JP2017007986A - Compound having anthracene skeleton, liquid crystal composition and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a liquid crystalline compound that has at least one sufficient property in physical properties such as high stability to heat or light, high clear point (or high maximum temperature), low minimum temperature of a liquid crystal phase, small viscosity, suitable optical anisotropy, negatively large dielectric anisotropy, suitable elastic modulus, and excellent compatibility with other liquid crystal compounds; a liquid crystal composition comprising the above compound; and a liquid crystal display element including the composition.SOLUTION: A compound represented by formula (1) is provided. In the formula (1), Rand Reach represent hydrogen, an alkyl group having 1 to 20 carbon atoms, or the like; ring Aand ring Aeach represent 1,4-cyclohexylene, 1,4-phenylene, or the like; Zand Zeach represent a single bond, an alkylene group having 1 to 6 carbon atoms, or the like; and a and b each independently represent 0, 1, 2, or 3, where the sum of a and b ranges from 0 to 4.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal compound, a liquid crystal composition, and a liquid crystal display element. More specifically, the present invention relates to a liquid crystal compound having an anthracene skeleton, a liquid crystal composition containing this compound and having a nematic phase, and a liquid crystal display device including the composition.

  Liquid crystal display elements are widely used in displays such as personal computers and televisions. This element utilizes physical properties such as optical anisotropy and dielectric anisotropy of a liquid crystalline compound. As an operation mode of the liquid crystal display element, PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (bistable twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS There are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and PSA (polymer sustained alignment). In the PSA mode element, a liquid crystal composition containing a polymer is used. In this composition, the alignment of liquid crystal molecules can be controlled by the polymer.

  In such a liquid crystal display element, a liquid crystal composition having appropriate physical properties is used. In order to further improve the characteristics of the device, it is preferable that the liquid crystalline compound contained in the composition has physical properties shown in the following (1) to (8). (1) high stability to heat and light, (2) high clearing point, (3) low minimum temperature of liquid crystal phase, (4) small viscosity (η), (5) appropriate optical anisotropy (Δn), (6) Negatively large dielectric anisotropy (Δε), (7) Appropriate elastic constant (K), (8) Excellent compatibility with other liquid crystal compounds.

  The effects of the physical properties of the liquid crystal compound on the device characteristics are as follows. As in (1), a compound having high stability to heat and light increases the voltage holding ratio of the device. This increases the lifetime of the device. A compound having a high clearing point as in (2) widens the usable temperature range of the device. As in (3), a compound having a lower minimum temperature of the liquid crystal phase such as a nematic phase or a smectic phase, particularly a lower minimum temperature of the nematic phase also extends the usable temperature range of the device. As in (4), a compound having a small viscosity shortens the response time of the device.

  Depending on the design of the device, a compound having an appropriate optical anisotropy, that is, a large optical anisotropy or a small optical anisotropy is required as shown in (5). When the response time is shortened by reducing the cell gap of the element, a compound having a large optical anisotropy is suitable. A compound having a large negative dielectric anisotropy as in (6) lowers the threshold voltage of the device. This reduces the power consumption of the element. On the other hand, a compound having a small dielectric anisotropy shortens the response time of the device by lowering the viscosity of the composition. This compound widens the usable temperature range of the device by increasing the maximum temperature of the nematic phase.

  Regarding (7), a compound having a large elastic constant shortens the response time of the device. A compound having a small elastic constant lowers the threshold voltage of the device. Therefore, an appropriate elastic constant is required according to the characteristics to be improved. A compound having excellent compatibility with other liquid crystal compounds as in (8) is preferred. This is because liquid crystal compounds having different physical properties are mixed to adjust the physical properties of the composition.

Until now, various liquid crystal compounds having a large negative dielectric anisotropy have been synthesized. Various liquid crystalline compounds having large optical anisotropy have been synthesized. This is because the new compound is expected to have excellent physical properties not found in conventional compounds. This is because it is expected that an appropriate balance between at least two physical properties in the composition can be obtained by adding the novel compound to the liquid crystal composition. Under such circumstances, a compound having an excellent balance between the physical properties (1) to (8) and an appropriate balance is desired.

On page 48 of Patent Document 1, the following compounds are described.

International Publication No. 2005/5557

  The first problem is high stability against heat and light, high clearing point (or high maximum temperature of nematic phase), low minimum temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, large negative dielectric constant. It is to provide a liquid crystal compound satisfying at least one of physical properties such as isotropic property, appropriate elastic constant, and excellent compatibility with other liquid crystal compounds. It is to provide a compound having a large optical anisotropy or a large dielectric anisotropy as compared with a similar compound. The second problem is that it contains this compound and has high stability to heat and light, high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, negatively large dielectric constant. The object is to provide a liquid crystal composition satisfying at least one of physical properties such as isotropic, large specific resistance, and appropriate elastic constant. An object of the present invention is to provide a liquid crystal composition having an appropriate balance regarding at least two physical properties. A third problem is to provide a liquid crystal display device comprising 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, and a long lifetime. That is.

式（１）において、
Ｒ^１およびＲ^２は独立して、水素または炭素数１から２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−、または−ＳｉＨ_２−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；
環Ａ^１および環Ａ^２は独立して、１，４−シクロへキシレン、１，４−フェニレン、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり、この１，４−シクロへキシレン、１，４−フェニレン、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−、または−ＳｉＨ_２−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−ＣＨ＝Ｎ−で置き換えられてもよく、そしてこれらにおいて、少なくとも１つの水素は、フッ素、塩素、−Ｃ≡Ｎ、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆで置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−、または−ＳｉＨ_２−で置き換えられてもよく、１つまたは２つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；
Ｌ^１、Ｌ^２、Ｌ^３、およびＬ^４は独立して、水素、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆであり、そしてＬ^１、Ｌ^２、およびＬ^４の少なくとも１つは、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆであり；
ａおよびｂは独立して、０、１、２、または３であり、ａおよびｂの和は０から４である。 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 including the composition.

In equation (1),
R ¹ and R ² are independently hydrogen or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — is —O—, —S—, —CO—, or —SiH _2. - may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, in these, is replaced with at least one hydrogen fluorine or chlorine May be;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6. -Diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene- In 2,6-diyl or naphthalene-2,6-diyl, at least one —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —. one of _-CH 2 CH ₂ - may be replaced -CH = CH- or -CH = N-, and in these, at least one of hydrogen, fluorine, chlorine, -C≡N, -CF _{, -CHF 2, -CH 2 F,} -OCF 3, -OCHF 2, or may be replaced by -OCH ₂ F;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 6 carbon atoms, in which at least one —CH ₂ — is —O—, —S—, —CO—, or —SiH. _2- may be replaced, and one or two -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen is fluorine or chlorine May be replaced by;
L ¹ , L ² , L ³ , and L ⁴ are independently hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. And at least one of L ¹ , L ² , and L ⁴ is fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F ;
a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0 to 4.

  The first advantage is high stability against heat and light, high clearing point (or high maximum temperature of nematic phase), low minimum temperature of liquid crystal phase, small viscosity, appropriate optical anisotropy, large negative dielectric constant. It is to provide a liquid crystal compound satisfying at least one of physical properties such as isotropic property, appropriate elastic constant, and excellent compatibility with other liquid crystal compounds. It is to provide a compound having a large optical anisotropy or a negatively large dielectric anisotropy as compared with a similar compound. The second advantage is that it contains this compound and has high stability against heat and light, high maximum temperature of nematic phase, low minimum temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric constant. The object is to provide a liquid crystal composition satisfying at least one of physical properties such as isotropic, large specific resistance, and appropriate elastic constant. The advantage is to provide a liquid crystal composition having an appropriate balance regarding at least two physical properties. The third advantage is to provide a liquid crystal display device comprising 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, and a long lifetime. That is.

  The usage of 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 compounds” are compounds having a liquid crystal phase such as a nematic phase and a smectic phase, and having no liquid crystal phase, but adjusting the physical properties of the composition such as maximum temperature, minimum temperature, viscosity and dielectric anisotropy. It is a general term for compounds that are added for the purpose. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. “Liquid crystal display element” is a general term for liquid crystal display panels and liquid crystal display modules. The “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The ratio (content) of the liquid crystal compound is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition. This composition requires additives such as polymerizable compounds, polymerization initiators, polymerization inhibitors, optically active compounds, antioxidants, UV absorbers, light stabilizers, heat stabilizers, dyes, and antifoaming agents. Added accordingly. The ratio (addition amount) of the additive is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Weight parts per million (ppm) may be used. The ratio of the polymerization initiator or the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

  The “clearing point” is a transition temperature between a liquid crystal phase and an isotropic phase in a liquid crystal compound. “Lower limit temperature of liquid crystal phase” is a transition temperature of a solid-liquid crystal phase (such as a smectic phase or a nematic phase) in a liquid crystal compound. The “maximum temperature of a nematic phase” is a transition temperature of a nematic phase to an isotropic phase in a mixture or liquid crystal composition of a liquid crystal compound and a mother liquid crystal, and may be abbreviated as “maximum temperature”. “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”. The expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.

The compound represented by Formula (1) may be abbreviated as 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. In formulas (1) to (15), symbols such as A ¹ , B ¹ , and C ¹ surrounded by hexagons correspond to rings such as ring A ¹ , ring B ¹ , and ring C ¹ , respectively. The hexagon represents a six-membered ring such as cyclohexane or benzene. The hexagon may represent a condensed ring such as naphthalene or a bridged ring such as adamantane.

In the chemical formula, the symbol of the terminal group R ¹ is used for a plurality of compounds. In these compounds, two groups represented by two arbitrary R ¹ may be the same or different. For example, there is a case where R ^{1 of} the compound (1-1) is ethyl and R ¹ of the compound (1-2) is ethyl. In some cases, R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to symbols such as R ¹¹ and Z ¹¹ . In compound (15), when i is 2, two rings E ¹ exist. In this compound, two groups represented by two rings E ¹ 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. The expression “at least one 'A' may be replaced by 'B'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, it means that their positions can be selected without limitation. This rule also applies to the expression “at least one 'A' is replaced by 'B'”. The expression “at least one 'A' may be replaced with 'B', 'C', or 'D'" is used when any 'A' is replaced with 'B' When A 'is replaced with' C ', and when any' A 'is replaced with' D ', more than one' A 'can be' B ',' C ', and / or' D ' It means that the case where at least two are replaced is included. For example, “alkyl in which at least one —CH ₂ — may be replaced by —O— or —CH═CH—” includes alkyl, alkoxy, alkoxyalkyl, alkenyl, alkoxyalkenyl, alkenyloxyalkyl. Note that it is not preferable that two consecutive —CH ₂ — are replaced by —O— to form —O—O—. In alkyl and the like, it is not preferable that —CH ₂ — in the methyl moiety (—CH ₂ —H) is replaced by —O— to become —O—H.

Halogen means fluorine, chlorine, bromine and iodine. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine. The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyl is generally preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis for increasing 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 divalent groups such as tetrahydropyran-2,5-diyl.

  The present invention includes the following items.

