WO2019107394A1

WO2019107394A1 - Compounds having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element

Info

Publication number: WO2019107394A1
Application number: PCT/JP2018/043725
Authority: WO
Inventors: 章博高田
Original assignee: Jnc株式会社; Jnc石油化学株式会社
Priority date: 2017-11-30
Filing date: 2018-11-28
Publication date: 2019-06-06
Also published as: TW201925435A; JP2021028299A

Abstract

The present invention addresses the problem of providing a liquid crystal compound that satisfies at least one physical property including a low minimum temperature for the liquid crystal phase, a low viscosity, a suitable optical anisotropy, a large negative dielectric constant anisotropy, and an excellent compatibility with other liquid crystal compounds at room temperature and low temperatures; a liquid crystal composition containing this compound; and a liquid crystal display element containing this composition. The problem is addressed by, for example, a compound represented by formula (1). Herein, for example, R1 and R2 are hydrogen, alkyl having 1 to 10 carbons, or alkoxy having 2 to 9 carbons; rings A1 and A2 are cycloalkylene having 3 to 5 carbons; Y1 and Y2 are, e.g., hydrogen or fluorine; Z1, Z2, Z3, and Z4 are, e.g., a single bond or alkylene having 1 to 6 carbons; rings N1 and N2 are, e.g., 1,4-cyclohexylene or 1,4-phenylene; a and d are 0 or 1 and 1 ≤ a + d ≤ 2; and b and c are 0, 1, or 2.

Description

Compound having dibenzothiophene ring, liquid crystal composition and liquid crystal display device

The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display device. More specifically, the present invention relates to a liquid crystal compound having a negative dielectric constant anisotropy having a dibenzothiophene ring, a liquid crystal composition containing the same, and a liquid crystal display device including the composition.

In liquid crystal display devices, classification based on the operation mode of liquid crystal molecules is as follows: phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), IPS These modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving system of elements is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc.

A liquid crystal composition is enclosed in this element. The physical properties of this composition relate to the characteristics of the device. Examples of physical properties of the composition include stability against heat and light, temperature range of nematic phase, viscosity, optical anisotropy, dielectric anisotropy, specific resistance, elastic constant and the like. The composition is prepared by mixing many liquid crystal compounds. Physical properties necessary for the compound include high stability to environment such as water, air, heat, light, etc., wide temperature range of liquid crystal phase, small viscosity, appropriate optical anisotropy, large dielectric anisotropy, appropriate elastic constant And good compatibility with other liquid crystal compounds at room temperature and low temperature. Compounds having a high upper limit temperature of the nematic phase are preferred. Compounds having a lower limit temperature in liquid crystal phase such as nematic phase, smectic phase and the like are preferred. Compounds with low viscosity contribute to the short response time of the device. The appropriate value of the optical anisotropy depends on the mode of the element. Compounds having large positive or negative dielectric anisotropy are preferred to drive the device at low voltage. Compounds having good compatibility with other liquid crystal compounds are preferred for preparing the composition. Compounds that have good compatibility at low temperatures are preferred, as the devices may be used at temperatures below freezing.

Heretofore, many liquid crystal compounds having large dielectric anisotropy have been synthesized. Development of new liquid crystalline compounds is still continued. This is because the novel compounds are expected to have good physical properties which are not present in conventional compounds. Also, the novel compound may provide an appropriate balance between at least two physical properties in the composition.

The following compounds (S-1) are disclosed in Table 1-1 of paragraph [0095] of Patent Document 2 (Japanese Patent Application Laid-Open No. 2015-205879). This compound has large dielectric anisotropy and large optical anisotropy, but the compatibility at low temperature is not sufficient.

Japanese Patent Publication No. 2004-529867 JP, 2015-205879, A

The first problems are high stability against heat and light, high clearing point (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, negative large dielectric constant difference It is an object of the present invention to provide a liquid crystal compound which satisfies at least one of physical properties such as linearity, an appropriate elastic constant, and good compatibility with other liquid crystal compounds at room temperature and low temperature. It is to provide a compound having large dielectric anisotropy as compared with similar compounds and further having good compatibility with other liquid crystal compounds at a low temperature.
The second problem is that the compound contains this compound and has high stability against heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, negative large dielectric constant difference It is an object of the present invention to provide a liquid crystal composition satisfying at least one of physical properties such as anisotropy, large specific resistance, and a suitable elastic constant. An object of the present invention is to provide a liquid crystal composition having an appropriate balance with respect to at least two physical properties.
The third problem is a liquid crystal display containing this composition and having a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long lifetime. It is providing a device.

The present invention relates to a compound represented by the formula (1), a liquid crystal composition containing the compound, and a liquid crystal display device containing the composition.

In equation (1),
R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbons, and in this alkyl, at least one —CH ₂ — is —O—, —S—, —CO— or —SiH _2- and at least one -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine May be replaced;
Rings A ¹ and A ² are independently cycloalkylene having 3 to 5 carbon atoms, and in this cycloalkylene, at least one —CH ₂ — may be replaced by —O—, at least one — CH ₂ CH ₂ -may be replaced by -CH = CH-;
Rings N ¹ and N ² are independently 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl or 1,4-phenylene, and in these groups, at least one —CH ₂ — is And -O-, -S-, -CO-, or -SiH _2- , and at least one -CH ₂ CH ₂ -is replaced by -CH = CH- or -CH = N- In these divalent groups, at least one hydrogen may be fluorine, chlorine, -C≡N, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , or -OCH May be replaced by ₂ F;
Y ¹ and Y ² are independently hydrogen, fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ or -OCH ₂ F;
a and d are independently 0 or 1, and 1 ≦ a + d ≦ 2,
b and c are independently 0, 1 or 2, and b + c ≦ 2;
Z ¹ , Z ² , Z ³ and Z ⁴ are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —S—, Or —CO— and one or two of —CH ₂ CH ₂ — may be replaced by —CH = CH— or —C≡C—, and in these divalent groups, at least One hydrogen may be replaced by fluorine.

The first advantage is high stability to heat and light, high clearing point (or high upper limit temperature of nematic phase), lower lower limit temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, negative large dielectric constant difference It is an object of the present invention to provide a liquid crystal compound which satisfies at least one of physical properties such as linearity, an appropriate elastic constant, and good compatibility with other liquid crystal compounds. It is to provide a compound having good compatibility with other liquid crystal compounds at a low temperature as compared with similar compounds (Comparative Example 1).
The second advantage is that it contains this compound and has high stability to heat and light, high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, negative large dielectric constant difference It is an object of the present invention to provide a liquid crystal composition satisfying at least one of physical properties such as anisotropy, large specific resistance, and a suitable elastic constant. An advantage of this is to provide a liquid crystal composition having an appropriate balance regarding at least two physical properties.
The third advantage is a liquid crystal display containing this composition and having a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker rate, and a long lifetime. It is providing a device.

Hereinafter, embodiments of the present invention will be described in detail. The following embodiments are examples (representative examples) of the embodiments of the present invention, and the present invention is not limited thereto. In addition, the present invention can be implemented with arbitrary modifications without departing from the scope of the invention.

The usage of the terms in this specification is as follows. The terms "liquid crystal compound", "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "compound", "composition" and "element", respectively. "Liquid crystalline compound" is a compound having a liquid crystal phase such as a nematic phase or smectic phase, and has no liquid crystal phase, but controls physical properties of the composition such as upper limit temperature, lower limit temperature, viscosity, dielectric anisotropy Is a generic term for compounds added for the purpose of The molecular structure of this compound is rod-like. "Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The "polymerizable compound" is a compound to be added for the purpose of forming a polymer in the composition. Liquid crystalline compounds having an alkenyl are not polymerizable in that sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives are added to the composition for the purpose of further adjusting physical properties. Additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents are added as necessary. Ru. Liquid crystal compounds and additives are mixed in such a procedure.

The proportion (content) of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not including the additive, even when the additive is added. The proportion (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition without the additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total weight of the liquid crystal compound. Parts per million by weight (ppm) may be used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the weight of the polymerizable compound.

The “clearing point” is the transition temperature of the liquid crystal phase to the isotropic phase in the liquid crystal compound. The “lower limit temperature of the liquid crystal phase” is the transition temperature of the solid phase—liquid crystal phase (smectic phase, nematic phase, etc.) in the liquid crystal compound. The “upper limit temperature of the nematic phase” is a transition temperature of the nematic phase-isotropic phase in the mixture of the liquid crystal compound and the base liquid crystal or the liquid crystal composition, and may be abbreviated as the “upper limit temperature”. The “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”. The expression "increase the dielectric anisotropy" means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively. The "high voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and after a long period of use it shows a large voltage not only at room temperature but also at a temperature close to the upper limit. It means having a retention rate. The characteristics of the composition or element may be examined before and after the aging test (including the accelerated aging test).

The compound represented by Formula (1) may be abbreviated as a compound (1). At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as compound (1). "Compound (1)" means one compound represented by Formula (1), a mixture of two compounds, or a mixture of three or more compounds. These rules also apply to compounds represented by other formulas.
Further, in the ring A ¹ and A ² in the formula (1), adjacent R ¹ , R ² , Z ¹ and Z ⁴ may be bonded to any carbon atom constituting the ring of A ¹ and A ² Good. Also, in the formulas (1) to (13) and the formulas (21) to (24) and sub formulas thereof, symbols such as A ¹ , B ¹ and C ¹ surrounded by a circle or a hexagon are ring A ¹ , respectively It corresponds to a ring such as ring B ¹ and ring C ¹ . The hexagon represents a six-membered ring such as cyclohexane or benzene. A hexagon may represent a fused ring such as naphthalene or a bridged ring such as adamantane.
In addition, although only the structure having only the ring of A ¹ (in the case of d = 0) among the above A ¹ and A ^{2 is} shown in the formulas except for the formula (1), the ring of A ² is introduced into these structures The structure (in the case of d = 1) is also included in the liquid crystal compound. In addition, the aspect which is a = 1 and d = 0 can be mentioned preferably.

In the chemical formulas of component compounds, the symbol of terminal group R ¹¹ was used for a plurality of compounds. In these compounds, two groups represented by any two R ¹¹ may be identical or different. For example, there is a case where R ^{11 of} compound (2) is ethyl and R ¹¹ of compound (3) is ethyl. In some cases, R ^{11 of} compound (2) is ethyl and R ¹¹ of compound (3) is propyl. The same ^rule applies to the symbols, such as ^{^{R 12, R 13, Z 11}} , Z 12. In compound (24), when i is 2, two rings E ¹ are present. Two groups represented by two rings E ¹ in this compound may be the same or different. When i is greater than 2, it also applies to any two rings E ¹ . This rule also applies to other symbols.

The expression "at least one 'A'" means that the number of 'A' is arbitrary. In the expression “at least one 'A' may be replaced by 'B'”, when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Also in the case of three or more, it means that those positions can be selected without limitation. This rule also applies to the expression "at least one 'A' has been replaced by 'B'". The expression “at least one 'A' may be replaced by 'B', 'C', or 'D'” is optional when any 'A' is replaced by 'B'. If A 'is replaced by' C ', and any' A 'is replaced by' D ', then more' A 'may be' B ',' C ', and / or' D ' It is meant to include the case where at least two are replaced. For example, "alkyl at least one of -CH ₂ -may be replaced by -O- or -CH = CH-" includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkoxyalkenyl, alkenyloxy, alkenyloxyalkyl Is included. In addition, it is not preferable that two successive -CH ₂ -be replaced by -O- to be -O-O-. In alkyl and the like, it is also not preferable that —CH ₂ — of the methyl moiety (—CH ₂ —H) is replaced by —O— to form —O—H.

