir for 15 hours at room temperature to remove 99% of all amine terminal groups of the polymer chain. It was sealed with a carboxycyclohexylamide group. The reaction rate at this time can be easily calculated by tracking the remaining amount of the charged 1,2-cyclohexyldicarboxylic acid anhydride by high performance liquid chromatography (HPLC). After that, the above reaction solution was added dropwise to 2 L of water under high-speed stirring to disperse and precipitate the polymer, which was recovered, washed with water as appropriate, dehydrated, vacuum dried, and measured by a gel permeation chromatography (GPC) method. A crude polybenzoxazole precursor having a weight average molecular weight of 9,000 (polystyrene equivalent) was obtained.
The crude polybenzoxazole precursor obtained above is redissolved in γ-butyrolactone (GBL), treated with a cation exchange resin and an anion exchange resin, and the resulting solution is prepared in ion exchange water. The precipitated polymer was filtered, washed with water, and vacuum-dried to obtain a purified polybenzoxazole precursor (polymer D).

<Synthesis Example 7: Synthesis of Polymer E>
2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6F-BAPH) 50.0 g (0.137 mol) and 2,2-bis (4-carboxy) in 300 g of PPA (polyphosphoric acid) Phenyl) Hexafluoropropane (BIS-B-AF) 53.5 g (0.137 mol) is added and heated to 100 ° C. under a nitrogen stream, and then heated to 200 ° C. at a heating rate of about 10 ° C./min. Then, the temperature was maintained at 200 ° C. for 150 minutes to obtain polymer E which is a polybenzoxazole.

<Synthesis Example 8: Synthesis of Polymer F>
123 ml of N-methylpyrrolidone and 54.97 g (0.124 mol) of 6FDA (manufactured by Tokyo Chemical Industry Co., Ltd., product number: H0771) are added to a three-necked flask and dissolved at 40 ° C., and the mixture is stirred under a nitrogen stream. By the way, 2,3,5,6-tetramethylphenylenediamine TeMPD (manufactured by Tokyo Chemical Industry Co., Ltd., product number: T1457) 8.13 g (0.049 mol), m-phenylenediamine (Fujifilm Wako Pure Chemical Industries, Ltd.) ), Product number: 164-01515) 6.69 g (0.062 mol), 3,5-diaminobenzoic acid DABA (manufactured by Tokyo Chemical Industry Co., Ltd., product number: D0294) 1.971 g (0.012 mol) N A 84.0 ml solution of -methylpyrrolidone was added dropwise over 30 minutes while maintaining the temperature in the system at 40 ° C. After stirring the reaction solution at 40 ° C. for 2.5 hours, 2.94 g (0.037 mol) of pyridine (manufactured by Wako Pure Chemical Industries, Ltd., product number: 166-22575), acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., product) No .: 018-00286) 31.58 g (0.31 mol) was added, and the mixture was further stirred at 80 ° C. for 3 hours. Then, 676.6 mL of acetone was added to the reaction solution to dilute it. 1.15 L of methanol and 230 mL of acetone were added to a stainless steel container and stirred, and a diluted acetone solution of the reaction solution was added dropwise. The obtained polymer crystals were suction-filtered and air-dried at 60 ° C. to obtain 60.1 g of polymer F.

<Examples and Comparative Examples>
In each Example or Comparative Example, among the components shown in Tables 2 to 8 below, components other than the basic compound were mixed to obtain a curable resin composition or a comparative composition.
The numerical values in the columns of each component other than the solvent shown in Tables 2 to 8 represent the content (parts by mass) of each component.
The numerical value in the solvent column represents the content (parts by mass) of the solvent used.
The obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 μm.
Further, in Tables 2 to 8, the description of "-" indicates that the composition does not contain the corresponding component.

Details of each component listed in Tables 2 to 8 are as follows.

〔resin〕
-A-1, B-1, A-2, B-2, C to F: Polymer A-1, polymer B-1, polymer A-2, polymer B-2, polymer C synthesized in the above synthesis example. ~ F

[Specific compound (compound having a triazole structure)]
G-1: 1H-benzotriazole (pKa = 11.9 in DMSO)
G-2: 5-methyl-1H-benzotriazole (pKa = 11.9 in DMSO)
G-3: 4-methyl-1H-benzotriazole (pKa = 11.9 in DMSO)
G-4: Triltriazole (isomer mixture of 5-methyl-1H-benzotriazole and 4-methyl-1H-benzotriazole, pKa = 11.9 in DMSO)
G-5: 1,2,3-triazole (pKa = 13.9 in DMSO)
G-6: 1,2,4-triazole (pKa = 14.8 in DMSO)
G-7: benzimidazole (pKa in DMSO = 16.4)
G-8: Indole (pKa in DMSO = 21.0)
G-9: 1H-tetrazole (pKa in DMSO = 8.2)
G-7, G-8 and G-9 are compounds having no triazole structure.