式（１）において、
Ｒ^１およびＲ^２は独立して、水素または炭素数１から２０のアルキルであり、このアルキルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−、または−ＳｉＨ_２−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；
環Ａ^１および環Ａ^２は独立して、１，４−シクロへキシレン、１，４−フェニレン、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり、この１，４−シクロへキシレン、１，４−フェニレン、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−、または−ＳｉＨ_２−で置き換えられてもよく、少なくとも１つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−ＣＨ＝Ｎ−で置き換えられてもよく、そしてこれらにおいて、少なくとも１つの水素は、フッ素、塩素、−Ｃ≡Ｎ、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆで置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、単結合または炭素数１から６のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−、または−ＳｉＨ_２−で置き換えられてもよく、１つまたは２つの−ＣＨ_２ＣＨ_２−は−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素または塩素で置き換えられてもよく；
Ｌ^１、Ｌ^２、Ｌ^３、およびＬ^４は独立して、水素、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆであり、そしてＬ^１、Ｌ^２、およびＬ^４の少なくとも１つは、フッ素、塩素、−ＣＦ_３、−ＣＨＦ_２、−ＣＨ_２Ｆ、−ＯＣＦ_３、−ＯＣＨＦ_２、または−ＯＣＨ_２Ｆであり；
ａおよびｂは独立して、０、１、２、または３であり、ａおよびｂの和は０から４である。 Item 1. The compound represented by Formula (1).

In equation (1),
R ¹ and R ² are independently hydrogen or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — is —O—, —S—, —CO—, or —SiH _2. - may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, in these, is replaced with at least one hydrogen fluorine or chlorine May be;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6. -Diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene- In 2,6-diyl or naphthalene-2,6-diyl, at least one —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —. one of _-CH 2 CH ₂ - may be replaced -CH = CH- or -CH = N-, and in these, at least one of hydrogen, fluorine, chlorine, -C≡N, -CF _{, -CHF 2, -CH 2 F,} -OCF 3, -OCHF 2, or may be replaced by -OCH ₂ F;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 6 carbon atoms, in which at least one —CH ₂ — is —O—, —S—, —CO—, or —SiH. _2- may be replaced, and one or two -CH ₂ CH ₂ -may be replaced by -CH = CH- or -C≡C-, in which at least one hydrogen is fluorine or chlorine May be replaced by;
L ¹ , L ² , L ³ , and L ⁴ are independently hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. And at least one of L ¹ , L ² , and L ⁴ is fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F ;
a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0 to 4.

式（１−１）から（１−６）において、
Ｒ^１およびＲ^２は独立して、水素、炭素数１から１０のアルキル、炭素数１から９のアルコキシ、炭素数２から９のアルコキシアルキル、炭素数２から１０のアルケニル、または炭素数２から９のアルケニルオキシであり；
環Ａ^１および環Ａ^２は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、テトラヒドロ−２Ｈ−ピラン−２−オン−３，６−ジイル、１，３−ジオキサン−２，５−ジイル、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルであり、この１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、テトラヒドロ−２Ｈ−ピラン−２−オン−３，６−ジイル、１，３−ジオキサン−２，５−ジイル、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、またはナフタレン−２，６−ジイルにおいて、少なくとも１つの水素は、フッ素、塩素、−ＣＦ_３、または−ＣＨＦ_２で置き換えられてもよく；
Ｚ^１およびＺ^２は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＦ_２ＣＦ_２−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−ＣＦ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＨ_２ＣＯ−、−ＣＯＣＨ_２−、−ＣＨ_２ＳｉＨ_２−、−ＳｉＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ＝ＣＨＣＨ_２−、−（ＣＨ_２）_２ＣＯＯ−、−（ＣＨ_２）_２ＯＣＯ−、−ＯＣＯ（ＣＨ_２）_２−、−ＣＯＯ（ＣＨ_２）_２−、−（ＣＨ_２）_２ＣＦ_２Ｏ−、−（ＣＨ_２）_２ＯＣＦ_２−、−ＯＣＦ_２（ＣＨ_２）_２−、−ＣＦ_２Ｏ（ＣＨ_２）_２−、−（ＣＨ_２）_３Ｏ−、または−Ｏ（ＣＨ_２）_３−であり；
Ｌ^１、Ｌ^２、Ｌ^３、およびＬ^４は独立して、水素、フッ素、−ＣＦ_３、または−ＣＨ_２Ｆであり、そしてＬ^１、Ｌ^２、およびＬ^４の少なくとも１つは、フッ素、−ＣＦ_３、または−ＣＨ_２Ｆである。 Item 2. Item 6. The compound according to item 1, represented by any one of formulas (1-1) to (1-6).

In the formulas (1-1) to (1-6),
R ¹ and R ² are independently 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 2 to carbons 9 alkenyloxy;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, tetrahydro-2H-pyran-2- On-3,6-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2 , 5-diyl, tetrahydro-2H-pyran-2-one-3,6-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2, In diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, It may be replaced by -CF ₃ or -CHF _2,;
Z ¹ and Z ² are each independently a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CH═CH—, —CF ₂ CF ₂ —, —CF═CH—, —CH═CF—, —CF═CF—, —C≡C—, —CH ₂ CO—, —COCH ₂ —, —CH ₂ SiH ₂ —, —SiH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —CH ₂ CH═CHCH ₂ —, — (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 —;
L ¹ , L ² , L ³ , and L ⁴ are independently hydrogen, fluorine, —CF ₃ , or —CH ₂ F, and at least one of L ¹ , L ² , and L ⁴ is fluorine , -CF _3, or -CH ₂ F.

Item 3. In the formulas (1-1) to (1-6) according to item 2, R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or carbon 2 To Alkoxyalkyl of 1 to 9, Alkenyl of 2 to 10 carbons, or Alkenyloxy of 2 to 9 carbons; Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene Or 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹ and Z ² are independently a single bond, —COO—, —OCO—, —CH ₂ O—, — _{OCH 2 -, - CF 2 O} -, - OCF 2 -, - CH 2 CH 2 -, - CH = CH -, - CF 2 CF 2 -, - (CH 2) 4 -, or _-CH 2 CH = CHCH _2- ; L ¹ , L ² Item 3. The compound according to Item 2, wherein L ³ , and L ⁴ are independently hydrogen, fluorine, or —CF ₃ , and at least one of L ¹ , L ² , and L ⁴ is fluorine.

Item 4. In formulas (1-1) to (1-6) according to item 2, R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or carbon number 2 to 10 alkenyl; ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-chloro-1,4 -Phenylene, 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4 -Phenylene or 2,3,5-trifluoro-1,4-phenylene; Z ¹ and Z ² are independently a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—. , -OCF ₂ -, or _-CH 2 CH ₂ And ^{a; L 1, L 2, L} 3, and ^{L 4} are each independently hydrogen or fluorine, and ^L 1, ^{L 2,} and at least two ^{L 4} are a fluorine, according to claim 2 Compound.

Item 5. In formulas (1-1) to (1-6) according to item 2, R ¹ and R ² are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or 2 to carbons. 10 alkenyl; ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1, Item 3. The compound according to Item 2, wherein the compound is 4-phenylene; Z ¹ and Z ² are a single bond; L ¹ and L ² are fluorine, and L ³ and L ⁴ are independently hydrogen or fluorine.

式（１−１）、（１−２）、および（１−３）において、
Ｒ^１およびＲ^２は独立して、炭素数１から１０のアルキルまたは炭素数１から９のアルコキシであり；
環Ａ^１および環Ａ^２は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、または２，３−ジフルオロ−１，４−フェニレンであり；
Ｚ^１およびＺ^２は独立して単結合、−ＣＨ_２Ｏ−、または−ＯＣＨ_２−であり；
Ｌ^１、Ｌ^２、およびＬ^４がフッ素であり、Ｌ^３が水素、フッ素、または−ＣＦ_３である。 Item 6. Item 2. The compound according to item 1, represented by formula (1-1), (1-2), or (1-3).

In formulas (1-1), (1-2), and (1-3),
R ¹ and R ² are independently alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene;
Z ¹ and Z ² are each independently a single bond, —CH ₂ O—, or —OCH ₂ —;
L ¹ , L ² , and L ⁴ are fluorine, and L ³ is hydrogen, fluorine, or —CF ₃ .

式（ａ）または（ｂ）において、
Ｒ^１およびＲ^２は独立して、水素、炭素数１から１０のアルキル、炭素数１から９のアルコキシ、または炭素数２から１０のアルケニルであり；
環Ａ^１および環Ａ^２は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２−クロロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２−クロロ−３−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、または２，３，５−トリフルオロ−１，４−フェニレンであり：
Ｚ^１およびＺ^２は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、または−ＣＨ＝ＣＨ−であり；
ａおよびｂは独立して、０、１、または２であり、ａおよびｂの和は０、１、または２である。 Item 7. Item 2. The compound according to item 1, represented by formula (a) or (b):

In formula (a) or (b):
R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyl having 2 to 10 carbons;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-chloro-1,4-phenylene, 2,3-difluoro. -1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or 2,3 5-trifluoro-1,4-phenylene is:
Z ¹ and Z ² are each independently a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, Or -CH = CH-;
a and b are independently 0, 1, or 2, and the sum of a and b is 0, 1, or 2.

Item 8. In formula (a) or (b), the R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or 2 to 10 carbons Alkenyl; ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4- Z ¹ and Z ² are independently a single bond, —CH ₂ O—, or —OCH ₂ —; a and b are independently 0 or 1, and the sum of a and b Item 8. The compound according to Item 7, wherein is 0, 1, or 2.

式（ａ−１）から（ａ−３）、および式（ｂ−１）から（ｂ−３）において、
Ｒ^１およびＲ^２は独立して、炭素数１から１０のアルキルまたは炭素数１から９のアルコキシであり；環Ａ^１および環Ａ^２は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、または２，３−ジフルオロ−１，４−フェニレンであり；Ｚ^１およびＺ^２は独立して、単結合、−ＣＨ_２Ｏ−、または−ＯＣＨ_２−である。 Item 9. Item 8. The compound according to item 7, represented by any one of formulas (a-1) to (a-3) and formulas (b-1) to (b-3).

In formulas (a-1) to (a-3) and formulas (b-1) to (b-3),
R ¹ and R ² are independently alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons; ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene; Z ¹ and Z ² are independently a single bond, —CH ₂ O—, or —OCH. _2- .

Item 10. Item 10. A liquid crystal composition containing at least one compound according to any one of items 1 to 9.

式（２）から（４）において、
Ｒ^１１およびＲ^１２は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルまたはアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｂ^１、環Ｂ^２、環Ｂ^３、および環Ｂ^４は独立して、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，５−ジフルオロ−１，４−フェニレン、またはピリミジン−２，５−ジイルであり；
Ｚ^１１、Ｚ^１２、およびＺ^１３は独立して、単結合、−ＣＯＯ−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、または−Ｃ≡Ｃ−である。 Item 11. Item 11. The liquid crystal composition according to item 10, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the 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 or alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, in these, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are 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 each independently a single bond, —COO—, —CH ₂ CH ₂ —, —CH═CH—, or —C≡C—.

式（５）から（１１）において、
Ｒ^１３およびＲ^１４は独立して、炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルまたはアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｒ^１５は、水素、フッ素、炭素数１から１０のアルキル、または炭素数２から１０のアルケニルであり、このアルキルおよびアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく；
環Ｃ^１、環Ｃ^２、環Ｃ^３、および環Ｃ^４は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
環Ｃ^５および環Ｃ^６は独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、またはデカヒドロナフタレン−２，６−ジイルであり；
Ｚ^１４、Ｚ^１５、Ｚ^１６、およびＺ^１７は独立して、単結合、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、または−ＯＣＦ_２ＣＨ_２ＣＨ_２−であり；
Ｌ^１１およびＬ^１２は独立して、フッ素または塩素であり；
Ｓ^１１は、水素またはメチルであり；
Ｘは、−ＣＨＦ−または−ＣＦ_２−であり；
ｊ、ｋ、ｍ、ｎ、ｐ、ｑ、ｒ、およびｓは独立して、０または１であり、ｋ、ｍ、ｎ、およびｐの和は、１または２であり、ｑ、ｒ、およびｓの和は、０、１、２、または３であり、ｔは、１、２、または３である。 Item 12. Item 12. The liquid crystal composition according to item 10 or 11, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (11).