“R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl and alkenyl, at least one —CH ₂ — is replaced by —O— In these groups, at least one hydrogen may be replaced by fluorine ". In this expression, "in these groups" may be interpreted literally. In this expression, "these groups" mean alkyl, alkenyl, alkoxy, alkenyloxy and the like. That is, "these groups" represent all of the groups described earlier than the term "in these groups". This common sense interpretation applies to the terms "in these monovalent groups" and "in these divalent groups". For example, "these monovalent groups" represent all of the groups listed before the term "in these monovalent groups".

Halogen means fluorine, chlorine, bromine and iodine. Preferred halogens are fluorine and chlorine. A further preferred halogen is fluorine. The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyls are generally preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. 2-fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric bivalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl.

The present invention includes the following items.

Item 1.
The compound represented by Formula (1).

The following items 2 to 7 are shown as preferable embodiments of the above compound (1).

Item 2.
In equation (1),
R ¹ and R ² independently represent hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, or From 9 alkenyloxy;
Rings N ¹ and N ² are independently 1,4-cyclohexylene or 1,4-phenylene, and in these groups, at least one —CH ₂ — may be replaced by —O— At least one —CH ₂ CH ₂ — may be replaced by —CH = CH—, and in these divalent groups, at least one hydrogen may be replaced by fluorine;
Y ¹ and Y ² are independently hydrogen or fluorine;
b and c are independently 0 or 1, and b + c ≦ 1;
And Z ¹ , Z ² , Z ³ and Z ⁴ independently represent a single bond or alkylene having 1 to 6 carbon atoms, and at least one —CH ₂ — may be replaced by —O— The compound as described in.

Item 3.
Item 4. The compound according to item 1, represented by formulas (1-1) to (1-3).

In formulas (1-1) to (1-3),
R ¹ and R ² independently represent hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, or 9 alkenyloxy;
Ring A ¹ is 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentylene in which one —CH ₂ — is replaced by —O— And
Ring N ¹ and ring N ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by halogen, Or tetrahydropyran-2,5-diyl;
Z ¹ , Z ² and Z ³ are independently a single bond or alkylene having 1 to 6 carbon atoms, and at least one —CH ₂ — may be replaced by —O—.

Item 4.
In formulas (1-1) to (1-3),
The compound according to Item 3, wherein ring A ¹ is 1,2-cyclopropylene, 1,3-cyclobutylene or 1,3-cyclopentylene, and Z ² and Z ³ are a single bond.

Item 5.
Item 4. The compound according to item 1, represented by any one of formulas (1-4) to (1-45).

In formulas (1-4) to (1-45),
R ¹ and R ² independently represent hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, or L ¹ and L ² are independently hydrogen or fluorine.

Item 6.
In formulas (1-4) to (1-45),
The compound according to item 5, wherein R ¹ is hydrogen and R ² is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyl having 2 to 10 carbons.

Item 7.
Item 6. The compound according to item 1, represented by formulas (1-46) to (1-51):

In formulas (1-46) to (1-51), R ² is alkoxy having 1 to 9 carbons.

Item 8.
Item 8. A liquid crystal composition containing at least one compound according to any one of Items 1 to 7.

Item 9.
Item 9. The liquid crystal composition according to item 8, further containing at least one compound selected from the group of compounds represented by formulas (2) to (4).

In equations (2) to (4),
R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — is replaced by —O— Also, in these groups, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , ring B ² , ring B ³ and ring B ⁴ are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
Z ¹¹ , Z ¹² and Z ¹³ are independently a single bond, -COO-, -CH ₂ CH _2- , -CH = CH-, or -C≡C-.

Item 10.
Item 10. The liquid crystal composition according to item 8 or 9, further containing at least one compound selected from the group of compounds represented by formulas (5) to (13).

In equations (5) to (13),
R ¹³ , R ¹⁴ and R ¹⁵ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — is —O— Optionally substituted, in these groups at least one hydrogen may be replaced by fluorine and R ¹⁵ may be hydrogen or fluorine;
Ring C ¹ , ring C ² , ring C ³ and ring C ⁴ are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, or at least one hydrogen optionally substituted by fluorine 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring C ⁵ and ring C ⁶ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6 -Is diil;
^{^{^{Z 14, Z 15, Z 16}}} , and ^{Z 17} are independently a single _{bond, -COO -, - CH 2 O} -, - OCF 2 -, - CH 2 CH 2 -, or -OCF _{_₂} CH ₂ CH ₂ -Is;
L ¹¹ and L ¹² are independently fluorine or chlorine;
S ¹¹ is hydrogen or methyl;
X is -CHF- or -CF _2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2 or 3 and t is 1, 2 or 3.

Item 11.
11. The liquid crystal composition according to any one of items 8 to 10, further containing at least one compound selected from the group of compounds represented by formulas (21) to (23).

In equations (21) to (23),
R ¹⁶ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and these groups In which at least one hydrogen may be replaced by fluorine;
X ¹¹ is fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ , -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ ;
Ring D ¹ , ring D ² and ring D ³ are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z ^18, ^{Z 19,} and ^{Z 20} are independently a single _{_{bond, -COO -, - CH 2 O}} -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CH = CH- , -C≡C-, or - _(CH _{2) 4} - a and;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine.

Item 12.
Item 12. The liquid crystal composition according to any one of items 8 to 11, further containing at least one compound selected from the group of compounds represented by formula (24).

In equation (24),
R ¹⁷ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, and these groups In which at least one hydrogen may be replaced by fluorine;
X ¹² is -C≡N or -C≡C-C≡N;
Ring E ¹ is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl;
Z ²¹ represents a single bond, -COO-, -CH ₂ O-, -CF ₂ O-, -OCF _2- , -CH ₂ CH _2- , or -C≡C-;
L ¹⁵ and L ¹⁶ are independently hydrogen or fluorine;
i is 1, 2, 3 or 4;

Item 13.
Item 13. A liquid crystal display device comprising the liquid crystal composition according to any one of items 8 to 12.

The present invention also includes the following items.
Item (a). A composition as described above, further comprising at least one optically active compound and / or polymerizable compound.
Item (b). A composition as described above which additionally comprises at least one antioxidant and / or UV absorber.

The present invention also includes the following items.
Item (c). One or two selected from the group of polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, ultraviolet light absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents Or a composition as described above which additionally contains at least three additives.
Item (d). The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (measured at 25 ° C.) at a wavelength of 589 nm is 0.08 or more, and the dielectric anisotropy (measured at 25 ° C.) at a frequency of 1 kHz is − The above composition, which is 2 or less.

The present invention also includes the following items.
Item (e). A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, FPA, or PSA.
Item (f). An AM device comprising the above composition.
Item (g). A transmission type element comprising the above composition.
Item (h). Use of the above composition as a composition having a nematic phase.
Item (i). Use as an optically active composition by adding an optically active compound to the above composition.

The aspect of compound (1), the synthesis of compound (1), the liquid crystal composition, and the liquid crystal display device will be described in order.

1. Embodiments of Compound (1) The compound (1) of the present invention has a dibenzothiophene ring and a three-membered ring, a four-membered ring or a five-membered ring structure.
This compound is extremely physically and chemically stable under the conditions in which the device is usually used, has a large dielectric anisotropy, and has good compatibility with other liquid crystal compounds. The composition containing this compound is stable under the conditions in which the device is usually used. When the composition is stored at low temperature, the compound is less likely to precipitate as a crystal (or smectic phase). This compound has the general physical properties necessary for the components of the composition, the appropriate optical anisotropy, and the appropriate dielectric anisotropy.

The compound (1) has a dibenzothiophene ring, and has advantages such as a high upper limit temperature and a low viscosity, as compared with a compound having a dibenzofuran ring in which the sulfur of the dibenzothiophene ring is oxygenated.

The terminal group R ¹ and R ² in the compound (1), the ring A ¹ and A ² , the ring N ¹ and N ² , the linking group Z ¹ , Z ² , Z ³ and Z ⁴ , and the lateral groups Y ¹ and Y ² Preferred examples are as follows. This example also applies to the subformula of compound (1).
In the compound (1), physical properties can be arbitrarily adjusted by appropriately combining these groups. Compound (1) may contain isotopes such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance ratio, because there is no large difference in the physical properties of the compounds. In addition, the definition of the symbol of compound (1) is as having described in the item 1.

In formula (1), R ¹ and R ² are independently hydrogen or alkyl having 1 to 10 carbon atoms, and in this alkyl, at least one —CH ₂ — is —O—, —S—, — CO— or —SiH ₂ — may be replaced, and at least one —CH ₂ CH ₂ — may be replaced by —CH = CH— or —C≡C—, and in these groups at least One hydrogen may be replaced by fluorine.

Preferred R ¹ or R ² is independently hydrogen, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, acyl, acylalkyl, acyloxy, acyloxyalkyl, alkoxycarbonyl, alkoxycarbonylalkyl, alkenyl, alkenyloxy, Alkenyloxyalkyl, alkoxyalkenyl, alkynyl, alkynyloxy, silalalkyl, and dicyralalkyl. In these groups, at least one hydrogen may be replaced by fluorine or chlorine.
This example includes groups in which at least two hydrogens have been replaced by both fluorine and chlorine. Groups in which at least one hydrogen is replaced only by fluorine are more preferred. In these groups, straight chain is preferable to branched chain. Even when R ¹ or R ² is a branched chain, it is preferable when it is optically active. More preferred R ¹ or R ² is hydrogen, alkyl, alkoxy, alkoxyalkyl, alkenyl, alkenyloxy, monofluoroalkyl and monofluoroalkoxy.

The preferred configuration of —CH = CH— in alkenyl depends on the position of the double bond. The trans configuration is preferred in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl. The cis configuration is preferred in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

Specific R ¹ or R ² is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, methoxymethyl , Methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, butoxymethyl, pentoxymethyl, vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1- Pentanyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy, 2-pentenyloxy, 1-propynyl, and 1-pentenyl.

Preferred R ¹ or R ² is independently hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, methoxymethyl, ethoxymethyl, propoxymethyl, vinyl, 1-propenyl 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-propenyloxy, 2-butenyloxy and 2-pentenyloxy. Most preferred R ¹ is hydrogen and most preferred R ² is methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy.

In Formula (1), rings A ¹ and A ² are independently cycloalkylene having 3 to 5 carbon atoms, and in this cycloalkylene, at least one —CH ₂ — is replaced by —O— Well, at least one -CH ₂ CH ₂ -may be replaced by -CH = CH-.

Preferred rings A ¹ and A ² are independently 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3-cyclopentenylene, 1,4-cyclopentenyl Lene is 3,5-cyclopentenylene, 2,4-tetrahydronyl or 2,5-tetrahydrofuranyl. Particularly preferred rings A ¹ and A ² are 1,3-cyclopentylene.

a and d are independently 0 and 1 and 1 ≦ a + d ≦ 2.
An embodiment in which a = 1 and d = 0 can be preferably mentioned.

In general, a compound having a large absolute value of dielectric anisotropy, that is, a compound having a large polarity tends to deteriorate the low temperature compatibility. However, compounds having rings A ¹ and A ² , which are cycloalkylene having 3 to 5 carbon atoms, have dielectric anisotropy similar to this and are compared with compounds having no such cycloalkylene, It shows good compatibility with other liquid crystal compounds at low temperatures.

In the formula (1), the rings N ¹ and N ² are independently 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl or 1,4-phenylene, and at least one of these groups is And one —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —, and at least one —CH ₂ CH ₂ — is —CHCHCH— or —CH = it may be replaced by N-, in these divalent groups, at least one of hydrogen, fluorine, _{_{_{chlorine, -C≡N, -CF 3, -CHF 2}}} , -CH 2 F, -OCF 3, - It may be replaced by OCHF ₂ or -OCH ₂ F.