[Polymerization inhibitor]
・ H-1: p-benzoquinone ・ H-2: 4-methoxyphenol ・ H-3: 2-nitroso-1-naphthol

[Photosensitizer or sensitizer]
-I-1: 1-Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) -oxime-I-2: NCI 831 (manufactured by ADEKA)
-I-3: Irgacure OXE01 (manufactured by BASF)
-I-4: Irgacure OXE02 (manufactured by BASF)
・ I-5: Irgacure 784 (manufactured by BASF)
-I-6: Irgacure 379 (manufactured by BASF)
・ I-7: 7-diethylamino-3-ethoxycarbonylcoumarin ・ I-8: diazonaphthoquinone ・ I-9: Wako WPAG-145 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[Crosslinking agent]
・ J-1: Tetraethylene glycol dimethacrylate ・ J-2: Light ester BP-6EM (manufactured by Kyoeisha Chemical Co., Ltd.)
・ J-3: Daicel Celoxide CEL2081 (manufactured by Daicel Co., Ltd.)
・ J-4: Hexamethoxymethylmelamine

[Adhesive (silane coupling agent)]
・ K-1: N- [3- (triethoxysilyl) propyl] phthalamic acid ・ K-2: N- [3- (triethoxysilyl) propyl] maleamic acid ・ K-3: 3-methacryloxypropyltrimethoxy Silane K-4: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane K-5: A compound having a structure represented by the following formula (K-5). In formula (K-5), R represents an ethyl group.

[Other additives]
L-1: A compound represented by the following formula (L-1)

[PH regulator]
-M-1: N-Phenyldiethanolamine-M-2: CyDTA (trans-1,2 cyclohexanediaminetetraacetic acid)

[Thermal base generator]
N-1 to N-3: Compounds having a structure represented by the following formulas (N-1) to (N-3).

〔solvent〕
-S-1: N-methylpyrrolidone-S-2: Ethyl lactate-S-3: γ-Butyrolactone-S-4: Dimethyl sulfoxide-S-5: Cyclopentanone

<Evaluation>
[Corrosion suppression (void of copper-resin interface after high temperature and high humidity retention) evaluation]
In each Example and Comparative Example, each curable resin composition or each comparative composition was applied (coated) in layers on a copper substrate by a spin coating method to form a curable resin composition layer. ..
In each Example and Comparative Example, the copper substrate to which the obtained composition layer was applied was dried on a hot plate at 100 ° C. for 4 minutes to form a curable resin composition layer having a thickness of 20 μm on the copper substrate. ..
In the example in which "i" is described in the "exposure condition" column of "corrosion suppression" in Tables 2 to 8, the curable resin composition layer on the m-copper substrate is formed by i-line (wavelength of about 365 nm). With an exposure energy of 400 mJ / cm ² , exposure was performed using a photomask having a 100 μm square non-masked portion, and further, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere. After reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
In the example in which "h" is described in the "exposure condition" column of "corrosion suppression" in Tables 2 to 8, the curable resin composition layer on the m-copper substrate is formed by h-line (wavelength of about 405 nm). With an exposure energy of 400 mJ / cm ² , exposure was performed using a photomask having a 100 μm square non-masked portion, and further, the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere. After reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
In the example in which "b" is described in the "exposure condition" column of "corrosion suppression" in Tables 2 to 8, the curable resin composition layer on the m copper substrate is subjected to broadband light (high pressure mercury lamp). , 400 mJ / cm ² exposure energy using a photomask having a 100 μm square non-masked portion, and further, under a nitrogen atmosphere, the temperature was raised at a heating rate of 10 ° C./min to 230. After reaching the temperature, the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.
In Tables 2 to 8, in the example in which "-" is described in the "Exposure condition" column of "Corrosion suppression", the curable resin composition layer on the copper substrate is not exposed and is placed in a nitrogen atmosphere. The temperature was raised at a heating rate of 10 ° C./min, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to obtain a copper substrate on which a cured film was formed.

The copper substrate on which the cured film was formed was heated in a constant temperature bath (ESPEC STH-120) for 500 hours in air at 150 ° C. and 90% relative humidity.
Subsequently, the laminated body portion of the copper layer (copper substrate) and the cured film on the substrate was cut, and the cross section was further surface-treated with an ion milling apparatus (ArBlade5000, manufactured by Hitachi High-Technologies Corporation).
The cross section of the laminated body of the obtained copper layer (Cu layer) and the cured film was observed from the side by FE-SEM (S-4800 type, manufactured by Hitachi High-Technologies Corporation), and the area ratio of voids to the surface of the Cu layer was observed. Was calculated. That is, the void portion of the SEM image and the Cu layer portion were visually separated. The area ratio of the voids was calculated by dividing the area of the void portion by the area of the entire Cu layer.
From the above area ratio, evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the column of "corrosion suppression" in Tables 2 to 8. It can be said that the smaller the area ratio of the voids, the more the metal corrosion is suppressed.