In the equations (5) to (11),
R ¹³ and R ¹⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, in these, at least one hydrogen may be replaced by fluorine;
R ¹⁵ is hydrogen, fluorine, 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 which at least one hydrogen may be replaced by fluorine;
Ring C ¹ , Ring C ² , Ring C ³ , and Ring C ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen replaced with fluorine 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{C 5} and ring ^{C 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Diyl;
^{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, 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.

式（１２）から（１４）において、
Ｒ^１６は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルまたはアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１１は、フッ素、塩素、−ＣＦ₃、−ＣＨＦ₂、−ＣＨ₂Ｆ、−ＯＣＦ₃、−ＯＣＨＦ₂、−ＯＣＦ₂ＣＨＦ₂、または−ＯＣＦ₂ＣＨＦＣＦ₃であり；
環Ｄ^１、環Ｄ^２、および環Ｄ^３は独立して、１，４−シクロヘキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^１８、Ｚ^１９、およびＺ^２０は独立して、単結合、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、または−（ＣＨ_２）_４−であり；
Ｌ^１３およびＬ^１４は独立して、水素またはフッ素である。 Item 13. Item 13. The liquid crystal composition according to any one of items 10 to 12, further containing at least one compound selected from the group of compounds represented by formulas (12) to (14):

In the equations (12) to (14),
R ¹⁶ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—, in which at least 1 Two hydrogens 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, 1,4-phenylene in which at least one hydrogen is 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 each 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 —;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine.

式（１５）において、
Ｒ^１７は炭素数１から１０のアルキルまたは炭素数２から１０のアルケニルであり、このアルキルまたはアルケニルにおいて、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく、これらにおいて、少なくとも１つの水素はフッ素で置き換えられてもよく；
Ｘ^１２は、−Ｃ≡Ｎまたは−Ｃ≡Ｃ−Ｃ≡Ｎであり；
環Ｅ^１は、１，４−シクロヘキシレン、１，４−フェニレン、少なくとも１つの水素がフッ素で置き換えられた１，４−フェニレン、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはピリミジン−２，５−ジイルであり；
Ｚ^２１は、単結合、−ＣＯＯ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＨ_２ＣＨ_２−、または−Ｃ≡Ｃ−であり；
Ｌ^１５およびＬ^１６は独立して、水素またはフッ素であり；
ｉは、１、２、３、または４である。 Item 14. Item 14. The liquid crystal composition according to any one of items 10 to 13, further containing at least one compound selected from the group of compounds represented by formula (15).

In equation (15),
R ¹⁷ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — may be replaced by —O—, in which at least 1 Two hydrogens 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, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2 , 5-diyl, or pyrimidine-2,5-diyl;
Z ²¹ is 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 15. Item 15. A liquid crystal display device comprising the liquid crystal composition according to any one of items 10 to 14.

  The present invention also includes the following items. (A) one selected from the group of a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent The liquid crystal composition as described above, further comprising two or at least three additives. (B) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.). ) Is 2 or more. (C) The above liquid crystal display element in which the operation mode of the liquid crystal display element is a TN mode, an ECB mode, an OCB mode, an IPS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix (AM) method .

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

1. Embodiment of Compound (1) The compound (1) of the present invention has an anthracene skeleton. The compound (1) is characterized by having a large optical anisotropy compared to a similar compound. The compound (1) is characterized by having a negatively large dielectric anisotropy compared to a similar compound. A preferred example of compound (1) will be described. Preferred examples of the terminal groups R ¹ and R ² , the rings A ¹ and A ² , the bonding groups Z ¹ and Z ² , and the substituents L ¹ , L ² , L ³ , and L ^{4 in} the compound (1) are the compounds ( This also applies to the sub-formula of compound (1) such as 1-1) to (1-6). In the compound (1), physical properties can be arbitrarily adjusted by appropriately combining these groups. Since there is no great difference in the physical properties of the compound, the compound (1) may contain an isotope such as ² H (deuterium) and ¹³ C in an amount larger than the natural abundance. In addition, the definition of the symbol of the compound (1) is as described in item 1.

In the formula (1), R ¹ and R ² are independently hydrogen or alkyl having 1 to 20 carbons, and in this alkyl, at least one —CH ₂ — is —O—, —S—, —CO. -, or -SiH ₂ - may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, in these, at least one hydrogen It may be replaced with fluorine or chlorine. Here, “these” in the definition of R ¹ and R ² in the formula (1) is “hydrogen or alkyl having 1 to 20 carbon atoms, and in this alkyl, at least one —CH ₂ — is — O—, —S—, —CO—, or —SiH ₂ — may be substituted, and at least one —CH ₂ CH ₂ — may be substituted with —CH═CH— or —C≡C—. Group ".

Preferred R ¹ or R ² is 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 2 to 9 carbons Alkenyloxy.

Preferred _{alkyl, -CH 3, -C 2 H 5} , -C 3 H 7, -C 4 H 9, -C 5 H 11, a -C _{6 H 13} or _-C 7 _{H 15,.}

Preferred alkoxy is —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OC ₄ H ₉ , —OC ₅ H ₁₁ , —OC ₆ H ₁₃ , or —OC ₇ H ₁₅ .

Preferred alkoxyalkyl is —CH ₂ OCH ₃ , —CH ₂ OC ₂ H ₅ , —CH ₂ OC ₃ H ₇ , — (CH ₂ ) ₂ —OCH ₃ , — (CH ₂ ) ₂ —OC ₂ H ₅ , — It is (CH ₂ ) ₂ —OC ₃ H ₇ , — (CH ₂ ) ₃ —OCH ₃ , — (CH ₂ ) ₄ —OCH ₃ , or — (CH ₂ ) ₅ —OCH ₃ .

Preferred alkenyl _{is, -CH = CH 2, -CH =} CHCH 3, -CH 2 CH = CH 2, -CH = CHC 2 H 5, -CH 2 CH = CHCH 3, - (CH 2) 2 -CH = CH ₂ , —CH═CHC ₃ H ₇ , —CH ₂ CH═CHC ₂ H ₅ , — (CH ₂ ) ₂ —CH═CHCH ₃ , or — (CH ₂ ) ₃ —CH═CH ₂ .

Preferred alkenyloxy is —OCH═CH ₂ , —OCH ₂ CH═CH ₂ , —OCH ₂ CH═CHCH ₃ , or —OCH ₂ CH═CHC ₂ H ₅ .

Preferred R ¹ is hydrogen, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H ₁₁ , —C ₆ H ₁₃ , —OCH ₃ , —OC ₂ H _{5. , -OC 3 H 7, -OC 4} H 9, -OC 5 H 11, -CH 2 OCH 3, -CH = CH 2, -CH = CHCH 3, - (CH 2) 2 -CH = CH 2, - _{CH 2 CH = CHC 2 H 5} , - (CH 2) 2 -CH = CHCH 3, -OCH 2 CH = CH 2, -OCH 2 CH = CHCH 3, or _{-OCH 2 CH = CHC 2 H 5} . More preferable R ¹ is hydrogen, —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —C ₄ H ₉ , —C ₅ H ₁₁ , —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H. _{7, -OC} 4 _H 9, is -OC _{5 H 11.} Particularly preferred R ¹ is —CH ₃ , —C ₂ H ₅ , —C ₃ H ₇ , —OCH ₃ , —OC ₂ H ₅ , or —OC ₃ H ₇ .

R ¹ is preferably linear, but may be branched. When R ¹ is linear, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R ¹ is a branched chain, the compatibility with other liquid crystal compounds is good. A compound in which R ¹ is optically active is useful as a chiral dopant. By adding this compound to the composition, a reverse twisted domain generated in the liquid crystal display device can be prevented. A compound in which R ¹ is not optically active is useful as a component of the composition. When R ¹ is alkenyl, the preferred configuration depends on the position of the double bond. An alkenyl compound having a preferred configuration has a low viscosity, a high maximum temperature, or a wide temperature range of the liquid crystal phase.

The preferred configuration of —CH═CH— in alkenyl depends on the position of the double bond. _{-CH = CHCH 3, -CH = CHC} 2 H 5, -CH = CHC 3 H 7, -CH = CHC 4 H 9, -C 2 H 4 CH = CHCH 3, and _{-C 2 H} 4 CH = CHC 2 In alkenyl having a double bond at odd positions such as H ₅ , the trans configuration is preferable. -CH ₂ CH ₌ CHCH _3, cis configuration in the alkenyl having an even position to the double bond, such as _{-CH 2 CH = CHC 2 H 5} , and _-CH 2 CH = _CHC 3 _{H 7} are preferred. An alkenyl compound having a preferred configuration has a high clearing point or a wide temperature range of a liquid crystal phase. Mol. Cryst. Liq. Cryst., 1985, 131, 109 and Mol. Cryst. Liq. Cryst., 1985, 131, 327 have detailed descriptions.

In formula (1), ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4- Tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3 , 4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, at least one —CH ₂ — is replaced by —O—, —S—, —CO—, or —SiH ₂ —. And at least one —CH ₂ CH ₂ — may be replaced by —CH═CH— or —CH═N—, and in these, at least one hydrogen is fluorine, chlorine, _{-C≡N, -CF 3, -CHF 2,} -CH 2 F, -OCF 3, -OCHF 2, or may be replaced by -OCH ₂ F. Here, “these” in the definition of ring A ¹ and ring A ² in formula (1) means “1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl”. 1,2,3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2, In 6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, or naphthalene-2,6-diyl, at least one —CH ₂ — is —O—, —S—, —CO—. , Or —SiH ₂ —, wherein at least one —CH ₂ CH ₂ — represents a ring optionally substituted with —CH═CH— or —CH═N— ”.

Preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, tetrahydro-2H-pyran-2-one- 3,6-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2,3 4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5 -Diyl, tetrahydro-2H-pyran-2-one-3,6-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2, In diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, -CF ₃ or may be replaced by -CHF _2,. More preferable ring A ¹ or ring A ² is 1,4-cyclohexylene or 1,4-phenylene, and in this 1,4-cyclohexylene or 1,4-phenylene, at least one hydrogen is fluorine or chlorine. May be replaced.

Particularly preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-chloro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or 2,3,5 -Trifluoro-1,4-phenylene. Most preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene.

When ring A ¹ or ring A ² is 1,4-cyclohexylene, the clearing point is high and the viscosity is small. When ring A ¹ or ring A ² is 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine, the optical anisotropy is large and the orientation order parameter ( orientational order parameter) is relatively large. When ring A ¹ or ring A ² is 1,4-phenylene in which at least one hydrogen is replaced by fluorine, the dielectric anisotropy is large.

In Formula (1), Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —S—, — CO—, or —SiH ₂ — may be substituted, and one or two —CH ₂ CH ₂ — may be substituted with —CH═CH— or —C≡C—, in which at least 1 One hydrogen may be replaced by fluorine or chlorine. Here, “these” in the definition of Z ¹ and Z ² in the formula (1) is “a single bond or alkylene having 1 to 6 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —S—, —CO—, or —SiH ₂ — may be substituted, and one or two —CH ₂ CH ₂ — is replaced by —CH═CH— or —C≡C—. Group ".

Preferred Z ¹ or Z ² is a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CH. _{= CH -, - CF 2 CF} 2 -, - CF = CH -, - CH = CF -, - CF = CF -, - C≡C -, - CH 2 CO -, - COCH 2 -, - CH 2 SiH _{2 -, - SiH 2 CH 2} -, - (CH 2) 4 -, - CH 2 CH = CHCH 2 -, - (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} - is.