“In these groups, at least one —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —, and at least one —CH ₂ CH ₂ — is Preferred examples of “—CHCHCH— or —CH = N—” are bivalent groups represented by the following formulas (25-1) to (25-50). Further preferable examples are formulas (25-1) to (25-4), formulas (25-15), formulas (25-23), formulas (25-27) to (25-29) and formulas (25-36). And a divalent group represented by Formula (25-39) and Formula (25-45).

"In these divalent groups, at least one hydrogen is fluorine, chlorine, -C≡N, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ or -OCH ₂ F Preferred examples of “which may be substituted” are divalent groups represented by the following formulas (26-1) to (26-71). Further preferred examples are formulas (26-1) to (26-4), formulas (26-6), formulas (26-10) to (26-15), and formulas (26-54) to (26-59). It is a bivalent group represented by).

Further preferred rings N ¹ and N ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro- 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro -1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-2,5-diyl, decahydronaphthalene-2,6- Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, and naphthalene-2,6-diyl. The configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl is preferably trans rather than cis.

Particularly preferred rings N ¹ and N ² are independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2, 3-Difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyridine-2,5-diyl, and pyrimidine-2,5-diyl It is. Most preferred ring N ¹ and ring N ² are 1,4-cyclohexylene and 1,4-phenylene.

In formula (1), Z ¹ , Z ² , Z ³ and Z ⁴ are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O -, -S-, or -CO-, and one or two of -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-; In divalent radicals, at least one hydrogen may be replaced by fluorine.

Specific examples of Z ¹ , Z ² , Z ³ and Z ⁴ are independently a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF _{_{_{_{2 O -, - OCF 2 -}}}} , - CH 2 -, - CH 2 CH 2 -, - CH = CH -, - CF = CH -, - CH = CF -, - CF = CF -, - C≡C- , -CH ₂ CO-, -COCH ₂ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₂ COO-,-(CH ₂ ) ₂ OCO-, -OCO (CH ₂ ) _2- , -COO ( _{_{_{_{CH 2) 2 -, - (}}}} CH 2) 2 CF 2 O -, - (CH 2) 2 OCF 2 -, - OCF 2 (CH 2) 2 -, - CF 2 O (CH 2) 2 -, - ( CH ₂ ) ₃ O- or -O (CH ₂ ) _3- . The configuration of double bonds of linking groups such as -CH = CH-, -CF = CF-, -CH = CH-CH ₂ O-, and -OCH ₂ -CH = CH- is more trans than cis than cis preferable.

Preferred Z ¹ , Z ² , Z ³ and Z ⁴ are independently a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-,- _{_{_{_{OCF 2 -, - CH 2 -}}}} , - CH 2 CH 2 -, - CH = CH -, - CF = CF -, - C≡C-, and - _(CH _{2) 4} - a. More preferably ^{Z 1} and ^{Z 4} are each independently a single _{bond, -O -, - CH 2 O} -, - CH 2 -, and _-CH 2 CH ₂ -. Most preferred Z ¹ and Z ⁴ are independently -O- and -CH ₂ O-, and most preferred Z ² and Z ³ are independently single bond, -CH ₂ O- and -OCH _2- is there.

Y ¹ and Y ² are independently hydrogen, fluorine, chlorine, -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₃ , -OCHF ₂ or -OCH ₂ F. Preferred Y ¹ and Y ² are independently hydrogen or fluorine. Particularly preferred Y ¹ and Y ² are fluorine.

In formula (1), b and c are independently 0, 1 or 2, and b + c is 0, 1 or 2. The compound (1) has one to three rings in total, excluding rings A ¹ and A ² which are three-, four-, or five-membered rings. Ring types include, in addition to ordinary six-membered rings, fused rings and bridged six-membered rings, and fused rings are counted as part. When the compound (1) is a part, the compatibility with other liquid crystal compounds is very good. When the compound (1) has one or two rings, the viscosity is small. When the compound (1) has two or three rings, the upper limit temperature is high.

Physical properties such as optical anisotropy and dielectric anisotropy can be arbitrarily adjusted by appropriately selecting the terminal group, ring and linking group of compound (1). Types of terminal groups R ¹ and R ² , rings A ¹ and A ² , rings N ¹ and N ² , side groups Y ¹ and Y ² , linking groups Z ¹ , Z ² , Z ³ and Z ⁴ are compounds ( The effects on the physical properties of 1) are described below.

In the compound (1), when R ¹ or R ² is linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R ¹ or R ² is a branched chain, the compatibility with other liquid crystal compounds is good. Compounds in which R ¹ or R ² is an optically active group are useful as chiral dopants. By adding this compound to the composition, it is possible to prevent the reverse twist domain generated in the device. Compounds in which R ¹ or R ² is not an optically active group are useful as components of the composition. When R ¹ or R ² is alkenyl, the preferred configuration depends on the position of the double bond. An alkenyl compound having a preferred configuration has a high upper temperature limit or a wide temperature range of liquid crystal phase. A detailed description is given in Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327.

When the rings A ¹ and A ² are independently 1,2-cyclopropylene, 1,3-cyclobutylene or 1,3-cyclopentylene, the viscosity is small.

1,4-phenylene in which rings N ¹ and N ² may be independently substituted with at least one hydrogen with fluorine or chlorine, pyridine-2,5-diyl, pyrimidine-2,5-diyl, or pyridazine- When it is 3,6-diyl, the optical anisotropy is large. When the rings N ¹ and N ² are 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3-dioxane-2,5-diyl, the optical anisotropy is small.

Binding groups ^Z ^1, Z 2, ^{Z 3} and ^{Z 4} are independently a single _{_{_{bond, -CH 2 O -, - CF}}} 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CH = CH- The viscosity is small when —CF = CF— or — (CH ₂ ) ₄ —. When the linking group is a single bond, -OCF _2- , -CF ₂ O-, -CH ₂ CH _2- , or -CH = CH-, the viscosity is smaller. When the bonding group is —O— or —CH ₂ O—, the dielectric anisotropy is large.

When the side groups Y ¹ and Y ² are F, the compound (1) has a large dielectric anisotropy.

The viscosity is small when compound (1) has ^one or two rings as counted excluding rings A ¹ and A ² . The upper limit temperature is high when the compound (1) is counted excluding rings A ¹ and A ² and has a bicyclic or tricyclic ring. As described above, compounds having necessary physical properties can be obtained by appropriately selecting the types of terminal groups, rings, lateral groups, and linking groups. Therefore, the compound (1) is useful as a component of a composition used for a device having a mode such as PC, TN, STN, ECB, OCB, IPS, VA and the like.

Preferred examples of the compound (1) include the compounds (1-1) to (1-3) described in Item 3, and the compound (1-1) is particularly preferable. Further preferable examples are the compounds represented by the subformulae in Item 4 and the like.
The compound (1) is also suitable for devices having modes such as VA, IPS and PSA.

2. Synthesis of Compound (1) Hereinafter, a synthesis method of compound (1) will be described. The following synthetic methods are examples (representative examples) of the embodiments of the present invention, and the present invention is not limited thereto. Compound (1) can be synthesized by appropriately combining the methods of synthetic organic chemistry. Methods to introduce the required end groups, rings and linking groups into the starting material are “Organic Synthesis” (Organic Syntheses, John Wiley & Sons, Inc.), “Organic Reactions” (Organic Reactions, John Wiley & Sons) , Inc.), “Comprehensive Organic Synthesis” (Pergamon Press), “New Experimental Chemistry Course” (Maruzen), etc.

2-1. On how to generate bonding groups ^Z ^1, Z 2, ^{Z 3} and generate bonding groups ^Z 1 to ^{^Z ^4, Z} ^2, ^Z ³ and ^{Z 4,} illustrating a first scheme.
Next, the reactions described in the schemes in methods (1) to (11) will be described. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having one of a three-, four-, five-, six-membered or fused ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ² ) used in the scheme may be identical or different. Compounds (1A) to (1J) correspond to compound (1).

(1) Formation of a single bond The aryl boric acid (31) and the halide (32) synthesized by a known method are reacted in the presence of a carbonate and a catalyst such as tetrakis (triphenylphosphine) palladium, Compound (1A) is synthesized. This compound (1A) is obtained by reacting n-butyllithium and then zinc chloride with a halide (33) synthesized by a known method, and halogen in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. It is also synthesized by reacting the compound (32).

(2) Formation of -COO- The halide (33) is reacted with n-butyllithium and then carbon dioxide to obtain a carboxylic acid (34). Compound (35) and carboxylic acid (34) synthesized by a known method are dehydrated in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to give compound (1B) Synthesize.

(3) Formation of —CF ₂ O— Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to give thiono ester (36). The thionoester (36) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C). See M. Kuroboshi et al., Chem. Lett., 1992, 827. The compound (1C) can also be synthesized by fluorinating the thionoester (36) with DAST ((diethylamino) sulfur trifluoride). See W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. It is also possible to generate this linking group by the method described in Peer. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

(4) Formation of —CH = CH— The halide (32) is treated with n-butyllithium and then reacted with DMF (N, N-dimethylformamide) to obtain an aldehyde (38). The phosphonium salt (37) synthesized by the known method is treated with a base such as potassium t-butoxide to generate a phosphorus ylide. This phosphorus ylide is reacted with aldehyde (38) to synthesize compound (1D). Depending on the reaction conditions, a cis form is formed, and if necessary, the cis form is isomerized to a trans form by a known method.

(5) Formation of —CH ₂ CH ₂ — Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(6) Formation of (CH ₂ ) _4-Using phosphonium salt (39) in place of phosphonium salt (37), a compound having-(CH ₂ ) ₂ -CH = CH- according to the method of method (4) obtain. This is catalytically hydrogenated to synthesize a compound (1F).

(7) Formation of -CH ₂ CH = CHCH ₂ -According to the method of method (4), using phosphonium salt (40) instead of phosphonium salt (37) and aldehyde (41) instead of aldehyde (38), Compound (1G) is synthesized. Depending on the reaction conditions, a trans form is formed, and if necessary, the trans form is isomerized to a cis form by a known method.

(8) Formation of -C≡C- After reacting 2-methyl-3-butyn-2-ol with halide (33) in the presence of a catalyst of dichloropalladium and copper halide, basic conditions Deprotection below gives compound (32). The compound (42) is reacted with a halide (32) in the presence of a catalyst of dichloropalladium and copper halide to synthesize a compound (1H).

(9) Formation of —CF = CF— After treating the halide (33) with n-butyllithium, tetrafluoroethylene is reacted to obtain a compound (43). A halide (32) is treated with n-butyllithium and then reacted with a compound (43) to synthesize a compound (1I).

(10) Formation of —OCH ₂ — The aldehyde (38) is reduced with a reducing agent such as sodium borohydride to give a compound (44). Compound (44) is brominated with hydrobromic acid or the like to give bromide (45). Bromide (45) is reacted with compound (46) in the presence of a base such as potassium carbonate to synthesize compound (1J).

Formation of (11)-(CF ₂ ) _2-According to the method described in J. Am. Chem. Soc., 2001, 123, 5414. diketone (-COCO-) in the presence of a hydrogen fluoride catalyst, Fluorination with sulfur tetrafluoride gives compounds with-(CF ₂ ) _2- .

2-2. Generating ring ^{N 1} and ring ^{N 2} will now be described generation method related to the ring ^{N 1} and ring ^{N 2.} 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, pyridine-2 For rings such as 5, 5-diyl, pyrimidine-2, 5-diyl, etc., starting materials are commercially available or methods of production are well known. Thus, compounds (64), (67) and (71) shown below will be described.

Decahydronaphthalene-2,6-dione (64) is the starting material for compounds with decahydronaphthalene-2,6-diyl. This compound (64) is obtained by catalytic hydrogen reduction of diol (63) in the presence of ruthenium oxide and further oxidation with chromium oxide according to the method described in JP-A-2000-239564. This compound is converted to compound (1) by a conventional method.