-Evaluation criteria-
A: The area ratio was 5% or less.
B: The area ratio was more than 5% and less than 15%.
C: The area ratio exceeded 15%.

[Evaluation of liquid storage stability]
-Measurement of pre-aging film thickness-
In each Example and Comparative Example, a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 μm on the silicon wafer. The film thickness of the curable resin composition layer on the silicon wafer was measured, and this value was taken as the pre-aging film thickness. The film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill).

-Measurement of film thickness after aging-
In each Example and Comparative Example, the curable resin composition or the comparative composition was placed in a glass container, sealed, and allowed to stand in a light-shielded environment at 25 ° C. for 14 days, and then the pre-aging film thickness was determined. A curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method at the same number of revolutions as in the case of the above to form a curable resin composition layer. The silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness on the silicon wafer. The film thickness of the obtained curable resin composition layer was measured by the same method as the film thickness measuring method in the above-mentioned pre-aging film thickness measuring method, and this value was taken as the post-aging film thickness.

-Film thickness change rate-
The film thickness change rate was calculated by the following formula.
Film thickness change rate (%) = | Pre-aging film thickness-Post-aging film thickness | / Pre-aging film thickness x 100
The calculated film thickness change rate was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Storage stability evaluation" column of Tables 2 to 8. It can be said that the smaller the rate of change in film thickness, the better the storage stability of the curable resin composition.

-Evaluation criteria-
A: The rate of change in film thickness was less than 10%.
B: The rate of change in film thickness was 10% or more and less than 15%.
C: The film thickness change rate was 15% or more.

From the above results, a composition containing at least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof, a compound having a triazole structure, and a solvent according to the present invention. According to the curable resin composition having a pH of less than 7.0, it can be seen that a cured film having excellent suppression of corrosion of adjacent metals can be obtained.
The comparative compositions according to Comparative Examples 1 and 2 contain a compound having a triazole structure, and have a pH of 7.0 or higher. It can be seen that the comparative compositions according to Comparative Examples 1 and 2 are inferior in suppressing corrosion of the metal adjacent to the cured film and in liquid storage stability.
The comparative compositions according to Comparative Examples 3 to 4 do not contain a compound having a triazole structure and have a pH of 7.0 or higher. It can be seen that the comparative compositions according to Comparative Examples 1 and 2 are inferior in suppressing corrosion of the metal adjacent to the cured film and in liquid storage stability.
The comparative composition according to Comparative Example 5 has a pH of less than 7.0, but does not contain a compound having a triazole structure. It can be seen that the comparative composition according to Comparative Example 5 is inferior in suppressing corrosion of the metal adjacent to the cured film.

<Example 101>
The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 5 minutes. After forming a curable resin composition layer having a thickness of 20 μm, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was performed by irradiating light having a wavelength of 365 nm through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 μm). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
Then, it was heated at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. The interlayer insulating film for the rewiring layer was excellent in insulating property.
Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Claims

At least one resin selected from the group consisting of polyimide, polybenzoxazole, and precursors thereof.
Compounds having a triazole structure, as well as
Contains solvent,
A curable resin composition in which the pH of the composition is less than 7.0.
The curable resin composition according to claim 1, wherein the pKa in dimethyl sulfoxide of the compound having a triazole structure is less than 15.
The curable resin composition according to claim 1 or 2, wherein the compound having a triazole structure contains a compound having a 1,2,3-triazole structure.
The curable resin composition according to any one of claims 1 to 3, wherein the compound having a triazole structure contains a compound having a benzotriazole structure.
Any of claims 1 to 4, which comprises 1 to 40 parts by mass of a photosensitizer, 0.05 to 20 parts by mass of the compound having a triazole structure, and 50 to 300 parts by mass of the solvent with respect to 100 parts by mass of the resin. The curable resin composition according to item 1.
The curable resin composition according to any one of claims 1 to 5, which contains a solvent containing no nitrogen atom as the solvent.
The curable resin composition according to any one of claims 1 to 6, wherein the solvent contains a solvent composed of only carbon atoms, oxygen atoms and hydrogen atoms.
The curable resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer.
A cured film obtained by curing the curable resin composition according to any one of claims 1 to 8.
A laminate containing two or more layers of the cured film according to claim 9 and containing a metal layer between any of the cured films.
A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of claims 1 to 8 to a substrate to form a film.
The method for producing a cured film according to claim 11, further comprising an exposure step of exposing the film and a developing step of developing the film.
The method for producing a cured film according to claim 11 or 12, which comprises a heating step of heating the film at 50 to 450 ° C.
A semiconductor device comprising the cured film according to claim 9 or the laminate according to claim 10.