More preferable Z ¹ or Z ² is a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, — _{CH = CH -, - CF 2} CF 2 -, - (CH 2) 4 -, or _{-CH 2} CH = CHCH 2 - a. Particularly preferred Z ¹ or Z ² is a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, or -CH = CH-. Most preferred Z ¹ or Z ² is a single bond, —CH ₂ O—, or —OCH ₂ —. Most preferred Z ¹ or Z ² is also a single bond.

When Z ¹ or Z ² is a single bond, the chemical stability is high and the viscosity is low. When Z ¹ or Z ² is —CF ₂ O—, the viscosity is small, the dielectric anisotropy is large, and the maximum temperature is high.

In the formula (1), L ¹ , L ² , L ³ , and L ⁴ are independently hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or a -OCH ₂ F, and at least one of ^L 1, ^{L 2,} and ^{L 4} is fluorine, _{chlorine, -CF 3, -CHF 2, -CH} 2 F, -OCF 3, -OCHF 2 or, it is a -OCH ₂ F.

Preferred L ¹ , L ² , L ³ , or L ⁴ is hydrogen, fluorine, —CF ₃ , or —CH ₂ F, and at least one of L ¹ , L ² , and L ⁴ is fluorine, — CF ₃ or —CH ₂ F. More preferred L ¹ , L ² , L ³ , or L ⁴ is hydrogen, fluorine, or —CF ₃ , and at least one of L ¹ , L ² , and L ⁴ is fluorine. Particularly preferred L ¹ , L ² , L ³ , or L ⁴ is hydrogen or fluorine, and at least two of L ¹ , L ² , and L ⁴ are fluorine. Most preferably, L ¹ and L ² are fluorine and L ³ and L ⁴ are independently hydrogen or fluorine.

  In formula (1), a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0 to 4. A preferred sum of a and b is 0, 1, or 2. A more preferable sum of a and b is 0 or 1. A particularly preferred sum of a and b is 0. When the sum of a and b is 0, the viscosity is small. When the sum of a and b is 1, the clearing point is high.

  Examples of preferred compound (1) are compounds (1-1) to (1-6) described in item 2. More desirable compound (1) is compound (1-1), (1-2), or (1-3). Particularly preferred compound (1) is compound (1-1). The compound (1-1) is preferable from the viewpoint of low viscosity. Compounds (1-2) and (1-3) are preferred from the viewpoint of a high clearing point. The compound (1-1) is preferable from the viewpoint of large optical anisotropy.

2. Synthesis of Compound (1) A method for synthesizing compound (1) will be described. Compound (1) can be synthesized by appropriately combining organic synthetic chemistry methods. Methods for introducing the desired end groups, rings, and linking groups into the starting materials are “Organic Syntheses, John Wiley & Sons, Inc.”, “Organic Reactions” (Organic Reactions, John Wiley & Sons). , Inc.), "Comprehensive Organic Synthesis, Pergamon Press", and "New Experimental Chemistry Course" (Maruzen).

2-1. Generation of the linking group Z A scheme is first shown for the method of generating the linking groups Z ¹ and Z ² . Next, the reaction described in the scheme in the methods (1) to (11) will be described. In this scheme, MSG ¹ (or MSG ² ) is a monovalent organic group having at least one ring. The monovalent organic groups represented by a plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1J) correspond to compound (1).

(1) Formation of a single bond Arylboric acid (21) and halide (22) are reacted in the presence of a catalyst such as carbonate and tetrakis (triphenylphosphine) palladium to synthesize compound (1A). This compound (1A) is obtained by reacting halide (23) with n-butyllithium, then zinc chloride, and reacting halide (22) in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. Is also synthesized.

(2) Formation of —COO— The halide (23) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (24). Compound (1B) is synthesized by dehydrating compound (25) and carboxylic acid (24) in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine).

(3) Formation of —CF ₂ O— The compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain the thionoester (26). The thionoester (26) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize the compound (1C). See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating thionoester (26) with DAST ((diethylamino) sulfur trifluoride). See WH 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 (22) is treated with n-butyllithium and then reacted with formamide such as DMF (N, N-dimethylformamide) to obtain aldehyde (28). The phosphonium salt (27) is treated with a base such as potassium t-butoxide to generate phosphorus ylide. This phosphorus ylide is reacted with aldehyde (28) to synthesize compound (1D). Depending on the reaction conditions, a cis isomer is formed, and the cis isomer is isomerized to a trans isomer as necessary.

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

(6) Formation of — (CH ₂ ) ₄ — A compound having — (CH ₂ ) ₂ —CH═CH— is obtained by using the phosphonium salt (29) instead of the phosphonium salt (27) and according to the method of the method (4). obtain. This is catalytically hydrogenated to synthesize compound (1F).

(7) Formation of —CH ₂ CH═CHCH ₂ — A compound according to the method of method (4) using phosphonium salt (30) instead of phosphonium salt (27) and aldehyde (31) instead of aldehyde (28) Synthesize (1G). Depending on the reaction conditions, a trans isomer is produced, and the trans isomer is isomerized to a cis isomer as necessary.

(8) Formation of -C≡C- After reacting 2-methyl-3-butyn-2-ol with halide (23) in the presence of a catalyst of dichloropalladium and copper halide, basic conditions To obtain compound (32). Compound (1H) is synthesized by reacting compound (32) with halide (22) in the presence of a catalyst of dichloropalladium and copper halide.

(9) Formation of —CF═CF— The halide (23) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (33). The halide (22) is treated with n-butyllithium and then reacted with the compound (33) to synthesize the compound (1I).

(10) Formation of —OCH ₂ — Compound (34) is obtained by reducing aldehyde (28) with a reducing agent such as sodium borohydride. The bromide (35) is obtained by brominating the compound (34) with hydrobromic acid or the like. Compound (1J) is synthesized by reacting bromide (35) with compound (36) in the presence of a base such as potassium carbonate.

(11) Formation of —CF ₂ CF ₂ —
According to the method described in J. Am. Chem. Soc., 2001, 123, 5414., a diketone (—COCO—) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to — (CF ₂ ). A compound having _2- is obtained.

.
2-2. Ring formation Starting materials are commercially available for rings such as 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene. Or generation methods are well known. For the production of tetrahydropyran-2,5-diyl, see paragraphs 0084 to 0107 of JP2013-241397. For the production of 1,3-dioxane-2,5-diyl, see paragraphs 0096 to 0119 of JP-A-2009-132927. See paragraphs 0086 to 0094 of WO 2010/047260 for the production of pyrimidine-2,5-diyl and pyridine-2,5-diyl. The anthracene ring can be synthesized by the synthesis route shown in the following scheme.

A synthesis method of the compound (1-A) in which L ³ is hydrogen in the formula (1) and the compound (1-B) in which L ³ is fluorine will be described. Compound (S-3) is obtained by lithiation of compound (S-1) and reaction with aldehyde (S-2). Compound (S-4) is obtained by reacting triethylsilane in the presence of a Lewis acid such as boron trifluoride diethyl ether complex. The compound (S-4) is lithiated with 2 equivalents of s-butyllithium and reacted with dimethylcarbamoyl chloride to obtain the compound (S-5). This compound is reduced with sodium borohydride to obtain the desired compound (1-A) and compound (S-6). The target compound (1-B) is obtained by reacting the compound (S-6) with diethylaminosulfur trifluoride (DAST).

A method for synthesizing the compound (1-C) in which L ³ is —CF ₃ in the formula (1) will be described. The compound (1-C) is obtained by reacting the compound (S-5) with trifluoromethyltriethylsilane in the presence of a catalytic amount of tetrabutylammonium fluoride (TBAF).

3. Liquid crystal composition 3-1. Component Compound The liquid crystal composition of the present invention will be described. This composition contains at least one compound (1) as component (a). The composition may comprise two or more compounds (1). The component of the composition may be only compound (1). The composition preferably contains at least one compound (1) in the range of 1% by weight to 50% by weight in order to develop excellent physical properties. A more desirable ratio is in the range of 5% to 30% by weight.

  This composition preferably contains the compound (1) as the component (a) and further contains a liquid crystal compound selected from the components (b) to (e) shown below. Component (b) is compounds (2) to (4). Component (c) is compound (5) to (11). Component (d) is compounds (12) to (14). Component (e) is compound (15). The composition may contain other liquid crystal compounds different from the compounds (2) to (15). This composition may not contain other liquid crystalline compounds. When preparing this composition, it is preferable to select from components (b) to (e) in consideration of the sign of dielectric anisotropy and the magnitude. A composition with appropriately selected ingredients has high stability to heat and light, high maximum temperature, low minimum temperature, low viscosity, appropriate optical anisotropy (ie, large optical anisotropy or small optical anisotropy) , Large dielectric anisotropy, large specific resistance, and appropriate elastic constant (ie, large elastic constant or small elastic constant).

Component (b) is a compound in which two terminal 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 the compound of component (b), R ¹¹ and R ¹² are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — is -O- may be replaced, in which at least one hydrogen may be replaced by fluorine. Here, “these” in the definition of R ¹¹ and R ¹² in the compound of component (b) is “alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl or alkenyl, “At least one —CH ₂ — may be replaced by —O—”.

  Component (b) has a small dielectric anisotropy. Component (b) is close to neutrality. Compound (2) is effective in reducing viscosity or adjusting optical anisotropy. Compounds (3) and (4) are effective in expanding the temperature range of the nematic phase by increasing the maximum temperature, or adjusting the optical anisotropy.

  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 element is satisfied, the content is preferably large. When preparing a composition for a mode such as IPS or VA, the content of component (b) is preferably 30% by weight or more, more preferably 40% by weight or more based on the weight of the liquid crystal composition. is there.

Component (c) is compounds (5) to (11). 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 (5-8), compounds (6-1) to (6-17), compound (7-1), and compounds (8-1) to ( 8-3), compounds (9-1) to (9-11), compounds (10-1) to (10-3), and compounds (11-1) to (11-3). In these compounds, R ¹³ and R ¹⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, in which at least one —CH ₂ — is —O—. In which at least one hydrogen may be replaced by fluorine. Here, “these” in the definition of R ¹³ and R ¹⁴ in the compound of component (c) is “alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl or alkenyl, “At least one —CH ₂ — may be replaced by —O—”. R ¹⁵ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — is replaced by —O—. In these, at least one hydrogen may be replaced by fluorine. Here, “these” in the definition of R ^{15 in} the compound of component (c) is “hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and the alkyl or alkenyl In which at least one —CH ₂ — may be replaced by —O— ”.

  Component (c) has a large negative dielectric anisotropy. Component (c) is used in preparing a composition for a mode such as IPS, VA, PSA. As the content of component (c) is increased, the dielectric anisotropy of the composition increases negatively, but the viscosity increases. Therefore, as long as the threshold voltage requirement of the element is satisfied, the content is preferably small. Considering that the dielectric anisotropy is about −5, the content is preferably 40% by weight or more for sufficient voltage driving.

  Of the component (c), since the compound (5) is a bicyclic compound, it is effective in reducing the viscosity, adjusting the optical anisotropy, or increasing the dielectric anisotropy. Since the compounds (5) and (6) are tricyclic compounds, they have the effect of increasing the maximum temperature, increasing the optical anisotropy, or increasing the dielectric anisotropy. Compounds (8) to (11) have the effect of increasing the dielectric anisotropy.