The structural unit of 2,3- (bistrifluoromethyl) phenylene is synthesized by the method described in Org. Lett., 2000, 2 (21), 3345. Aniline (66) is synthesized by reaction of furan (65) with 1,1,1,4,4,4-hexafluoro-2-butyne at high temperature in a Diels-Alder type reaction. This compound is subjected to a Sandmeyer reaction according to the method described in Org. Synth. Coll., Vol. 2, 1943, 355 to obtain an iodide (67). This compound is converted to compound (1) by a conventional method.

The structural unit of 2-difluoromethyl-3-fluorophenylene is synthesized by the following method. The hydroxyl group of compound (68) is protected with a suitable protecting group to give compound (69). P represents a protecting group. Compound (69) is reacted with s-butyllithium and subsequently reacted with N, N-dimethylformamide (DMF) to obtain aldehyde (70). The compound is fluorinated with diethylaminosulfur trifluoride (DAST) and subsequently deprotected to give phenol (71). This compound is converted to compound (1) by a conventional method.

2-3. The introduction of rings ^A 1, ^{A 2} will now be described generation method relates to ring ^A 1, ^{A 2.} Starting materials such as cyclopropanemethanol, cyclobutanemethanol, cyclopentanone, cyclopentanol, bromocyclopentane, 4-bromocyclopentene, 3-bromocyclopentene, 1-bromocyclopentene, 2-bromotetrahydrofuran, 3-bromotetrahydrofuran are commercially available Or the methods of production are well known and can be used for the synthesis of compound (1) by conventional methods.

2-4. Formation of Dibenzothiophene Ring A method for forming a dibenzothiophene ring is well known, and can be synthesized with reference to the method described in JP-A-2015-205879.

2-5. Synthetic Method of Compound (1) An example of a synthetic method of Compound (1) is shown below.

The hydroxyl group of compound (72) is protected with a suitable protecting group to give compound (73). P represents a protecting group. With reference to a method of forming linking groups Z ¹ , Z ² , Z ³ and Z ^{4 and} a method of forming rings N ¹ and N ² , s-butyllithium is allowed to act on a compound (74) obtained from a known method, Reaction with trimethyl borate gives compound (75). Compound (73) and compound (75) are coupled using a metal catalyst to synthesize compound (76). Subsequently, deprotection is performed to obtain a compound (77). Compound (77) is reacted with trifluoromethanesulfonic anhydride to give compound (78). Compound (78) is reacted with ethyl 3-mercaptopropionate in the presence of a metal catalyst to give compound (79). Compound (79) is heated in the presence of potassium t-butoxide to cyclize to give compound (80). Compound (80) is reacted with n-butyllithium, reacted with trimethyl borate and hydrogen peroxide to obtain compound (81). This compound is converted to compound (1) by a conventional method. In these compounds, the definitions of R ¹ , R ² , A ¹ , A ² , N ¹ , N ² , Y ¹ , Y ² , Z ¹ , Z ² , Z ³ , Z ⁴ , a, b, c and d Is the same as the definition of the symbol described in the item 1.

3. Liquid Crystal Composition 3-1. Component Compounds The liquid crystal composition will be described. This composition contains at least one compound (1) as component (a). The composition may contain two or more compounds (1). The component of the composition may be only the compound (1). The composition preferably contains at least one of the compounds (1) in the range of 1% by weight to 99% by weight in order to develop good physical properties. In the composition having negative dielectric anisotropy, the preferred content of the compound (1) is in the range of 5% by weight to 60% by weight. In the composition having positive dielectric anisotropy, the content of the compound (1) is usually 30% by weight or less, preferably 20% by weight or less, more preferably 15% by weight based on the total weight of the liquid crystal composition. % Or less, more preferably 10% by weight or less, and usually 1% by weight or more, preferably 3% by weight or more, more preferably 5% by weight or more.

This composition contains compound (1) as component (a). The composition preferably further contains a liquid crystal compound selected from components (b) to (e) shown in Table 1. When preparing this composition, it is preferable to select components (b) to (e) in consideration of the plus and minus of the dielectric anisotropy and the size. The composition may contain liquid crystal compounds different from the compounds (1) to (13) and (21) to (24). This composition may not contain such a liquid crystal compound.

Component (b) is a compound in which the two end groups are alkyl or the like. Preferred examples of component (b) include compounds (2-1) to (2-11), compounds (3-1) to (3-19), and compounds (4-1) to (4-7). be able to. In these compounds, R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — is —O And in these groups at least one hydrogen may be replaced by fluorine.

Component (b) has a small dielectric anisotropy and is near neutral. The compound (2) has the effect of reducing the viscosity or adjusting the optical anisotropy. Compounds (3) and (4) have the effect of extending the temperature range of the nematic phase or raising the optical anisotropy by raising the upper limit temperature.

As the content of component (b) is increased, the viscosity of the composition decreases but the dielectric anisotropy decreases. Therefore, as long as the required value of the threshold voltage of the device is satisfied, it is preferable that the content be as high as possible. When preparing a composition for a mode such as IPS or VA, the content of the component (b) is preferably 30% by weight or more, more preferably 40% by weight or more based on the total weight of the liquid crystal composition. It is.

Component (c) is compounds (5) to (13). These compounds have phenylene in which the lateral position is substituted with two halogens, such as 2,3-difluoro-1,4-phenylene. Preferred examples of component (c) include compounds (5-1) to (5-9), compounds (6-1) to (6-19), compounds (7-1) and (7-2), compounds (c) 8-1) to (8-3), compounds (9-1) to (9-3), compounds (10-1) to (10-11), compounds (11-1) to (11-3), Compounds (12-1) to (12-3) and compound (13-1) can be mentioned. In these compounds, R ¹³ , R ¹⁴ and R ¹⁵ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — May be replaced by —O—, in these groups at least one hydrogen may be replaced by fluorine, and R ¹⁵ may be hydrogen or fluorine.

Component (c) has a large negative dielectric anisotropy. Component (c) is used when preparing a composition for modes such as IPS, VA, PSA and the like. As the content of the component (c) is increased, the dielectric anisotropy of the composition is negatively increased but the viscosity is increased. Therefore, the smaller the content, the better, as long as the required value of the threshold voltage of the device is satisfied. Considering that the dielectric anisotropy is about -5, the content is preferably 40% by weight or more based on the total weight of the liquid crystal composition in order to achieve sufficient voltage driving.

Among the components (c), since the compound (5) is a bicyclic compound, it has an effect of lowering the viscosity, adjusting the optical anisotropy or improving the dielectric anisotropy. Compounds (6) and (7) are tricyclic compounds, and compound (8) is a tetracyclic compound. Therefore, the effects of increasing the maximum temperature, optical anisotropy, or dielectric anisotropy are obtained. is there. Compounds (9) to (13) have the effect of increasing the dielectric anisotropy.

When preparing a composition for a mode such as IPS, VA, or PSA, the content of component (c) is preferably 40% by weight or more based on the total weight of the liquid crystal composition, and more preferably It is in the range of 50% by weight to 95% by weight. When component (c) is added to a composition having a positive dielectric anisotropy, the content of component (c) is preferably 30% by weight or less. By adding the component (c), it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component (d) is a compound having a halogen or fluorine-containing group at the right end. Preferred examples of the component (d) include the compounds (21-1) to (21-16), the compounds (22-1) to (22-116), and the compounds (23-1) to (23-59). Can. In these compounds, R ¹⁶ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — is replaced by —O— Well, in these groups, at least one hydrogen may be replaced by fluorine. X ¹¹ is fluorine, chlorine, -OCF ₃ , -OCHF ₂ , -CF ₃ , -CHF ₂ , -CH ₂ F, -OCF ₂ CHF ₂ , or -OCF ₂ CHFCF ₃ .

The component (d) is used when preparing a composition for modes such as IPS, FFS, and OCB because the dielectric anisotropy is positive and the stability to heat and light is very good. The content of component (d) is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, more preferably 40% by weight, based on the total weight of the liquid crystal composition. % To 95% by weight. When component (d) is added to a composition having a negative dielectric anisotropy, the content of component (d) is preferably 30% by weight or less. By adding the component (d), it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

Component (e) is a compound (24) in which the right terminal group is —C≡N or —C≡C—C≡N. Preferred examples of component (e) include compounds (24-1) to (24-64). In these compounds, R ¹⁷ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH ₂ — is replaced by —O— Well, in these groups, at least one hydrogen may be replaced by fluorine. X ¹² is —C≡N or —C≡C—C≡N.

Component (e) is used when preparing a composition for a mode such as TN since the dielectric anisotropy is positive and the value thereof is large. By adding this component (e), the dielectric anisotropy of the composition can be increased. The component (e) has the effect of widening the temperature range of the liquid crystal phase, adjusting the viscosity, or adjusting the optical anisotropy. Component (e) is also useful for adjusting the voltage-transmittance curve of the device.

When preparing a composition for a mode such as TN, the content of component (e) is suitably in the range of 1% by weight to 99% by weight based on the total weight of the liquid crystal composition, and is preferably It is in the range of 10% by weight to 97% by weight, more preferably in the range of 40% by weight to 95% by weight. When component (e) is added to a composition having negative dielectric anisotropy, the content of component (e) is preferably 30% by weight or less based on the total weight of the liquid crystal composition. By adding the component (e), it is possible to adjust the elastic constant of the composition and adjust the voltage-transmittance curve of the device.

By combining a compound appropriately selected from the above components (b) to (e) and the compound (1), high stability to heat and light, high upper limit temperature, low lower limit temperature, small viscosity, suitable Optical anisotropy (ie large optical anisotropy or small optical anisotropy), positive or negative large dielectric anisotropy, large specific resistance, appropriate elastic constant (ie large elastic constant or small elastic constant) A liquid crystal composition satisfying at least one of physical properties such as) can be prepared. A device comprising such a composition has a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a small flicker ratio, and a long lifetime.

When the device is used for a long time, flicker may occur on the display screen. The flicker rate (%) can be expressed by (| luminance when applying a positive voltage−luminance when applying a negative voltage |) / average luminance) × 100. An element whose flicker rate is in the range of 0% to 1% is less likely to cause flicker on the display screen even when the element is used for a long time. This flicker is related to image burn-in and is estimated to be generated by a potential difference between positive and negative frames when driven with an alternating current. The composition containing the compound (1) is also useful for reducing the occurrence of flicker.

3-2. Additives The liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and dissolved together by heating. Depending on the application, additives may be added to the composition. Examples of the additives are a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer, a dye, an antifoaming agent and the like. Such additives are well known to those skilled in the art and are described in the literature.

In a liquid crystal display device having a PSA (polymer sustained alignment) mode, the composition contains a polymer. The polymerizable compound is added in order to form a polymer in the composition. A polymer is formed in the composition by polymerizing the polymerizable compound by irradiation with ultraviolet light in a state where a voltage is applied between the electrodes. By this method, an appropriate pretilt is achieved, so that the response time is shortened and an element with improved image sticking is produced.

Preferred examples of the polymerizable compound are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), and vinyl ketones. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples also include compounds having both acryloyloxy and methacryloyloxy.

Further preferred examples are compounds (M-1) to (M-18). In these compounds, R ²⁵ to R ³¹ are independently hydrogen or methyl; R ³² , R ³³ and R ³⁴ are independently hydrogen or alkyl having 1 to 5 carbon atoms, R ³² , At least one of R ³³ and R ³⁴ is alkyl having 1 to 5 carbons; v, w and x are independently 0 or 1; u and y are independently 1 to 10 Is an integer of L ²¹ to L ²⁶ are independently hydrogen or fluorine; L ²⁷ and L ²⁸ are independently hydrogen, fluorine or methyl.

The polymerizable compound can be rapidly polymerized by adding a polymerization initiator such as a photo radical polymerization initiator. By optimizing the reaction conditions, the amount of remaining polymerizable compound can be reduced. Examples of photo radical polymerization initiators are TPO, 1173, and 4265 from Darrocure series of BASF, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, from Irgacure series. 1850 and 2959 can be mentioned.

