JP2019077792A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition satisfying at least one of demands for characteristics such as a high maximum temperature, low minimum temperature, small viscosity, large optical anisotropy, large dielectric anisotropy, and large elastic modulus or having a suitable balance relating to at least two of the above characteristics, and an AM element comprising the above composition.SOLUTION: The liquid crystal composition comprises a specific compound having negatively large dielectric anisotropy as a first component, and may contain a specific compound having a high maximum temperature or a small viscosity as a second component, a specific compound having negative dielectric anisotropy as a third component, or a specific compound having a polymerizable group as a first additive.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display device containing the composition and having a mode such as IPS, VA, FFS, or FPA. The present invention also relates to a polymer supported alignment type liquid crystal display device.

  In liquid crystal display devices, classification based on the operation mode of liquid crystal molecules is as follows: phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), IPS These modes are modes such as (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the driving system of elements is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc. The classification of TFT is amorphous silicon and polycrystal silicon. The latter are classified into high temperature type and low temperature type according to the manufacturing process. Source based classifications are reflective based on natural light, transmissive based on back light, and semi-transmissive based on both natural light and back light.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM element having good properties can be obtained. The associations in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. The preferred upper temperature limit of the nematic phase is about 70 ° C. or higher, and the preferred lower temperature limit of the nematic phase is about -10 ° C. or lower. The viscosity of the composition is related to the response time of the device. Short response times are preferred for displaying motion pictures on the device. Even shorter response times of 1 millisecond are desirable. Thus, low viscosity in the composition is preferred. Smaller viscosities at lower temperatures are more preferred. The elastic constant of the composition is related to the contrast of the element. In order to increase the contrast in the device, a large elastic constant in the composition is more preferred.

  The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large or small optical anisotropy, ie a suitable optical anisotropy, is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. This value is in the range of about 0.30 μm to about 0.40 μm in the VA mode device and in the range of about 0.20 μm to about 0.30 μm in the IPS mode or FFS mode device. In these cases, compositions with large optical anisotropy are preferred for small cell gap devices. The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, large dielectric anisotropy is preferred. The large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large specific resistance at the initial stage is preferred. After prolonged use, compositions having high specific resistance are preferred. The stability of the composition to ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM element used for a liquid crystal monitor, a liquid crystal television or the like.

  In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a liquid crystal display device of the polymer supported alignment (PSA) type, a polymer is combined with an alignment film. 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 light 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, the polymer can control the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the image sticking. Such an effect of the polymer can be expected to devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  On the other hand, in a liquid crystal display element having no alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition to which a small amount of polymerizable compound and a small amount of polar compound are added is injected into the device. Here, the polar compound is adsorbed on the substrate surface of the device and arranged. The liquid crystal molecules are oriented according to this arrangement. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of the device. Here, the polymerizable compound is polymerized to stabilize the alignment of liquid crystal molecules. In this composition, it is possible to control the alignment of liquid crystal molecules by the polymer and the polar compound, so that the response time of the device is shortened and the image sticking is improved. Furthermore, in the element having no alignment film, the process of forming the alignment film is unnecessary. Since there is no alignment film, the interaction between the alignment film and the composition does not lower the electrical resistance of the device. Such an effect of the combination of a polymer and a polar compound can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In an AM device having a TN mode, a composition having positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having negative dielectric anisotropy is used. In an AM device having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer-supported oriented AM element, a composition having positive or negative dielectric anisotropy is used. In an element having no alignment film, a composition having positive or negative dielectric anisotropy is used.

JP, 2016-506434, A International Publication 2014-079147

  Problems of the present invention include: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, thermal It is to provide a liquid crystal composition satisfying at least one of the high stability, the large elastic constant, and the like. Another object is to provide a liquid crystal composition having a proper balance between at least two of these properties. Another object is to provide a liquid crystal display device containing such a composition. Another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

式（１）において、Ｒ^１およびＲ^２は独立して、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａは１，２−シクロプロピレン、１，３−シクロブチレン、１，３−シクロペンチレン、１，３−シクロペンテニレン、１，４−シクロペンテニレン、または３、５−シクロペンテニレンであり、これらの基において、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく；環Ｂは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルであり；Ｘ^１およびＸ^２は独立して、水素、フッ素、またはトリフルオロメチルであり；Ｚ^１およびＺ^２は独立して、酸素、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ａは、０、１、２、または３である。 A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1) as a first component, and having a nematic phase and negative dielectric anisotropy, and the composition The present invention relates to a liquid crystal display device.