  When preparing a composition for a mode such as IPS, VA, PSA, the content of the component (c) is preferably 40% by weight or more, more preferably 50%, based on the weight of the liquid crystal composition. The range is from wt% to 95 wt%. When component (c) is added to a composition having a positive dielectric anisotropy, the content of component (c) is preferably in the range of 1% by weight to 30% by weight. By adding the component (c), the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component (d) is a compound having a halogen- or fluorine-containing group at the right end. Preferred examples of component (d) include compounds (12-1) to (12-16), compounds (13-1) to (13-113), and compounds (14-1) to (14-57). Can do. In these compounds, R ¹⁶ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—, In these, at least one hydrogen may be replaced by fluorine. Here, “these” in the definition of R ^{16 in} the compound of component (d) is “alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — represents a group which may be replaced by —O— ”. 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) has a positive dielectric anisotropy and is very excellent in stability against heat and light, and is used when preparing a composition for a mode such as IPS, FFS, OCB. The content of component (d) is suitably in the range of 1% to 99% by weight based on the weight of the liquid crystal composition, preferably in the range of 10% to 97% by weight, more preferably from 40% by weight. It is in the range of 95% by weight. When component (d) is added to a composition having a negative dielectric anisotropy, the content of component (d) is preferably in the range of 1% by weight to 30% by weight. By adding the component (d), the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

Component (e) is a compound (15) in which the right terminal group is —C≡N or —C≡C—C≡N. Preferred examples of component (e) include compounds (15-1) to (15-64). In these compounds, R ¹⁷ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—, In these, at least one hydrogen may be replaced by fluorine. Here, “these” in the definition of R ^{17 in} the compound of component (e) is “alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — represents a group which may be replaced by —O—, and X ¹² represents —C≡N or —C≡C—C≡N.

  Since the component (e) has a positive dielectric anisotropy and a large value, the component (e) is used when a composition for a mode such as TN is prepared. By adding this component (e), the dielectric anisotropy of the composition can be increased. Component (e) has the effect of expanding 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 the component (e) is suitably in the range of 1% by weight to 99% by weight based on the weight of the liquid crystal composition, preferably 10% by weight. % To 97% by weight, more preferably 40% to 95% by weight. When component (e) is added to a composition having a negative dielectric anisotropy, the content of component (e) is preferably in the range of 1% by weight to 30% by weight. By adding the component (e), the elastic constant of the composition can be adjusted, and the voltage-transmittance curve of the device can be adjusted.

  High stability to heat and light, high maximum temperature, low minimum temperature, small viscosity, appropriate optical anisotropy, large dielectric constant by properly combining compound (a) and components (b) to (e) above A liquid crystal composition satisfying at least one of physical properties such as anisotropy, large specific resistance, large specific resistance, and an appropriate elastic constant can be prepared. If necessary, a liquid crystalline compound different from the components (b) to (e) may be added.

3-2. Additive The liquid crystal composition is prepared by a known method. For example, the component compounds are mixed and dissolved in each other by heating. Depending on the application, additives may be added to the composition. Examples of the additive include a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a dye, and an antifoaming agent. 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 for the purpose of forming a polymer in the composition. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, since the alignment of liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened, and image burn-in is improved.

  Preferred examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), and vinyl ketone. Further preferred examples are compounds having at least one acryloyloxy and compounds having at least one methacryloyloxy. Further preferred examples 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 of 1 to 5 carbons, R ³² , At least one of R ³³ and R ³⁴ is alkyl having 1 to 5 carbons; s, v, and x are independently 0 or 1; t and u are independently 1 to 10 It is an integer. 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 polymerized quickly by adding a polymerization initiator. By optimizing the reaction temperature, the amount of the remaining polymerizable compound can be reduced. Examples of photo radical polymerization initiators are BASF's Darocur series to TPO, 1173, and 4265, and Irgacure series to 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850. , And 2959.

  Additional examples of photoradical polymerization initiators include 4-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (4-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, benzyl Dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine mixture It is.

  After adding a radical photopolymerization initiator to the liquid crystal composition, the polymerization can be carried out by irradiating ultraviolet rays with an electric field applied. However, the unreacted polymerization initiator or the decomposition product of the polymerization initiator may cause display defects such as image burn-in on the device. In order to prevent this, photopolymerization may be performed without adding a polymerization initiator. A preferable wavelength of light to be irradiated is in a range of 150 nm to 500 nm. A more preferred wavelength is in the range of 250 nm to 450 nm, and a most preferred wavelength is in the range of 300 nm to 400 nm.

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

The optically active compound has an effect of preventing reverse twisting by inducing a helical structure in liquid crystal molecules to give 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 for the purpose of adjusting the temperature dependence of the helical pitch. Preferable examples of the optically active compound include the following compounds (Op-1) to (Op-18). In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R ²⁸ is alkyl having 1 to 10 carbons.

  Antioxidants are effective for maintaining a large voltage holding ratio. Preferred examples of the antioxidant include the following compounds (AO-1) and (AO-2); IRGANOX 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114, and IRGANOX 1098 (trade name; BASF). be able to. The ultraviolet absorber is effective for preventing a decrease in the maximum temperature. Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Specific examples include the following compounds (AO-3) and (AO-4); TINUVIN 329, TINUVIN P, TINUVIN 326, TINUVIN 234, TINUVIN 213, TINUVIN 400, TINUVIN 328, and TINUVIN 99-2 (trade name; BASF); and 1,4-diazabicyclo [2.2.2] octane (DABCO).

  Light stabilizers such as sterically hindered amines are preferred in order to maintain a large voltage holding ratio. Preferred examples of the light stabilizer include the following compounds (AO-5), (AO-6), and (AO-7); TINUVIN 144, TINUVIN 765, and TINUVIN 770DF (trade name; BASF); LA-77Y And LA-77G (trade name; ADEKA). A heat stabilizer is also effective for maintaining a large voltage holding ratio, and a preferred example is IRGAFOS 168 (trade name; BASF). A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt to a GH (guest host) mode device. Antifoaming agents are effective for preventing foaming. Preferred examples of the antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.

In the 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 , where R ⁴¹ is 1 carbon atom. To 20 alkyls. In the compounds (AO-2) and (AO-5), ^R42 is alkyl having 1 to 20 carbons. In the compound ^{(AO-5), R 43} is hydrogen, methyl or O ^· be (oxygen radicals); in the compound (AO-7); ring ^{G 1} is 1,4-cyclohexylene or 1,4-phenylene Ring G ² is 1,4-cyclohexylene, 1,4-phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine; in compounds (AO-5) and (AO-7) , Z is 1, 2 or 3.

4). Liquid crystal display element A liquid crystal composition has operation modes, such as PC, TN, STN, OCB, and PSA, and can be used for the liquid crystal display element driven by an active matrix. This composition has operation modes such as PC, TN, STN, OCB, VA, and IPS, and can also be used for a liquid crystal display element driven by a passive matrix method. These elements can be applied to any of a reflective type, a transmissive type, and a transflective type.

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

  The present invention will be described in more detail with reference to examples (including synthesis examples and usage examples). The invention is not limited by these examples. The present invention includes a mixture of the composition of Use Example 1 and the composition of Use Example 2. The present invention also includes compositions prepared by mixing at least two of the compositions of use examples.

1. Example of Compound (1) Compound (1) was synthesized by the following procedure. The synthesized compound was identified by a method such as NMR analysis. The physical properties of the compound and composition and the characteristics of the device were measured by the following methods.

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

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

  HPLC analysis: Prominence (LC-20AD; SPD-20A) manufactured by Shimadzu Corporation was used for measurement. As the column, YMC-Pack ODS-A (length 150 mm, inner diameter 4.6 mm, particle diameter 5 μm) manufactured by YMC was used. As an eluent, acetonitrile and water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector, or the like was appropriately used. When a UV detector was used, the detection wavelength was 254 nm. A sample was dissolved in acetonitrile to prepare a 0.1 wt% solution, and 1 μL of this solution was introduced into the sample chamber. As a recorder, C-R7 Plus manufactured by Shimadzu Corporation was used.

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

  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 measuring physical properties such as the upper limit temperature, viscosity, optical anisotropy, dielectric anisotropy of the nematic phase, a mixture of a compound and a mother liquid crystal was used as a sample.

  When a sample in which a compound was mixed with mother liquid crystals was used, an extrapolated value was calculated according to the following formula, 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>.

The components of the mother liquid crystal (A) and the ratio (% by weight) are as follows.

  The ratio of the compound and the mother liquid crystal (A) was 15% by weight: 85% by weight. When crystals (or smectic phases) are precipitated at this rate at 25 ° C., the ratio of the compound to the mother liquid crystal (A) is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99%. The sample was measured at a rate that the crystals (or smectic phase) did not precipitate at 25 ° C. in the order of weight%. Unless otherwise specified, the ratio of the compound to the mother liquid crystal (A) was 15% by weight: 85% by weight.

  Measuring method: Physical properties were measured by the following methods. Many of these are described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA). A modified version of this was also used. No thin film transistor (TFT) was attached to the TN device used for the measurement.

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

(2) Transition temperature (° C.): For the measurement, a scanning calorimeter manufactured by Perkin Elmer, Diamond DSC system, or a high-sensitivity differential scanning calorimeter manufactured by SII Nanotechnology, Inc., X-DSC7000 was used. The temperature of the sample was raised and lowered at a rate of 3 ° C./min, the end point of the endothermic peak or exothermic peak accompanying the phase change of the sample was obtained by extrapolation, and the transition temperature was determined. The melting point and polymerization initiation temperature of the compound 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 “lower limit temperature of liquid crystal phase”. The temperature at which the compound transitions from the liquid crystal phase to the liquid may be abbreviated as “clearing point”.

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

(3) Low temperature compatibility: A sample in which a mother liquid crystal and a compound are mixed so that the ratio of the compound is 20% by weight, 15% by weight, 10% by weight, 5% by weight, 3% by weight, and 1% by weight. Prepared and placed sample in glass bottle. The glass bottle was stored in a freezer at −10 ° C. or −20 ° C. for a certain period, and then it was observed whether crystals or smectic phases were precipitated.

(4) Maximum temperature of nematic phase (T _NI or NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. When the sample was a mixture of compound (1) and mother liquid crystals, it was indicated by the symbol _TNI . When the sample was a mixture of compound (1) and compounds such as components B, C and D, it was indicated by the symbol NI. The upper limit temperature of the nematic phase may be abbreviated as “upper limit temperature”.

(5) Minimum Temperature of a Nematic Phase _{(T C;} ° C.): A sample having a nematic phase was put in a glass bottle, 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ for 10 days in a freezer After storage, the liquid crystal phase was observed. For example, when the sample remained nematic at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C., the _TC was described as <−20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

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

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

(8) Specific resistance (ρ; measured at 25 ° C .; Ωcm)
1.0 mL of a sample was injected into a container equipped with an electrode. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Resistivity) = {(Voltage) × (Capacity of container)} / {(DC 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 (cell gap) between the two glass substrates was 5 μm. This element was sealed with an adhesive that was cured with ultraviolet rays after the sample was placed. The device was charged by applying a pulse voltage (60 microseconds at 5 V). The decaying voltage was measured for 16.7 milliseconds with a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit cycle was determined. Area B was the area when it was not attenuated. The voltage holding ratio was expressed as a percentage of area A with respect to area B.

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

  The measurement method of characteristics may differ between a sample having a positive dielectric anisotropy and a sample having a negative dielectric anisotropy. Measurement methods in the case where the dielectric anisotropy is negative are described in the measurements (11) to (15).

(11) Viscosity (Rotational viscosity; γ1; measured at 25 ° C .; mPa · s)
The measurement followed the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 μm. This element was applied stepwise in increments of 1 volt within a range of 39 to 50 volts. After no application for 0.2 seconds, the 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.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation formula (8) on page 40. As the dielectric anisotropy necessary for this calculation, the value measured in the following dielectric anisotropy term was used.