Furthermore, 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9 as photo radical polymerization initiators -Phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyldimethyl Ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanolamine mixture It can also be used .

After adding a photo radical polymerization initiator to the liquid crystal composition, polymerization can be performed by irradiating ultraviolet light in a state where an electric field is applied. However, unreacted polymerization initiator or decomposition products of the polymerization initiator may cause display defects such as image sticking to the device. In order to prevent this, photopolymerization may be performed without adding a polymerization initiator. The preferred wavelength of the light to be irradiated is in the range of 150 nm to 500 nm. A further preferred wavelength is in the range of 250 nm to 450 nm, and the most preferred wavelength is in the range of 300 nm to 400 nm.

When storing the polymerizable compound, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

The optically active compound has an effect of inducing a helical structure in liquid crystal molecules and preventing reverse twist by providing a necessary twist angle. The helical pitch can be adjusted by adding an optically active compound. Two or more optically active compounds may be added in order to adjust the temperature dependency of the helical pitch. As preferred examples of the optically active compounds, the following compounds (Op-1) to (Op-18) can be mentioned. In the compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is alkyl having 1 to 10 carbons. The symbol * represents an asymmetric carbon.

Antioxidants are effective to maintain a large voltage holding ratio. As preferable examples of the antioxidant, the following compounds (AO-1) and (AO-2); Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114, and Irganox 1098 (trade name; manufactured by BASF) can be mentioned.
UV absorbers are effective to prevent the lowering of the upper limit temperature. Preferred examples of UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like, and specific examples thereof include the following compounds (AO-3) and (AO-4); Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 326, Tinuvin 213, Tinuvin 400 , Tinuvin 328, and Tinuvin 99-2 (trade name; BASF Corporation); and 1,4-diazabicyclo [2.2.2] octane (DABCO).

Light stabilizers such as sterically hindered amines are preferred to maintain high voltage holding rates. As preferable examples of the light stabilizer, the following compounds (AO-5), (AO-6), and (AO-7); Tinuvin 144, Tinuvin 765, and Tinuvin 770 DF (trade name; BASF Corporation); LA-77Y and LA- 77G (trade name; ADEKA company) can be mentioned. A heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example is Irgafos 168 (trade name; BASF Corporation). In order to conform to a guest host (GH) mode device, a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition. Defoamers are effective to prevent foaming. Preferred examples of the antifoaming agent are dimethyl silicone oil, methylphenyl silicone oil and the like.

In compound (AO-1), R ⁴⁰ is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, -COOR ⁴¹ , or -CH ₂ CH ₂ COOR ⁴¹ , wherein R ⁴¹ is a carbon number It is an alkyl of 1 to 20. In compounds (AO-2) and (AO-5), R ⁴² is alkyl having 1 to 20 carbons. In the compound ^{(AO-5), R 43} is hydrogen, methyl or O ^· (oxygen radical); ring ^{G 1} is an 1,4-cyclohexylene or 1,4-phenylene; Compound (AO-7 In the above, ring G ² is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; compounds (AO-5) and (AO— In 7), z is 1, 2 or 3.

4. Liquid Crystal Display Element The liquid crystal composition has an operation mode such as PC, TN, STN, OCB or PSA, and can be used for a liquid crystal display element driven by an active matrix system. This composition can be used also for a liquid crystal display element driven by a passive matrix method, having an operation mode such as PC, TN, STN, OCB, VA, IPS and the like. These elements can be applied to any of reflective, transmissive, and semi-transmissive types.

The composition is also suitable for a nematic curvilinear aligned phase (NCAP) device, in which the composition is microencapsulated. This composition can also be used for polymer dispersed liquid crystal display (PDLCD) and polymer network liquid crystal display (PNLCD). In these compositions, a large amount of polymerizable compound is added. On the other hand, when the proportion of the polymerizable compound is 10% by weight or less based on the total weight of the liquid crystal composition, a PSA mode liquid crystal display device is produced. The preferred proportion is in the range of 0.1% by weight to 2% by weight. A further preferred ratio is in the range of 0.2% by weight to 1.0% by weight. The element in the PSA mode can be driven by a driving method such as an active matrix method or a passive matrix method. Such an element can be applied to any of reflective, transmissive and semi-transmissive types.

1. Examples of Compound (1) The present invention will be described in more detail by way of examples. The present invention is not limited by the examples, as the examples are typical examples. Compound (1) was synthesized by the following procedure. The compound synthesized was identified by a method such as NMR analysis. The physical properties of the compounds and compositions and the characteristics of the devices were measured by the following methods.

NMR analysis:
For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl ₃ and measured at room temperature, 500 MHz, under conditions of 16 times of integration. Tetramethylsilane was used as an internal standard. ^{In the 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the integration was performed 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.

Gas chromatography analysis:
For measurement, a GC-2010 gas chromatograph manufactured by Shimadzu Corporation was used. As a column, capillary columns DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. were used. Helium (1 mL / min) was used as a carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., and the temperature of the detector (FID) was set to 300 ° C. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the resulting solution was injected into the sample vaporization chamber. As a recorder, GCSolution system made by Shimadzu Corporation etc. was used.

Gas chromatograph mass spectrometry:
For measurement, a QP-2010 Ultra type gas chromatograph mass spectrometer manufactured by Shimadzu Corporation was used. As a column, capillary columns DB-1 (length 60 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. were used. Helium (1 ml / min) was used as a carrier gas. The temperature of the sample vaporization chamber was set to 300 ° C., the temperature of the ion source to 200 ° C., the ionization voltage to 70 eV, and the emission current to 150 uA. The sample was dissolved in acetone to prepare a 1% by weight solution, and 1 μl of the resulting solution was injected into the sample vaporization chamber. A GCMSsolution system manufactured by Shimadzu Corporation was used as a recorder.

HPLC analysis:
For measurement, Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used. As a column, YMC YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) was used. As the eluate, acetonitrile and water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector, etc. were used suitably. When a UV detector was used, the detection wavelength was 254 nm. The sample was dissolved in acetonitrile to prepare a 0.1% by weight solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7Aplus manufactured by Shimadzu Corporation was used.

UV-visible spectroscopy:
For measurement, PharmaSpec UV-1700 manufactured by Shimadzu Corporation was used. The detection wavelength was from 190 nm to 700 nm. The sample was dissolved in acetonitrile to prepare a 0.01 mmol / L solution, and placed in a quartz cell (optical path length: 1 cm) for measurement.

Measurement sample:
When measuring the phase structure and transition temperature (clearing point, melting point, polymerization initiation temperature, etc.), the compound itself was used as a sample. When physical properties such as the upper limit temperature of the nematic phase, viscosity, optical anisotropy, dielectric anisotropy and the like were measured, a mixture of the compound and the base liquid crystal was used as a sample.

In the case of using a sample in which the compound was mixed with mother liquid crystals, measurement was performed as follows. A sample was prepared by mixing 15% by weight of the compound and 85% by weight of mother liquid crystals. From the measured value of this sample, the extrapolated value was calculated according to the following equation, and this value was described. <Extrapolated value> = (100 × <measured value of sample> − <weight% of mother liquid crystal> × <measured value of mother liquid crystal>) / <weight% of compound>

When crystals (or smectic phase) precipitate at 25 ° C. in this ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% It changed in order of%, and the physical property of the sample was measured in the ratio in which a crystal (or smectic phase) stopped precipitating at 25 degreeC. The ratio of the compound to the mother liquid crystals is 15% by weight: 85% by weight unless otherwise specified.

When the dielectric anisotropy of the compound was positive from zero (0 <), the following mother liquid crystal (A) was used. The proportions of the respective components were expressed as% by weight based on the total weight of the liquid crystal composition.

When the dielectric anisotropy of the compound was negative (<0) from zero, the following mother liquid crystal (B) was used. The proportions of the respective components were expressed as% by weight based on the total weight of the liquid crystal composition.

Measuring method:
The physical properties were measured by the following method. Many of these are described in the JEITA standard (JEITA ED-2521B), which is deliberately established by the Japan Electronics and Information Technology Industries Association (JEITA). A modified method of this was also used. A thin film transistor (TFT) was not attached to the TN device used for the measurement.

(1) Phase structure:
The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope (Mettler FP-52 hot stage). While heating this sample at a rate of 3 ° C./min, the phase state and its change were observed with a polarization microscope to identify the type of phase.

(2) Transition temperature (° C.):
For measurement, a scanning calorimeter manufactured by Perkin Elmer, a Diamond DSC system, or a high-sensitive differential scanning calorimeter manufactured by SII Nano Technology, X-DSC7000 was used. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, and the transition point was determined by extrapolating the start point of the endothermic peak or exothermic peak associated with the phase change of the sample. The melting point of the compound and the polymerization initiation temperature were also measured using this apparatus. The temperature at which a compound transitions from a solid to a liquid crystal phase such as a smectic phase or a nematic phase may be abbreviated as "the lower limit temperature of the liquid crystal phase". The temperature at which a compound transitions from liquid crystal phase to liquid may be abbreviated as the "clearing point".

The crystal is designated C. When the crystals can be distinguished into two types, each is represented as C ₁ or C ₂ . The smectic phase is represented by S and the nematic phase is represented by N. When a phase such as smectic A phase, smectic B phase, smectic C phase, and smectic F phase can be distinguished, they are represented as S _A , S _B , S _C and S _F respectively. The liquid (isotropic) was designated as I. The transition temperature is expressed as, for example, "C 50.0 N 100.0 I". This indicates that the transition temperature from crystal to nematic phase is 50.0 ° C., and the transition temperature from nematic phase to liquid is 100.0 ° C.

(3) Compatibility of compounds:
A sample was prepared by mixing the base liquid crystal and the compound such that the proportion of the compound was 10% by weight, 3% by weight, or 1% by weight. The sample was placed in a glass bottle and stored in a −10 ° C. freezer for a fixed period of time. It was observed whether the nematic phase of the sample was maintained or crystals (or smectic phase) were precipitated. The conditions under which the nematic phase is maintained are used as a measure of compatibility. The ratio of compounds and the temperature of the freezer may be changed as needed.

(4) Upper limit temperature of nematic phase (T _NI or NI; ° C.):
The sample was placed on the hot plate of a melting point apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid. When the sample is a mixture of compound (1) and mother liquid crystals, it is indicated by the symbol _TNI . When the sample is a mixture of compound (1) and compounds selected from compounds (2) to (13) and compounds (21) to (24), it is indicated by the symbol NI. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

(5) Lower limit temperature of nematic phase (T _c ; ° C.):
The sample having the nematic phase was placed in a glass bottle and stored in a freezer at 0 ° C, -10 ° C, -20 ° C, -30 ° C, and -40 ° C for 10 days, and then the liquid crystal phase was observed. For example, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase was described as <-20 ° C. The T _C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

(6) Viscosity (bulk viscosity; ;; measured at 20 ° C .; mPa · s):
For measurement, an E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used.

(7) Optical anisotropy (refractive index anisotropy; measured at 25 ° C .; Δn):
The measurement was performed using an Abbe refractometer with a polarizing plate attached to the eyepiece, using light at a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, a sample was dropped on the main prism. The refractive index (n∥) was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy (Δn) was calculated from the equation Δn = nn−n⊥.

(8) Specific resistance (ρ; measured at 25 ° C .; Ω cm):
A sample of 1.0 mL was injected into a container equipped with an electrode. A direct current voltage (10 V) was applied to the container, and a direct current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Specific resistance) = {(voltage) × (electric capacity of container)} / {(direct current) × (dielectric constant of vacuum)}.