(12) Dielectric anisotropy (Δε; measured at 25 ° C.)
The value of dielectric anisotropy was calculated from the equation: 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 a well-cleaned glass substrate. The glass substrate was rotated with a spinner and then heated at 150 ° C. for 1 hour. A sample was put in a VA element in which the distance between two glass substrates (cell gap) was 4 μm, and the element was sealed with an adhesive that was cured with ultraviolet rays. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, the dielectric constant (ε‖) in the major axis direction of the liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A polyimide solution was applied to a well-cleaned glass substrate. After baking this glass substrate, the obtained alignment film was rubbed. A sample was put 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 the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

(13) Elastic constant (K ₁₁ and K ₃₃ ; measured at 25 ° C .; pN)
An EC-1 type elastic constant measuring instrument manufactured by Toyo Corporation was used for the measurement. A sample was put in a vertical alignment element in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 to 0 volts was applied to the device, and the capacitance (C) and applied voltage (V) were measured. These values are fitted using the formula (2.98) and formula (2.101) in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun), page 75, and the elastic constant is calculated from the formula (2.100). Got the value.

(14) Threshold voltage (Vth; measured at 25 ° C .; V)
An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V. 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 reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 10%.

(15) Response time (τ; measured at 25 ° C .; ms)
An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. A sample was put in a normally black mode PVA device in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was anti-parallel. The device was sealed using an adhesive that was cured with ultraviolet light. A voltage slightly exceeding the threshold voltage was applied to the device for 1 minute, and then 23.5 mW / cm ² of ultraviolet light 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 the maximum, and the transmittance was 0% when the light amount was the minimum. The response time was expressed as the time required to change the transmittance from 90% to 10% (fall time; millisecond).

  Raw material: Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), and was obtained from Nippon Alcohol Sales Co., Ltd. . Tetrahydrofuran may be abbreviated as THF.

[Synthesis Example 1] Synthesis of compounds (1-1-8) and (1-1-4)

<First step>
Under a nitrogen atmosphere, the compound (T-1) (138.2 g, 583.4 mmol) and diethyl ether (2500 ml) were added to the reactor and cooled to −70 ° C. or lower. Thereto, n-butyllithium (1.58M; n-hexane solution; 369.2 ml, 583.4 mmol) was added dropwise in the temperature range of −75 ° C. to −70 ° C., and the mixture was further stirred for 1 hour. A solution of compound (T-2) (89.2 g, 530.4 mmol) in THF (300 ml) was added dropwise in the temperature range of −75 ° C. to −70 ° C. and stirred for 3 hours. The reaction mixture was poured into ice-cooled saturated aqueous ammonium chloride solution (2000 ml), stirred for 30 minutes, and extracted with ethyl acetate. The combined organic layers were washed with water and then with saturated brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane / ethyl acetate = 1/4, volume ratio) to give compound (T-3) (169 g, 517.9 mmol; 88.8). %).

<Second step>
Under a nitrogen atmosphere, the compound (T-3) (169 g, 517.9 mmol) obtained in the first step and dichloromethane (850 ml) were added to the reactor and cooled to −70 ° C. or lower. Thereto, a solution of triethylsilane (75.3 g, 647.4 mmol) in dichloromethane (70 ml) and a solution of boron trifluoride diethyl ether complex (91.9 g, 647.4 mmol) in dichloromethane (80 ml) from −75 ° C. After dropwise addition in the temperature range of 70 ° C., the temperature was gradually raised and the mixture was stirred at room temperature for 10 hours. The reaction mixture was poured into water (1000 ml) and extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane / ethyl acetate = 1/20, volume ratio) and recrystallization (heptane / ethanol) to give compound (T-4) ( 113 g, 364.1 mmol; 70%).

<Third step>
Under a nitrogen atmosphere, the compound (T-4) (20 g, 64.45 mmol) obtained in the second step and THF (480 ml) were added to the reactor and cooled to −70 ° C. or lower. Thereto, s-butyllithium (1.07 M; cyclohexane solution; 126 ml, 135.35 mmol) was dropped in a temperature range of −75 ° C. to −70 ° C., and further stirred for 1 hour, and then cooled to −90 ° C. or lower. . A solution of N, N-dimethylcarbamoyl chloride (7.62 g, 70.9 mmol) in THF (15 ml) was added dropwise in the temperature range of −100 ° C. to −90 ° C., and 3 in the temperature range of −75 ° C. to −70 ° C. Stir for hours. The reaction mixture was poured into ice-cooled saturated aqueous ammonium chloride solution (300 ml) and stirred for 30 minutes. The obtained powder was recrystallized (dichloroethane) to obtain Compound (T-5) (2.3 g, 6.84 mmol; 10.6%).

<4th process>
The compound (T-5) (1.0 g, 2.97 mmol) obtained in the third step, dichloromethane (40 ml) and methanol (20 ml) were added to the reactor and ice-cooled. Thereto, sodium borohydride (0.225 g, 5.95 mmol) was added little by little in the temperature range of 0 ° C. to 10 ° C., and then stirred at room temperature for 3 hours. The reaction mixture was poured into water (ml) and extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane / ethyl acetate = 1/9, volume ratio) to give compound (1-1-8) (0.49 g, 1.54 mmol). 52%) and compound (T-6) (0.48 g, 1.43 mmol; 48%).

<5th process>
Under a nitrogen atmosphere, the compound (T-6) (0.1 g, 0.3 mmol) obtained in the fourth step and dichloromethane (4 ml) were added to the reactor, and the mixture was ice-cooled. Thereto, diethylaminosulfur trifluoride (DAST) (0.0575 g, 0.36 mmol) was added dropwise in a temperature range of 0 ° C. to 10 ° C., followed by stirring at room temperature for 10 hours. The reaction mixture was poured into ice-cooled saturated aqueous sodium hydrogen carbonate solution (10 ml) and extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane / ethyl acetate = 1/9, volume ratio) to give compound (1-1-4) (3.3 mg, 0.01 mmol). ; 3.3%).

Compound (1-1-8)
¹ H-NMR (CDCl ₃ ): δ 8.66 (s, 1H), 8.19 (s, 1H), 7.68 (d, 1H), 7.32 (dd, 1H), 7.02 (d , 1H), 4.36 (q, 2H), 4.27 (q, 2H), 1.60 (t, 3H), 1.52 (t, 3H). Phase transition temperature: C 136.2 Maximum temperature (NI) = 44.6 ° C .; dielectric anisotropy (Δε) = − 14.4; optical anisotropy (Δn) = 0.387.

Compound (1-1-4)
GC-MS (EI): 252, 281, 338 (M +).

[Synthesis Example 2] Synthesis of Compound (1-1-7)

<First step>
Under a nitrogen atmosphere, boron tribromide (1.0 M; dichloromethane solution; 400 ml, 400 mmol) was added to the reactor and cooled to −70 ° C. or lower. Thereto was added dropwise a solution of the compound (T-4) (35.23 g, 113.53 mmol) obtained in the second step of Synthesis Example 1 in a dichloromethane (100 ml) solution at a temperature range of −75 ° C. to −70 ° C. The temperature was gradually raised and the mixture was stirred at room temperature for 8 hours. The reaction mixture was poured into ice water (400 ml) and extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-7) (28.86 g, 113.53 mmol; 100%). Compound (T-7) was used for the next reaction without purification.

<Second step>
Under a nitrogen atmosphere, the compound (T-7) (28.86 g, 113.53 mmol) obtained in the first step, triethylamine (28.89 g, 265.83 mmol), and dichloromethane (400 ml) were placed in a reactor. And cooled to −10 ° C. or lower. Trifluoromethanesulfonic anhydride (75 g, 265.83 mmol) was added dropwise in the temperature range of −10 ° C. to 0 ° C., and the mixture was stirred at 0 ° C. or lower for 30 minutes. The reaction mixture was poured into water (400 ml) and extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane / toluene = 1/1, volume ratio) to give compound (T-8) (50.32 g, 97.08 mmol; 85. 5%).

<Third step>
Compound (T-8) (20 g, 38.59 mmol), Compound (T-7) (9.82 g, 86.18 mmol), tetrakistriphenylphosphine palladium (2.28 g) obtained in the second step into the reactor. , 1.97 mmol), potassium bromide (10.82 g, 90.92 mmol), potassium phosphate (25.0 g, 117.82 mmol), 1,4-dioxane (200 ml). The mixture was stirred for 5 hours under heating to reflux. After cooling to room temperature, the reaction mixture was extracted with toluene. The combined organic layers were washed with water and saturated brine, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane / toluene = 9/1, volume ratio) to give compound (T-9) (9.35 g, 26.1 mmol; 67.6). %).

<4th process>
The compound (T-9) obtained in the third step (9.35 g, 26.1 mmol), palladium-carbon (0.25 g), toluene (50 ml), and isopropanol (50 ml) were added, and under a hydrogen atmosphere. And stirred. After filtration, the filtrate was concentrated, and the residue was purified by silica gel chromatography (heptane) to obtain compound (T-10) (9.43 g, 26.02 mmol; 99.5%).

<5th process>
Compound (T-10) obtained in the fourth step (9.43 g, 26.02 mmol), s-butyllithium (1.07 M; cyclohexane solution; 54 ml, 57.78 mmol), dimethylcarbamoyl chloride (3.09 g) , 28.73 mmol), and THF (100 ml) solution, Compound (T-11) (1.52 g, 3.93 mmol; 15.1%) Got.

<Sixth step>
Using compound (T-11) obtained in the fifth step (1.52 g, 3.93 mmol), sodium borohydride (0.192 g, 5.07 mmol), THF (5 ml), and methanol (5 ml) The compound (1-1-7) (0.42 g, 1.12 mmol; 28.5%) was obtained by the same operation as in the fourth step of Synthesis Example 1.

Compound (1-1-7)
¹ H-NMR (CDCl ₃ ) δ 8.77 (s, 1H), 8.30 (s, 1H), 7.68 (d, 1H), 7.54 (d, 1H), 7.28 (dd, 1H), 2.86-2.83 (m, 4H), 1.76-1.69 (m, 4H), 1.41-1.36 (m, 8H), 0.92 (t, 3H) , 0.90 (t, 3H). Phase transition temperature: C 64.9 Maximum temperature (NI) = − 13.4 ° C .; dielectric anisotropy (Δ∈) = − 4.7; optical anisotropy (Δn) = 0.174.

[Synthesis Example 3] Synthesis of Compound (1-1-16)

  Under a nitrogen atmosphere, the compound (T-5) (0.3 g, 0.89 mmol) obtained in the third step of Synthesis Example 1 and THF (30 ml) were placed in a reactor and ice-cooled. Thereto, trifluoromethyltriethylsilane (0.13 g, 0.94 mmol) and tetrabutylammonium fluoride (TBAF, 1.0 M; THF solution; 20 μl, 0.02 mmol) were added in a temperature range from 0 ° C. to −10 ° C. And then stirred at room temperature for 10 hours. The reaction mixture was poured into water (30 ml) and extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine in that order, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane / ethyl acetate = 2/1, volume ratio) to give compound (1-1-16) (3.0 mg, 0.007 mmol; 7.8%).

Compound (1-1-16)
GC-MS (EI): 336, 388 (M +).

  Compound (1) is synthesized according to “2. Synthesis of Compound (1)” and Synthesis Examples described above. Examples of such compounds include the following compounds (1-1-1) to (1-1-24), compounds (1-2-1) to (1-2-24), and compounds (1-3 -1) to (1-3-24), compounds (1-4-1) to (1-4-48), compounds (1-5-1) to (1-5-48), and compound (1 -6-1) to (1-6-48).

2. Composition Examples The present invention includes a mixture of Use Example 1 composition and Use Example 2 composition. The present invention also includes a mixture in which at least two of the compositions of the use examples are mixed. The compounds in the use examples were represented by symbols based on the definitions in the following table. In the table, the configuration regarding 1,4-cyclohexylene is trans. In the usage examples, the number in parentheses after the symbol represents the chemical formula to which the compound belongs. The symbol (−) means other liquid crystal compounds different from the compounds (2) to (15). The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the physical properties of the composition are summarized. The physical properties were measured according to the method described above, and the measured values were described as they were (without extrapolation).

[Usage example 1]
2O-At (1F, 2F, 9F) -O2 (1-1-8) 1%
2-HB-C (15-1) 5%
3-HB-C (15-1) 12%
3-HB-O2 (2-5) 15%
2-BTB-1 (2-10) 3%
3-HHB-F (13-1) 4%
3-HHB-1 (3-1) 8%
3-HHB-O1 (3-1) 5%
3-HHB-3 (3-1) 14%
3-HHEB-F (13-10) 4%
5-HHEB-F (13-10) 3%
2-HHB (F) -F (13-2) 7%
3-HHB (F) -F (13-2) 7%
5-HHB (F) -F (13-2) 7%
3-HHB (F, F) -F (13-3) 5%
NI = 98.6 ° C .; η = 18.0 mPa · s; Δn = 0.102; Δε = 4.6.

[Usage example 2]
5-At (1F, 2F, 9F) -5 (1-1-7) 3%
3-HB-CL (15-1) 11%
3-HH-4 (2-1) 12%
3-HB-O2 (2-5) 7%
3-HHB (F, F) -F (13-3) 4%
3-HBB (F, F) -F (13-24) 29%
5-HBB (F, F) -F (13-24) 24%
5-HBB (F) B-2 (4-5) 5%
5-HBB (F) B-3 (4-5) 5%
NI = 70.3 ° C .; η = 21.3 mPa · s; Δn = 0.119; Δε = 5.3.

[Usage example 3]
2O-At (1F, 2F, 9F, 10F) -O2 (1-1-4) 1%
7-HB (F, F) -F (12-4) 3%
3-HB-O2 (2-5) 7%
2-HHB (F) -F (13-2) 10%
3-HHB (F) -F (13-2) 9%
5-HHB (F) -F (13-2) 10%
2-HBB (F) -F (13-23) 9%
3-HBB (F) -F (13-23) 9%
5-HBB (F) -F (13-23) 16%
2-HBB-F (13-22) 4%
3-HBB-F (13-22) 4%
5-HBB-F (13-22) 3%
3-HBB (F, F) -F (13-24) 5%
5-HBB (F, F) -F (13-24) 10%

[Usage example 4]
2O-At (1F, 2F, 9F, 10CF3) -O2 (1-1-16) 1%
5-HB-CL (12-2) 16%
3-HH-4 (2-1) 12%
3-HH-5 (2-1) 4%
3-HHB-F (13-1) 4%
3-HHB-CL (13-1) 3%
4-HHB-CL (13-1) 4%
3-HHB (F) -F (13-2) 10%
4-HHB (F) -F (13-2) 9%
5-HHB (F) -F (13-2) 8%
7-HHB (F) -F (13-2) 8%
5-HBB (F) -F (13-23) 4%
1O1-HBBH-5 (4-1) 3%
3-HHBB (F, F) -F (14-6) 2%
4-HHBB (F, F) -F (14-6) 3%
5-HHBB (F, F) -F (14-6) 3%
3-HH2BB (F, F) -F (14-15) 3%
4-HH2BB (F, F) -F (14-15) 3%

[Usage example 5]
3-H1OAt (1F, 2F, 9F, 10F) -O2 (1-2-9) 1%
5-HB-CL (12-2) 11%
3-HH-4 (2-1) 8%
3-HHB-1 (3-1) 5%
3-HHB (F, F) -F (13-3) 8%
3-HBB (F, F) -F (13-24) 20%
5-HBB (F, F) -F (13-24) 15%
3-HHEB (F, F) -F (13-12) 9%
4-HHEB (F, F) -F (13-12) 3%
5-HHEB (F, F) -F (13-12) 3%
2-HBEB (F, F) -F (13-39) 3%
3-HBEB (F, F) -F (13-39) 5%
5-HBEB (F, F) -F (13-39) 3%
3-HHBB (F, F) -F (14-6) 6%

[Usage Example 6]
2O-At (1F, 2F, 9F, 10CF3) O1H-3 (1-3-18) 1%
5-HB-F (12-2) 12%
6-HB-F (12-2) 9%
7-HB-F (12-2) 7%
2-HHB-OCF3 (13-1) 7%
3-HHB-OCF3 (13-1) 6%
4-HHB-OCF3 (13-1) 7%
5-HHB-OCF3 (13-1) 5%
3-HH2B-OCF3 (13-4) 4%
5-HH2B-OCF3 (13-4) 4%
3-HHB (F, F) -OCF2H (13-3) 4%
3-HHB (F, F) -OCF3 (13-3) 5%
3-HH2B (F) -F (13-5) 3%
3-HBB (F) -F (13-23) 10%
5-HBB (F) -F (13-23) 10%
5-HBBH-3 (4-1) 3%
3-HB (F) BH-3 (4-2) 3%

[Usage example 7]
2O-At (1F, 2F, 9F) -O2 (1-1-8) 1%
3-HHB (F, F) -F (13-3) 9%
3-H2HB (F, F) -F (13-15) 8%
4-H2HB (F, F) -F (13-15) 8%
5-H2HB (F, F) -F (13-15) 8%
3-HBB (F, F) -F (13-24) 20%
5-HBB (F, F) -F (13-24) 20%
3-H2BB (F, F) -F (13-27) 10%
5-HHBB (F, F) -F (14-6) 3%
5-HHEBB-F (14-17) 2%
3-HH2BB (F, F) -F (14-15) 3%
1O1-HBBH-4 (4-1) 4%
1O1-HBBH-5 (4-1) 4%
NI = 97.8 ° C .; η = 35.7 mPa · s; Δn = 0.119; Δε = 8.9.
The pitch when Op-05 was added to the above composition in a proportion of 0.25% by weight was 64.9 μm.

[Usage Example 8]
5-At (1F, 2F, 9F) -5 (1-1-7) 3%
3-HB-O1 (2-5) 15%
3-HH-4 (2-1) 5%
3-HB (2F, 3F) -O2 (5-1) 12%
5-HB (2F, 3F) -O2 (5-1) 11%
2-HHB (2F, 3F) -1 (6-1) 12%
3-HHB (2F, 3F) -1 (6-1) 11%
3-HHB (2F, 3F) -O2 (6-1) 12%
5-HHB (2F, 3F) -O2 (6-1) 13%
3-HHB-1 (3-1) 6%
NI = 83.1 ° C .; η = 36.3 mPa · s; Δn = 0.092; Δε = −3.4.

[Usage example 9]
2O-At (1F, 2F, 9F, 10F) -O2 (1-1-4) 1%
3-HB-CL (12-2) 6%
5-HB-CL (12-2) 4%
3-HHB-OCF3 (13-1) 5%
3-H2HB-OCF3 (13-13) 5%
5-H4HB-OCF3 (13-19) 15%
V-HHB (F) -F (13-2) 5%
3-HHB (F) -F (13-2) 5%
5-HHB (F) -F (13-2) 5%
3-H4HB (F, F) -CF3 (13-21) 8%
5-H4HB (F, F) -CF3 (13-21) 10%
5-H2HB (F, F) -F (13-15) 4%
5-H4HB (F, F) -F (13-21) 7%
2-H2BB (F) -F (13-26) 5%
3-H2BB (F) -F (13-26) 10%
3-HBEB (F, F) -F (13-39) 5%

[Usage Example 10]
2O-At (1F, 2F, 9F, 10CF3) -O2 (1-1-16) 1%
5-HB-CL (12-2) 17%
7-HB (F, F) -F (12-4) 3%
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%
2-HHB (F) -F (13-2) 7%
3-HHB (F) -F (13-2) 7%
5-HHB (F) -F (13-2) 7%
3-HHB (F, F) -F (13-3) 6%
3-H2HB (F, F) -F (13-15) 5%
4-H2HB (F, F) -F (13-15) 5%

[Usage Example 11]
3-H1OAt (1F, 2F, 9F, 10F) -O2 (1-2-9) 1%
5-HB-CL (12-2) 3%
7-HB (F) -F (12-3) 7%
3-HH-4 (2-1) 9%
3-HH-5 (2-1) 10%
3-HB-O2 (2-1) 13%
3-HHEB-F (13-10) 8%
5-HHEB-F (13-10) 8%
3-HHEB (F, F) -F (13-12) 9%
4-HHEB (F, F) -F (13-12) 5%
3-GHB (F, F) -F (13-109) 5%
4-GHB (F, F) -F (13-109) 6%
5-GHB (F, F) -F (13-109) 7%
2-HHB (F, F) -F (13-3) 4%
3-HHB (F, F) -F (13-3) 5%

[Usage example 12]
2O-At (1F, 2F, 9F, 10CF3) O1H-3 (1-3-18) 1%
1V2-BEB (F, F) -C (15-15) 6%
3-HB-C (15-1) 18%
2-BTB-1 (2-10) 10%
5-HH-VFF (2-1) 30%
3-HHB-1 (3-1) 3%
VFF-HHB-1 (3-1) 8%
VFF2-HHB-1 (3-1) 11%
3-H2BTB-2 (3-17) 5%
3-H2BTB-3 (3-17) 4%
3-H2BTB-4 (3-17) 4%

[Usage Example 13]
2O-At (1F, 2F, 9F) -O2 (1-1-8) 1%
2-HH-3 (2-1) 16%
7-HB-1 (2-5) 10%
5-HB-O2 (2-5) 7%
3-HB (2F, 3F) -O2 (5-1) 17%
5-HB (2F, 3F) -O2 (5-1) 16%
3-HHB (2F, 3CL) -O2 (6-12) 3%
4-HHB (2F, 3CL) -O2 (6-12) 3%
5-HHB (2F, 3CL) -O2 (6-12) 2%
3-HH1OCro (7F, 8F) -5 (9-6) 5%
5-HBB (F) B-2 (4-5) 10%
5-HBB (F) B-3 (4-5) 10%
NI = 76.2 ° C .; η = 24.0 mPa · s; Δn = 0.107; Δε = −2.6.

[Usage example 14]
5-At (1F, 2F, 9F) -5 (1-1-7) 3%
5-HB (F) B (F, F) XB (F, F) -F (14-41) 5%
3-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (14-47) 7%
5-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
3-HH-V (2-1) 39%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (12-1) 3%
3-BB (F, F) XB (F, F) -F (13-97) 10%
3-HHBB (F, F) -F (14-6) 3%
NI = 80.6 ° C .; η = 14.1 mPa · s; Δn = 0.108; Δε = 6.0.