(9) Voltage holding ratio (VHR-1; measured at 25 ° C .;%):
The TN device used for the measurement had a polyimide alignment film, and the distance between two glass substrates (cell gap) was 5 μm. The element was sealed with an adhesive that cures with ultraviolet light after the sample was placed. A pulse voltage (60 microseconds at 5 V) was applied to this element to charge it. The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. The area B is the area when not attenuated. The voltage holding ratio was expressed as a percentage of the area A to the area B.

(10) Voltage holding ratio (VHR-2; measured at 80 ° C .;%):
The voltage holding ratio was measured by the above method except that measurement was performed at 80 ° C. instead of 25 ° C. The obtained result is shown by the symbol of VHR-2.

(11) Flicker rate (measured at 25 ° C .;%):
A multimedia display tester 3298F manufactured by Yokogawa Electric Corporation was used for the measurement. The light source was an LED. The sample was placed in a normally black mode FFS element in which the distance between two glass substrates (cell gap) was 3.5 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A voltage was applied to this device, and the voltage at which the amount of light transmitted through the device became maximum was measured. While applying this voltage to the element, the sensor unit was brought close to the element, and the displayed flicker rate was read.

The measurement method of physical properties may be different between a sample with positive dielectric anisotropy and a sample with negative dielectric anisotropy. The measurement method when the dielectric anisotropy is positive was described in Measurement (12a) to Measurement (16a). When the dielectric anisotropy is negative, it was described in the measurement (12b) to the measurement (16b).

(12a) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s; sample with positive dielectric anisotropy):
The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). The sample was placed in a TN device having a twist angle of 0 degree and a distance between two glass substrates (cell gap) of 5 μm. The device was applied stepwise in steps of 0.5 V from 16 V to 19.5 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M. The rotational viscosity values were obtained from the article by Imai et al. And equation (8) on page 40. The value of dielectric anisotropy required for this calculation was determined by the method described below using the device for which this rotational viscosity was measured.

(12b) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s; sample having negative dielectric anisotropy):
The measurement was according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 20 μm. A voltage of 39 V to 50 V was applied stepwise to the device every 1 V. After 0.2 seconds of no application, application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M. The rotational viscosity values were obtained from the article by Imai et al. And equation (8) on page 40. The dielectric anisotropy required for this calculation was measured in the section of dielectric anisotropy described below.

(13a) dielectric anisotropy (Δε; measured at 25 ° C .; sample with positive dielectric anisotropy):
The value of dielectric anisotropy was calculated from the equation of Δε = ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
(1) Measurement of dielectric constant (ε∥):
The polyimide solution was applied to the well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of liquid crystal molecules was measured.
(2) Measurement of dielectric constant (ε⊥):
A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to the well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 μm, and this device was sealed with an adhesive cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured.

(13b) dielectric anisotropy (Δε; measured at 25 ° C .; sample with negative dielectric anisotropy):
The value of dielectric anisotropy was calculated from the equation of Δε = ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
(1) Measurement of dielectric constant (ε∥):
A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to the well-cleaned glass substrate. The glass substrate was rotated by a spinner and then heated at 150 ° C. for 1 hour. A sample was placed in a VA device in which the distance between two glass substrates (cell gap) was 4 μm, and this device was sealed with an adhesive cured with ultraviolet light. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (ε∥) in the major axis direction of liquid crystal molecules was measured.
(2) Measurement of dielectric constant (ε⊥):
The polyimide solution was applied to the well-cleaned glass substrate. After firing the glass substrate, the obtained alignment film was rubbed. The sample was placed in a TN device in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to this device, and after 2 seconds, the dielectric constant (⊥) in the minor axis direction of liquid crystal molecules was measured.

(14a) elastic constant (K; measured at 25 ° C .; pN; sample with positive dielectric anisotropy):
For measurement, an HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co. was used. The sample was placed in a horizontal alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 V to 20 V was applied to the device, and the capacitance (C) and the applied voltage (V) were measured. These measured values are fitted using the equation (2.98) and equation (2.101) in “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun Co., Ltd.), page 75, and from equation (2.99) The values of K ₁₁ and K ₃₃ were obtained. Then, the equation (3.18) on page 171, to calculate the _{K 22} using the values of _{K 11} and _{K 33} was determined previously. The elastic constant K was represented by the average value of K ₁₁ , K ₂₂ and K ₃₃ determined in this manner.

(14b) elastic constant (K ₁₁ and K ₃₃ ; measured at 25 ° C .; pN; negative dielectric anisotropy sample):
For measurement, an EC-1 type elastic constant measuring device manufactured by Toyo Technology Co., Ltd. was used. The sample was placed in a vertical alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 V to 0 V was applied to the device, and the capacitance (C) and the applied voltage (V) were measured. These values are fitted using the equation (2.98) and equation (2.101) in “Liquid Crystal Device Handbook” (Nippon Kogyo Shimbun Co., Ltd.), page 75, and from equation (2.100) The value of the elastic constant was obtained.

(15a) threshold voltage (Vth; measured at 25 ° C .; V; sample with positive dielectric anisotropy):
For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) is 0.45 / Δn (μm) and the twist angle is 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 10 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 90% transmittance.

(15b) Threshold voltage (Vth; measured at 25 ° C .; V; sample having negative dielectric anisotropy):
For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. A sample is placed in a normally black mode VA device in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel, and an adhesive for curing this device with ultraviolet light is used. Used and sealed. The voltage (60 Hz, rectangular wave) applied to this element was gradually increased by 0.02 V from 0 V to 20 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The threshold voltage was represented by the voltage at 10% transmittance.

(16a) response time (τ; measured at 25 ° C .; ms; sample with positive dielectric anisotropy):
An LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally white mode TN device in which the distance between two glass substrates (cell gap) was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The rise time (τr: millisecond) is the time taken for the transmittance to change from 90% to 10%. The fall time (τf: milliseconds) is the time taken to change from 10% transmission to 90% transmission. The response time is represented by the sum of the rise time and the fall time obtained in this manner.

(16b) response time (τ; measured at 25 ° C .; ms; sample with negative dielectric anisotropy):
For measurement, an LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally black mode PVA element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A voltage slightly higher than the threshold voltage was applied to the device for 1 minute, and then ultraviolet light of 23.5 mW / cm ² was applied for 8 minutes while applying a voltage of 5.6 V. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.

Synthesis Example 1
Synthesis of Compound (No. 17)

First Step: Synthesis of Compound (T-2) In a nitrogen atmosphere, Compound (T-1) (40.6 g), imidazole (31.8 g), and dichloromethane (300 mL) were placed in a reactor, and then placed on an ice bath It cooled. Chlorotriethylsilane (35.2 g) was added little by little and the mixture was returned to room temperature and stirred for 1 hour. After completion of the reaction, the reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The combined organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (heptane) to give compound (T-2) (53.6 g; 79%).

Step 2: Synthesis of Compound (T-4) Compound (T-2) (53.6 g), Compound (T-3) (37.2 g), toluene (200 ml), ethanol (200 ml), under a nitrogen atmosphere Water (200 ml), PdCl ₂ (Amphos) ₂ (Pd-132, 0.12 g), potassium carbonate (48.5 g), and tetrabutylammonium bromide (TBAB, 14.2 g) are charged to the reactor and Stir for 12 hours. The reaction mixture was poured into water, extracted with toluene, washed with water and brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, ethyl acetate: heptane = 1: 2) to give compound (T-4) (39.2 g; 83%).

Step 3: Synthesis of Compound (T-5) Under a nitrogen atmosphere, compound (T-4) (39.2 g), pyridine (17.3 g, 17.7 ml), and tetrahydrofuran (THF, 200 mL) were placed in a reactor The mixture was cooled to 0 ° C. Trifluoromethanesulfonic anhydride (49.5 g, 29.6 ml) was added dropwise and stirred for 1 hour. After completion of the reaction, the reaction mixture was poured into saturated aqueous sodium bicarbonate and the aqueous layer was extracted with toluene. The combined organic layer was washed with water and brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, ethyl acetate: heptane = 1: 7) to give compound (T-5) (41.2 g; 70%).

Step 4: Synthesis of Compound (T-6) Compound (T-5) (36.2 g), Ethyl 3-Mercaptopropionate (12.7 g), Toluene (200 ml), Bis (dibenzylideneacetone) under a nitrogen atmosphere ) Palladium (0) (4.2 g), bis [2- (diphenylphosphino) phenyl] ether (4.9 g), and potassium carbonate (31.2 g) were charged into the reactor and stirred at 90 ° C. for 12 hours . The reaction mixture was poured into water, extracted with t-butyl methyl ether, washed with water and brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, ethyl acetate: heptane = 1: 4) to give compound (T-6) (15.5 g; 36%).

Step 5: Synthesis of Compound (T-7) In a nitrogen atmosphere, compound (T-6) (19.9 g), potassium t-butoxide (7.0 g), THF (150 ml) were put in a reactor, and 70 ° C. The mixture was stirred for 3 hours. After completion of the reaction, the reaction mixture is cooled to room temperature, poured into water, extracted with toluene, washed with brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, ethyl acetate: heptane = 1: 3). Furthermore, purification was performed by recrystallization from a mixed solvent (volume ratio, 1: 1) of Solmix (registered trademark) A-11 and heptane to obtain a compound (T-7) (9.4 g).

Step 6: Synthesis of Compound (T-8) In a nitrogen atmosphere, compound (T-7) (9.6 g) and THF (200 mL) were charged into a reactor and cooled to -70.degree. n-Butyllithium (1.6 M; n-hexane solution; 29.7 ml) was added and stirred for 2 hours. Trimethyl borate (4.8 g) was added, and the mixture was returned to room temperature and stirred for 12 hours. Acetic acid (4.1 ml) was added at room temperature and stirred for 30 minutes, then aqueous hydrogen peroxide (35 wt%; 6.2 ml) was added and stirred for 1 hour. After completion of the reaction, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The combined organic layer was washed with water, aqueous sodium bisulfite solution and brine, then dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, ethyl acetate: heptane = 1: 2) to give compound (T-8) (10.0 g; 95%).

Step 7: Synthesis of Compound (No. 17) Compound (T-8) (5.0 g), cyclopentanol (1.5 g), triphenylphosphine (5.6 g), and THF (40 mL) under a nitrogen atmosphere ) Was cooled in an ice bath. Diethyl azodicarboxylate (DEAD, 2.2 M; toluene solution; 9.7 ml) was added and stirred at room temperature for 12 hours. After completion of the reaction, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The combined organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 2: 1) and further purified by recrystallization from heptane to give compound (No. 17) (4.0 g, 65%).

¹ H-NMR (CDCl ₃ ; δ ppm): 7.69-7.66 (m, 2H), 7.12 to 7.09 (m, 2H), 4.91 to 4.89 (m, 1H), 4.22 (q, J = 7.0 Hz, 2 H), 1.99-1.83 (m, 6 H), 1.69-1.61 (m, 2 H), 1.49 (t, J = 7) .0 Hz, 3 H).

Phase transition temperature: C1 53.4 ° C. C2 69.8 ° C. C3 76.7 ° C. I. Maximum temperature (NI) = 46.3 ° C .; dielectric anisotropy (Δε) = − 11.6; optical anisotropy (Δn) = 0.200; viscosity (η) = 72.8 mPa · s.

Synthesis Example 2
Synthesis of Compound (No. 26)

Using compound (T-8) (5.0 g) as a raw material, compound (No. 26) (3.7 g; 57%) was synthesized in the same manner as in the seventh step of Synthesis Example 1.

¹ H-NMR (CDCl ₃ ; δ ppm): 7.67-7.64 (m, 2H), 7.11-7.07 (m, 2H), 4.20 (q, J = 7.0 Hz, 2H) ), 4.00 (d, J = 7.0 Hz, 2 H), 2.47-2.38 (m, 1 H), 1.90 to 1.84 (m, 2 H), 1.70 to 1.58 (M, 4 H), 1.48 (t, J = 7.0 Hz, 3 H), 1.45-1. 35 (m, 2 H).