[Usage Example 15]
2O-At (1F, 2F, 9F, 10F) -O2 (1-1-4) 1%
2-HH-3 (2-1) 6%
3-HH-V1 (2-1) 10%
1V2-HH-1 (2-1) 8%
1V2-HH-3 (2-1) 7%
3-BB (2F, 3F) -O2 (5-3) 8%
5-BB (2F, 3F) -O2 (5-3) 4%
3-H1OB (2F, 3F) -O2 (5-5) 7%
2-HH1OB (2F, 3F) -O2 (6-5) 7%
3-HH1OB (2F, 3F) -O2 (6-5) 19%
3-HDhB (2F, 3F) -O2 (6-3) 7%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 2%
2-BB (2F, 3F) B-3 (7-1) 11%

[Usage Example 16]
2O-At (1F, 2F, 9F, 10CF3) -O2 (1-1-16) 1%
3-GB (F) B (F, F) XB (F, F) -F (14-57) 5%
3-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
4-BB (F) B (F, F) XB (F, F) -F (14-47) 6%
5-BB (F) B (F, F) XB (F, F) -F (14-47) 3%
3-HH-V (2-1) 41%
3-HH-V1 (2-1) 7%
3-HHEH-5 (3-13) 3%
3-HHB-1 (3-1) 4%
V-HHB-1 (3-1) 5%
V2-BB (F) B-1 (3-6) 5%
1V2-BB-F (12-1) 3%
3-BB (F, F) XB (F, F) -F (13-97) 6%
3-GB (F, F) XB (F, F) -F (13-113) 5%
3-HHBB (F, F) -F (14-6) 3%

[Usage Example 17]
3-H1OAt (1F, 2F, 9F, 10F) -O2 (1-2-9) 1%
2O-At (1F, 2F, 9F, 10CF3) O1H-3 (1-3-18) 1%
2-HH-5 (2-1) 3%
3-HH-4 (2-1) 15%
3-HH-5 (2-1) 4%
3-HB-O2 (2-5) 12%
3-H2B (2F, 3F) -O2 (5-4) 14%
5-H2B (2F, 3F) -O2 (5-4) 15%
3-HHB (2F, 3CL) -O2 (6-12) 5%
2-HBB (2F, 3F) -O2 (6-7) 3%
3-HBB (2F, 3F) -O2 (6-7) 8%
5-HBB (2F, 3F) -O2 (6-7) 9%
3-HHB-1 (3-1) 3%
3-HHB-3 (3-1) 4%
3-HHB-O1 (3-1) 3%

[Usage Example 18]
2O-At (1F, 2F, 9F) -O2 (1-1-8) 1%
2-HH-3 (2-1) 21%
3-HH-4 (2-1) 9%
1-BB-3 (2-8) 9%
3-HB-O2 (2-5) 2%
3-BB (2F, 3F) -O2 (5-3) 9%
5-BB (2F, 3F) -O2 (5-3) 6%
2-HH1OB (2F, 3F) -O2 (6-5) 13%
3-HH1OB (2F, 3F) -O2 (6-5) 21%
3-HHB-1 (3-1) 4%
3-HHB-O1 (3-1) 3%
2-BBB (2F) -5 (3-8) 2%
NI = 73.2 ° C .; η = 16.2 mPa · s; Δn = 0.100; Δε = −3.3.

[Usage Example 19]
5-At (1F, 2F, 9F) -5 (1-1-7) 3%
1-BB-3 (2-8) 9%
3-HH-V (2-1) 27%
3-BB (2F, 3F) -O2 (5-3) 13%
2-HH1OB (2F, 3F) -O2 (6-5) 20%
3-HH1OB (2F, 3F) -O2 (6-5) 14%
3-HHB-1 (3-1) 8%
2-BBB (2F) -5 (3-8) 6%
NI = 73.5 ° C .; η = 17.1 mPa · s; Δn = 0.109; Δε = −3.2.

  The liquid crystal composition of the present invention has excellent characteristics. This composition can be widely used for liquid crystal display elements used in personal computers, televisions and the like.

Claims (15)

The compound represented by Formula (1).

In equation (1),
R ¹ and R ² are independently hydrogen or alkyl having 1 to 20 carbons, in which at least one —CH ₂ — is —O—, —S—, —CO—, or —SiH _2. - may be replaced by at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, in these monovalent groups, at least one hydrogen fluorine or May be replaced by chlorine;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6. -Diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-phenylene, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene- In 2,6-diyl or naphthalene-2,6-diyl, at least one —CH ₂ — may be replaced by —O—, —S—, —CO—, or —SiH ₂ —. -CH ₂ CH ₂ — may be replaced by —CH═CH— or —CH═N—, and 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 may be substituted;
Z ¹ and Z ² are each independently a single bond or alkylene having 1 to 6 carbon atoms, in which at least one —CH ₂ — is —O—, —S—, —CO—, or —SiH. ₂ - may be replaced by one or two _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, in these divalent groups, at least one hydrogen May be replaced by fluorine or chlorine;
L ¹ , L ² , L ³ , and L ⁴ are independently hydrogen, fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F. And at least one of L ¹ , L ² , and L ⁴ is fluorine, chlorine, —CF ₃ , —CHF ₂ , —CH ₂ F, —OCF ₃ , —OCHF ₂ , or —OCH ₂ F ;
a and b are independently 0, 1, 2, or 3, and the sum of a and b is 0 to 4. The compound of Claim 1 represented by any one of Formula (1-1) to (1-6).

In the formulas (1-1) to (1-6),
R ¹ and R ² are independently 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 2 to carbons 9 alkenyloxy;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl, tetrahydro-2H-pyran-2- On-3,6-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, decahydronaphthalene-2,6-diyl, 1,2, 3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, which is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2 , 5-diyl, tetrahydro-2H-pyran-2-one-3,6-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2, In diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or naphthalene-2,6-diyl, at least one hydrogen is fluorine, chlorine, It may be replaced by -CF ₃ or -CHF _2,;
Z ¹ and Z ² are each independently a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CH═CH—, —CF ₂ CF ₂ —, —CF═CH—, —CH═CF—, —CF═CF—, —C≡C—, —CH ₂ CO—, —COCH ₂ —, —CH ₂ SiH ₂ —, —SiH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —CH ₂ CH═CHCH ₂ —, — (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 —;
L ¹ , L ² , L ³ , and L ⁴ are independently hydrogen, fluorine, —CF ₃ , or —CH ₂ F, and at least one of L ¹ , L ² , and L ⁴ is fluorine , -CF _3, or -CH ₂ F. In the formulas (1-1) to (1-6) according to claim 2, R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, carbon number 2 to 9 alkoxyalkyl, alkenyl having 2 to 10 carbons, or alkenyloxy having 2 to 9 carbons; ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4- Phenylene, or 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine; Z ¹ and Z ² are independently a single bond, —COO—, —OCO—, —CH ₂ O—, _{-OCH 2 -, - CF 2 O} -, - OCF 2 -, - CH 2 CH 2 -, - CH = CH -, - CF 2 CF 2 -, - (CH 2) 4 -, or _-CH 2 CH = CHCH ₂ - a ^{and; L} 1, ^{2, L 3,} and ^{L 4} are independently hydrogen, fluorine, or a -CF _3, and ^L 1, ^{L 2,} and at least one of ^{L 4} are a fluorine, according to claim 2 Compound. In formulas (1-1) to (1-6) according to claim 2, R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or carbon An alkenyl having a number of 2 to 10; ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-chloro-1, 4-phenylene, 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene or 2,3,5-trifluoro-1,4-phenylene; Z ¹ and Z ² are independently a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O -, - OCF ₂ -, or _-CH 2 CH _2- , L ¹ , L ² , L ³ , and L ⁴ are independently hydrogen or fluorine, and at least two of L ¹ , L ² , and L ⁴ are fluorine. 2. The compound according to 2. In formulas (1-1) to (1-6) according to claim 2, R ¹ and R ² are independently alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or 2 carbons. Ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1 3, 4-phenylene; Z ¹ and Z ² are single bonds; L ¹ and L ² are fluorine, and L ³ and L ⁴ are independently hydrogen or fluorine. Compound. The compound of Claim 1 represented by Formula (1-1), (1-2), or (1-3).

In formulas (1-1), (1-2), and (1-3),
R ¹ and R ² are independently alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene;
Z ¹ and Z ² are each independently a single bond, —CH ₂ O—, or —OCH ₂ —;
L ¹ , L ² , and L ⁴ are fluorine, and L ³ is hydrogen, fluorine, or —CF ₃ . The compound of Claim 1 represented by Formula (a) or (b).

In formula (a) or (b):
R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkenyl having 2 to 10 carbons;
Ring A ¹ and Ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-chloro-1,4-phenylene, 2,3-difluoro. -1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, or 2,3 5-trifluoro-1,4-phenylene is:
Z ¹ and Z ² are each independently a single bond, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, Or -CH = CH-;
a and b are independently 0, 1, or 2, and the sum of a and b is 0, 1, or 2. The formula (a) or (b) according to claim 7, wherein R ¹ and R ² are independently hydrogen, alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or 2 to 10 carbons. Ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4. -Phenylene; Z ¹ and Z ² are independently a single bond, —CH ₂ O—, or —OCH ₂ —; a and b are independently 0 or 1, and a and b 8. A compound according to claim 7, wherein the sum is 0, 1 or 2. The compound of Claim 7 represented by any one of Formula (a-1) to (a-3) and Formula (b-1) to (b-3).

In formulas (a-1) to (a-3) and formulas (b-1) to (b-3),
R ¹ and R ² are independently alkyl having 1 to 10 carbons or alkoxy having 1 to 9 carbons; ring A ¹ and ring A ² are independently 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, or 2,3-difluoro-1,4-phenylene; Z ¹ and Z ² are independently a single bond, —CH ₂ O—, or —OCH. _2- .   A liquid crystal composition comprising at least one compound according to any one of claims 1 to 9. The liquid crystal composition according to claim 10, further comprising at least one compound selected from the group of compounds represented by formulas (2) to (4).

In the 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 or alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, in these monovalent groups, at least one hydrogen may be replaced by fluorine;
Ring B ¹ , Ring B ² , Ring B ³ , and Ring B ⁴ are 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 each independently a single bond, —COO—, —CH ₂ CH ₂ —, —CH═CH—, or —C≡C—. The liquid crystal composition according to claim 10 or 11, further comprising at least one compound selected from the group of compounds represented by formulas (5) to (11).

In the equations (5) to (11),
R ¹³ and R ¹⁴ are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—. Well, in these monovalent groups, at least one hydrogen may be replaced by fluorine;
R ¹⁵ is hydrogen, fluorine, alkyl having 1 to 10 carbons, or alkenyl having 2 to 10 carbons, and in alkyl and alkenyl, at least one —CH ₂ — may be replaced by —O—, In these monovalent groups, at least one hydrogen may be replaced by fluorine;
Ring C ¹ , Ring C ² , Ring C ³ , and Ring C ⁴ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen replaced with fluorine 1,4-phenylene, tetrahydropyran-2,5-diyl, or decahydronaphthalene-2,6-diyl;
Ring ^{C 5} and ring ^{C 6} are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene, 2,6 -Diyl;
^{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, 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 10 to 12, further comprising at least one compound selected from the group of compounds represented by formulas (12) to (14).

In the equations (12) to (14),
R ¹⁶ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—, and these monovalent 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, 1,4-phenylene in which at least one hydrogen is 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 each 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 —;
L ¹³ and L ¹⁴ are independently hydrogen or fluorine. The liquid crystal composition according to any one of claims 10 to 13, further comprising at least one compound selected from the group of compounds represented by formula (15).

In equation (15),
R ¹⁷ is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in this alkyl or alkenyl, at least one —CH ₂ — may be replaced by —O—, and these monovalent 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, 1,4-phenylene in which at least one hydrogen is replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2 , 5-diyl, or pyrimidine-2,5-diyl;
Z ²¹ is 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.   The liquid crystal display element containing the liquid-crystal composition of any one of Claims 10-14.