Phase transition temperature: C 94.0 ° C. I. Maximum temperature (NI) = 62.3 ° C .; dielectric anisotropy (Δε) = − 10.1; optical anisotropy (Δn) = 0.200; viscosity (() = 71, 7 mPa · s.

The compounds shown below can be synthesized by known methods, referring to the method described in the synthesis examples and the section of “2. Synthesis of compound (1)”.

Comparative Example 1
Comparison of physical properties The following compound (S-1) was selected as a comparison compound. This compound is described in JP-A-2015-205879 and is similar to the compound according to the embodiment of the present invention.

¹ H-NMR (CDCl ₃ ; δ ppm): 7.70-7.68 (m, 2 H), 7.13-7. 10 (m, 2 H), 4.22 (q, J = 7.0 Hz, 2 H) ), 4.15 (t, J = 6.5 Hz, 2 H), 1.87-1.81 (m, 2 H), 1.58-1.47 (m, 5 H), 1.00 (t, J) = 7.3 Hz, 3 H).

Phase transition temperature: C 80.5 ° C. I. Maximum temperature (NI) = 79.0 ° C; dielectric anisotropy (Δε) = -11.6; optical anisotropy (Δn) = 0.200; viscosity (η) = 51.1 mPa · s.

The low temperature compatibility was compared between the compound (No. 17) obtained in Synthesis Example 1 and the compound (No. 26) obtained in Synthesis Example 2 and the comparison compound (S-1). The results are shown in Table 2. Composition (X-1) in which compound (No. 17) was added to 10 wt% to mother liquid crystals (B) or composition (X in which compound (No. 26) was added to 10 wt% -2) maintains the nematic phase even after 30 days in a freezer at -10 ° C, while the comparative compound (S-1) is added in a proportion of 10 wt% (X- Precipitation of crystals was observed in 3), and precipitation of crystals was also observed in the composition (X-6) added to 3% by weight. This indicates that the compounds (No. 17) and (No. 26) of the present application are superior in solubility to the base liquid crystal at a lower temperature than the comparative compound (S-1).

2. Composition Examples The invention will be further described by way of examples. The present invention is not limited by the examples, as the examples are typical examples. For example, the present invention includes, in addition to the composition of Use Example, a mixture of the composition of Use Example 1 and the composition of Use Example 2. The invention also includes mixtures prepared by mixing at least two of the compositions of the Use Examples. The compounds in the use examples are represented by symbols based on the definition of Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. In the example of use, the number in parentheses after the symbol represents the chemical formula to which the compound belongs. The symbol (−) means a liquid crystal compound different from the compounds (1) to (13) and the compounds (21) to (24). The proportion (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. Finally, the physical properties of the composition were summarized. Physical properties were measured according to the method described above, and the measured values were described as they were (without extrapolation).

[Example 1]
Cp-Odbt (4F, 6F) -O2 (No. 17) 4%

1-BB-3 (2-8) 6%
1-BB-5 (2-8) 7%
2-BTB-1 (2-10) 3%
3-HHB-1 (3-1) 8%
3-HHB-O1 (3-1) 5%
3-HHB-3 (3-1) 12%
3-HHB-F (22-1) 4%
2-HHB (F) -F (22-2) 7%
3-HHB (F) -F (22-2) 7%
5-HHB (F) -F (22-2) 7%
3-HHB (F, F) -F (22-3) 5%
3-HHEB-F (22-10) 4%
5-HHEB-F (22-10) 4%
2-HB-C (24-1) 5%
3-HB-C (24-1) 12%
NI = 95.0 ° C .; = 1 = 19.8 mPa · s; Δn = 0.111; Δε = 4.3.

[Example 2]
Cp-1 Odbt (4F, 6F)-O2 (No. 26) 3%

3-HH-4 (2-1) 12%
7-HB-1 (2-5) 3%
5-HB-O2 (2-5) 4%
5-HBB (F) B-2 (4-5) 5%
5-HBB (F) B-3 (4-5) 5%
3-HB-CL (21-2) 12%
3-HHB (F, F) -F (22-3) 3%
3-HBB (F, F) -F (22-24) 29%
5-HBB (F, F) -F (22-24) 24%
NI = 71.2 ° C; = 2 = 21.1 mPa · s; Δn = 0.117; Δε = 5.2.

[Example 3]
Cp-Odbt (4F, 6F) -O2 (No. 17) 6%
Cp-1 Odbt (4F, 6F)-O2 (No. 26) 6%

1V2-HH-1 (2-1) 3%
1V2-HH-3 (2-1) 4%
7-HB (F, F) -F (21-4) 3%
2-HHB (F) -F (22-2) 8%
3-HHB (F) -F (22-2) 8%
5-HHB (F) -F (22-2) 8%
2-HBB-F (22-22) 4%
3-HBB-F (22-22) 4%
5-HBB-F (22-22) 3%
2-HBB (F) -F (22-23) 8%
3-HBB (F) -F (22-23) 7%
5-HBB (F) -F (22-23) 14%
3-HBB (F, F) -F (22-24) 5%
5-HBB (F, F) -F (22-24) 9%
NI = 80.9 ° C .; = 2 = 29.6 mPa · s; Δn = 0.122; Δε = 3.4.

[Example 4]
Cp-Odbt (4F, 6F) -O4 (No. 19) 6%

2-HH-3 (2-1) 4%
3-HH-4 (2-1) 11%
1O1-HBBH-5 (4-1) 3%
5-HB-CL (21-2) 15%
3-HHB-F (22-1) 4%
3-HHB-CL (22-1) 3%
4-HHB-CL (22-1) 4%
3-HHB (F) -F (22-2) 9%
4-HHB (F) -F (22-2) 8%
5-HHB (F) -F (22-2) 9%
7-HHB (F) -F (22-2) 8%
5-HBB (F) -F (22-23) 3%
3-HBBB (F, F) -F (23-6) 2%
4-HBBB (F, F) -F (23-6) 3%
5-HBBB (F, F) -F (23-6) 3%
3-HH2BB (F, F) -F (23-15) 3%
4-HH2BB (F, F) -F (23-15) 2%

[Example 5]
Cp-dbt (4F, 6F) -O4 (No. 3) 5%

V-HBB-2 (3-4) 10%
1O1-HBBH-4 (4-1) 4%
1O1-HBBH-5 (4-1) 3%
3-HHB (F, F) -F (22-3) 8%
3-H2HB (F, F) -F (22-15) 7%
4-H2HB (F, F) -F (22-15) 8%
5-H2HB (F, F) -F (22-15) 8%
3-HBB (F, F)-F (22-24) 10%
5-HBB (F, F) -F (22-24) 20%
3-H2BB (F, F) -F (22-27) 9%
5-HBBB (F, F) -F (23-6) 3%
3-HH2BB (F, F) -F (23-15) 3%
5-HHEBB-F (23-17) 2%

[Example 6]
Cp-Odbt (4F, 6F) H-3 (No. 100) 4%

5-HBBH-3 (4-1) 3%
3-HB (F) BH-3 (4-2) 3%
5-HB-F (21-2) 12%
6-HB-F (21-2) 9%
7-HB-F (21-2) 7%
2-HHB-OCF3 (22-1) 7%
3-HHB-OCF3 (22-1) 7%
4-HHB-OCF3 (22-1) 7%
5-HHB-OCF3 (22-1) 5%
3-HHB (F, F) -OCF2H (22-3) 4%
3-HHB (F, F) -OCF3 (22-3) 4%
3-HH2B-OCF3 (22-4) 3%
5-HH2B-OCF3 (22-4) 4%
3-HH2B (F) -F (22-5) 3%
3-HBB (F) -F (22-23) 8%
5-HBB (F) -F (22-23) 10%

[Example 7]
Cp-Odbt (4F, 6F) B-3 (No. 98) 4%

3-HH-4 (2-1) 4%
2-HH-5 (2-1) 5%
5-B (F) BB-2 (3-8) 4%
5-HB-CL (21-2) 10%
3-HHB (F, F) -F (22-3) 8%
3-HHEB (F, F) -F (22-12) 9%
4-HHEB (F, F)-F (22-12) 3%
5-HHEB (F, F) -F (22-12) 3%
3-HBB (F, F) -F (22-24) 20%
5-HBB (F, F) -F (22-24) 14%
2-HBEB (F, F) -F (22-39) 3%
3-HBEB (F, F) -F (22-39) 4%
5-HBEB (F, F) -F (22-39) 3%
3-HBBB (F, F) -F (23-6) 6%

[Example 8]
Thf (3) -Odbt (4F, 6F) -O5 (No. 45) 3%

V2-HHB-1 (3-1) 5%
3-HB-CL (21-2) 5%
5-HB-CL (21-2) 4%
3-HHB-OCF3 (22-1) 4%
V-HHB (F) -F (22-2) 5%
5-HHB (F) -F (22-2) 5%
3-H2HB-OCF3 (22-13) 5%
5-H2HB (F, F) -F (22-15) 5%
5-H4HB-OCF3 (22-19) 15%
3-H4HB (F, F) -CF3 (22-21) 8%
5-H4HB (F, F) -CF3 (22-21) 10%
5-H4HB (F, F) -F (22-21) 7%
2-H2BB (F) -F (22-26) 5%
3-H2BB (F) -F (22-26) 10%
3-HBEB (F, F) -F (22-39) 4%
NI = 70.8 ° C .; = 2 = 24.1 mPa · s; Δn = 0.096; Δε = 7.8.

[Example 9]
Cp-Odbt (4F, 6F) -O3V (No, 64) 5%

3-HH-4 (2-1) 10%
3-HH-5 (2-1) 5%
3-HB-O2 (2-5) 14%
3-HHB-1 (3-1) 8%
3-HHB-O1 (3-1) 5%
5-HB-CL (21-2) 16%
7-HB (F, F) -F (21-4) 2%
2-HHB (F) -F (22-2) 6%
3-HHB (F) -F (22-2) 7%
5-HHB (F) -F (22-2) 7%
3-HHB (F, F) -F (22-3) 6%
3-H2HB (F, F) -F (22-15) 5%
4-H2HB (F, F) -F (22-15) 4%

[Usage example 10]
Cpe (1) -1Odbt (4F, 6F) -O5 (No. 58) 5%

3-HH-4 (2-1) 9%
3-HH-5 (2-1) 10%
4-HH-V (2-1) 14%
5-HB-CL (21-2) 3%
7-HB (F) -F (21-3) 6%
2-HHB (F, F) -F (22-3) 4%
3-HHB (F, F) -F (22-3) 5%
3-HHEB-F (22-10) 7%
5-HHEB-F (22-10) 8%
3-HHEB (F, F) -F (22-12) 9%
4-HHEB (F, F)-F (22-12) 5%
3-GHB (F, F) -F (22-109) 4%
4-GHB (F, F) -F (22-109) 6%
5-GHB (F, F) -F (22-109) 5%

[Example 11 of use]
3-Cp (1, 3) dbt (4F, 6F)-O2 (No. 4) 3%

3-HH-VFF (2-1) 4%
5-HH-VFF (2-1) 25%
2-BTB-1 (2-10) 9%
3-HHB-1 (3-1) 4%
VFF-HHB-1 (3-1) 8%
VFF2-HHB-1 (3-1) 10%
3-H2BTB-2 (3-17) 5%
3-H2BTB-3 (3-17) 4%
3-H2BTB-4 (3-17) 4%
3-HB-C (24-1) 18%
1V2-BEB (F, F) -C (24-15) 6%

[Example 12 of use]
Cpr-1 Odbt (4F, 6F)-O2 (No. 72) 4%

3-HH-V (2-1) 34%
3-HH-V1 (2-1) 4%
5-HH-V (2-1) 5%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
2-BB (F) B-3 (3-6) 5%
3-HHEH-5 (3-13) 3%
1V2-BB-F (21-1) 3%
3-BB (F, F) XB (F, F) -F (22-97) 9%
3-BB (2F, 3F) XB (F, F)-F (22-114) 3%
3-HBBB (F, F) -F (23-6) 3%
3-HBBXB (F, F) -F (23-32) 3%
5-HB (F) B (F, F) XB (F, F) -F (23-41) 4%
3-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
4-BB (F) B (F, F) X B (F, F)-F (23-47) 5%
5-BB (F) B (F, F) X B (F, F)-F (23-47) 3%

[Example 13 of use]
Cb-1 Odbt (4F, 6F)-O2 (No. 71) 4%

3-HH-V (2-1) 30%
3-HH-V1 (2-1) 6%
V-HH-V1 (2-1) 5%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
1-BB (F) B-2V (3-6) 4%
3-HHEH-5 (3-13) 3%
1V2-BB-F (21-1) 3%
3-BB (F, F) XB (F, F) -F (22-97) 5%
3-HHXB (F, F) -CF3 (22-100) 3%
3-GB (F, F) XB (F, F) -F (22-113) 4%
3-GB (F) B (F, F)-F (22-116) 4%
3-HBBB (F, F) -F (23-6) 3%
3-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
4-BB (F) B (F, F) X B (F, F)-F (23-47) 7%
5-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
3-GB (F) B (F, F) X B (F, F)-F (23-57) 4%

[Example 14]
3-Cp (1, 3) Bdbt (4F, 6F)-O2 (No. 164) 4%

3-HH-V (2-1) 35%
3-HH-V1 (2-1) 4%
3-HHB-1 (3-1) 3%
V-HHB-1 (3-1) 5%
3-HBB-2 (3-4) 5%
V2-BB (F) B-1 (3-6) 5%
3-HHEH-3 (3-13) 3%
3-HHEH-5 (3-13) 3%
1V2-BB-F (21-1) 3%
3-BB (F, F) XB (F, F) -F (22-97) 4%
3-GB (F, F) XB (F, F) -F (22-113) 3%
3-HBBB (F, F) -F (23-6) 2%
3-HBB (F, F) XB (F, F) -F (23-38) 3%
3-BB (F) B (F, F) X B (F)-F (23-46) 3%
4-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
5-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
3-GB (F) B (F, F) X B (F, F)-F (23-57) 5%
4-GB (F) B (F, F) X B (F, F)-F (23-57) 2%
5-GB (F) B (F, F) X B (F, F)-F (23-57) 2%

[Example 15 of use]
Cp-Odbt (4F, 6F) -O2 (No. 17) 5%

3-HH-V (2-1) 35%
3-HH-V1 (2-1) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 3%
V2-BB (F) B-1 (3-6) 4%
3-HHEH-5 (3-13) 3%
3-HHEBH-3 (4-6) 4%
1V2-BB-F (21-1) 3%
3-BB (F) B (F, F)-F (22-69) 3%
3-BB (F, F) XB (F, F) -F (22-97) 5%
3-HBBB (F, F) -F (23-6) 3%
5-HB (F) B (F, F) XB (F, F) -F (23-41) 4%
4-BB (F) B (F, F) X B (F, F)-F (23-47) 4%
5-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
2-dhBB (F, F) XB (F, F) -F (23-50) 1%
3-dhBB (F, F) XB (F, F) -F (23-50) 3%
3-GBB (F) B (F, F)-F (23-55) 3%
4-GBB (F) B (F, F)-F (23-55) 3%
3-BB (F, F) XB (F) B (F, F) -F (23-56) 4%
NI = 81.5 ° C .; = 2 = 20.1 mPa · s; Δn = 0.104; Δε = 4.3.

[Example 16]
Cp-1 Odbt (4F, 6F)-O2 (No. 26) 5%

3-HH-V (2-1) 35%
3-HH-V1 (2-1) 4%
3-HHB-1 (3-1) 3%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 4%
3-HHEH-5 (3-13) 3%
1V2-BB-F (21-1) 3%
3-BB (F) B (F, F)-CF3 (22-69) 3%
3-BB (F, F) XB (F, F) -F (22-97) 5%
3-HHXB (F, F) -F (22-100) 4%
3-GB (F, F) XB (F, F) -F (22-113) 3%
3-GB (F) B (F)-F (22-115) 3%
3-HBBB (F, F) -F (23-6) 3%
4-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
5-BB (F) B (F, F) X B (F, F)-F (23-47) 3%
3-GB (F) B (F, F) X B (F, F)-F (23-57) 3%
3-GBB (F, F) XB (F, F) -F (23-58) 2%
4-GBB (F, F) XB (F, F) -F (23-58) 2%
5-GBB (F, F) XB (F, F) -F (23-58) 2%
3-GB (F) B (F) B (F)-F (23-59) 2%
NI = 77.2 ° C .; = 1 = 16.8 mPa · s; Δn = 0.098; Δε = 5.0.

The liquid crystal compound according to the embodiment of the present invention has good physical properties. Liquid crystal compositions containing this compound can be widely used for liquid crystal display devices such as personal computers and televisions.

Claims

The compound represented by Formula (1).

In equation (1),
R 1 and R 2 are independently hydrogen or alkyl having 1 to 10 carbons, and in this alkyl, at least one —CH 2 — is —O—, —S—, —CO— or —SiH 2- and at least one -CH 2 CH 2 -may be replaced by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine May be replaced;
Rings A 1 and A 2 are independently cycloalkylene having 3 to 5 carbon atoms, and in this cycloalkylene, at least one —CH 2 — may be replaced by —O—, at least one — CH 2 CH 2 -may be replaced by -CH = CH-;
Rings N 1 and N 2 are independently 1,4-cyclohexylene, decahydronaphthalene-2,6-diyl or 1,4-phenylene, and in these groups, at least one —CH 2 — is And -O-, -S-, -CO-, or -SiH 2- , and at least one -CH 2 CH 2 -is replaced by -CH = CH- or -CH = N- In these divalent groups, at least one hydrogen may be fluorine, chlorine, -C≡N, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , or -OCH May be replaced by 2 F;
Y 1 and Y 2 are independently hydrogen, fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 or -OCH 2 F;
a and d are independently 0 or 1, and 1 ≦ a + d ≦ 2,
b and c are independently 0, 1 or 2, and b + c ≦ 2;
Z 1 , Z 2 , Z 3 and Z 4 are independently a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH 2 — is —O—, —S—, Or —CO— and one or two of —CH 2 CH 2 — may be replaced by —CH = CH— or —C≡C—, and in these divalent groups, at least One hydrogen may be replaced by fluorine.
In equation (1),
R 1 and R 2 independently represent hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, or 9 alkenyloxy;
Rings N 1 and N 2 are independently 1,4-cyclohexylene or 1,4-phenylene, and in these groups, at least one —CH 2 — may be replaced by —O— At least one —CH 2 CH 2 — may be replaced by —CH = CH—, and in these divalent groups, at least one hydrogen may be replaced by fluorine;
Y 1 and Y 2 are independently hydrogen or fluorine;
b and c are independently 0 or 1, and b + c ≦ 1;
Z 1 , Z 2 , Z 3 and Z 4 are independently a single bond or alkylene having 1 to 6 carbon atoms, and at least one —CH 2 — may be replaced by —O— The compound as described in.
The compound according to claim 1, which is represented by formulas (1-1) to (1-3).

In formulas (1-1) to (1-3),
R 1 and R 2 independently represent hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, or 9 alkenyloxy;
Ring A 1 is 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, or 1,3-cyclopentylene in which one —CH 2 — is replaced by —O— And
Ring N 1 and ring N 2 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by halogen, Or tetrahydropyran-2,5-diyl;
Z 1 , Z 2 and Z 3 are independently a single bond or alkylene having 1 to 6 carbon atoms, and at least one —CH 2 — may be replaced by —O—.
In formulas (1-1) to (1-3),
The compound according to claim 3, wherein ring A 1 is 1,2-cyclopropylene, 1,3-cyclobutylene or 1,3-cyclopentylene, and Z 2 and Z 3 are a single bond.
The compound according to claim 1, which is represented by any one of formulas (1-4) to (1-45).

In formulas (1-4) to (1-45),
R 1 and R 2 independently represent hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, alkoxyalkyl having 2 to 9 carbons, alkenyl having 2 to 10 carbons, or L 1 and L 2 are independently hydrogen or fluorine.
In formulas (1-4) to (1-45),
The compound according to claim 5, wherein R 1 is hydrogen and R 2 is alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyl having 2 to 10 carbons.
The compound according to claim 1, which is represented by formulas (1-46) to (1-51).

In formulas (1-46) to (1-51), R 2 is alkoxy having 1 to 9 carbons.
A liquid crystal composition comprising at least one compound according to any one of claims 1 to 7.
The liquid crystal composition according to claim 8, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In equations (2) to (4),
R 11 and R 12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — is replaced by —O— Also, in these groups, at least one hydrogen may be replaced by fluorine;
Ring B 1 , ring B 2 , ring B 3 and ring B 4 are each independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, or pyrimidine-2,5-diyl;
Z 11 , Z 12 and Z 13 are independently a single bond, -COO-, -CH 2 CH 2- , -CH = CH-, or -C≡C-.
The liquid crystal composition according to claim 8 or 9, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (13).

In equations (5) to (13),
R 13 , R 14 and R 15 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — is —O— Optionally substituted, in these groups at least one hydrogen may be replaced by fluorine and R 15 may be hydrogen or fluorine;
Ring C 1 , ring C 2 , ring C 3 and ring C 4 are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, or at least one hydrogen optionally substituted by fluorine 4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring C 5 and ring C 6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6 -Is diil;
Z 14, Z 15, Z 16 , and Z 17 are independently a single bond, -COO -, - CH 2 O -, - OCF 2 -, - CH 2 CH 2 -, or -OCF 2 CH 2 CH 2 -Is;
L 11 and L 12 are independently fluorine or chlorine;
S 11 is hydrogen or methyl;
X is -CHF- or -CF 2- ;
j, k, m, n, p, q, r, and s are independently 0 or 1, and the sum of k, m, n, and p is 1 or 2, q, r, and The sum of s is 0, 1, 2 or 3 and t is 1, 2 or 3.
The liquid crystal composition according to any one of claims 8 to 10, further comprising at least one compound selected from the group of compounds represented by formulas (21) to (23).

In equations (21) to (23),
R 16 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and these groups In which at least one hydrogen may be replaced by fluorine;
X 11 is fluorine, chlorine, -CF 3 , -CHF 2 , -CH 2 F, -OCF 3 , -OCHF 2 , -OCF 2 CHF 2 , or -OCF 2 CHFCF 3 ;
Ring D 1 , ring D 2 and ring D 3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl 1,3-dioxane-2,5-diyl, or pyrimidine-2,5-diyl;
Z 18, Z 19, and Z 20 are independently a single bond, -COO -, - CH 2 O -, - CF 2 O -, - OCF 2 -, - CH 2 CH 2 -, - CH = CH- , -C≡C-, or - (CH 2) 4 - a and;
L 13 and L 14 are independently hydrogen or fluorine.
The liquid crystal composition according to any one of claims 8 to 11, further comprising at least one compound selected from the group of compounds represented by formula (24).

In equation (24),
R 17 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and alkenyl, at least one —CH 2 — may be replaced by —O—, and these groups In which at least one hydrogen may be replaced by fluorine;
X 12 is -C≡N or -C≡C-C≡N;
Ring E 1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl Or pyrimidine-2,5-diyl;
Z 21 represents a single bond, -COO-, -CH 2 O-, -CF 2 O-, -OCF 2- , -CH 2 CH 2- , or -C≡C-;
L 15 and L 16 are independently hydrogen or fluorine;
i is 1, 2, 3 or 4;
A liquid crystal display device comprising the liquid crystal composition according to any one of claims 8 to 12.