In formula (1), R ¹ and R ² independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons Or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring A is 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1 , 3-cyclopentenylene, 1,4-cyclopentenylene, or 3, 5-cyclopentenylene, and in these groups, at least one -CH ₂ -may be replaced by -O- Ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine- or chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or X ¹ and X ² are independently hydrogen, fluorine, or trifluoromethyl; and Z ¹ and Z ² are independent, at least one hydrogen being chroman- ² , 6-diyl, wherein fluorine or chlorine is replaced; And oxygen, a single bond, ethylene, carbonyloxy or methyleneoxy; a is 0, 1, 2 or 3.

  The advantages of the present invention are: high upper limit temperature of nematic phase, lower lower limit temperature of nematic phase, small viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, thermal It is to provide a liquid crystal composition satisfying at least one of the high stability, the large elastic constant, and the like. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display device containing such a composition. Another advantage is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

  The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for liquid crystal display panels and liquid crystal display modules. The “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and has no liquid crystal phase, but has a composition for the purpose of adjusting properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a generic term for compounds mixed in a substance. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rod-like. The "polymerizable compound" is a compound to be added for the purpose of forming a polymer in the composition. Liquid crystalline compounds having an alkenyl are not polymerizable in that sense.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor and a polar compound are added to the liquid crystal composition as necessary. Ru. The proportion of the liquid crystal compound is represented by mass percentage (mass%) based on the mass of the liquid crystal composition not including the additive even when the additive is added. The proportion of the additive is represented by mass percentage (mass%) based on the mass of the liquid crystal composition containing no additive. That is, the proportions of the liquid crystal compound and the additive are calculated based on the total mass of the liquid crystal compound. Parts per million (ppm) by mass may be used. The proportions of the polymerization initiator and the polymerization inhibitor are exceptionally expressed based on the weight of the polymerizable compound.

  The “upper limit temperature of the nematic phase” may be abbreviated as the “upper limit temperature”. The “lower limit temperature of the nematic phase” may be abbreviated as the “lower limit temperature”. "High resistivity" means that the composition has high resistivity in the initial stage and has high resistivity after prolonged use. The "high voltage holding ratio" means that the device has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit at the initial stage, and after a long period of use it shows a large voltage not only at room temperature but also at a temperature near the upper limit. It means having a retention rate. The characteristics of the composition or the device may be examined by a time-dependent change test. The expression "increase the dielectric anisotropy" means that in the case of a composition having a positive dielectric anisotropy, the value increases positively, and a composition having a negative dielectric anisotropy. In the case of goods, it means that the value increases negatively.

  The compound represented by Formula (1) may be abbreviated as "compound (1)." The “compound (1)” means one compound, a mixture of two compounds or a mixture of three or more compounds represented by the formula (1). The expression “at least one compound selected from the compounds represented by the formula (1) and the formula (2)” means at least one compound selected from the group of the compound (1) and the compound (2) . The expression "at least one 'A'" means that the number of 'A' is arbitrary. In the expression “at least one 'A' may be replaced by 'B'”, when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is two Even in the case of three or more, their positions can be selected without limitation. This rule also applies to the expression "at least one 'A' replaced by 'B'".

Expressions such as “at least one —CH ₂ — may be replaced by —O—” are used herein. In this case, -CH ₂ -CH ₂ -CH ₂ -may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, adjacent -CH _2- is not replaced by -O-. This replacement is -O-O-CH ₂ - is because (peroxide) is produced. That is, this expression includes both "one -CH _2- may be replaced by -O-" and "at least two non-adjacent -CH _2- may be replaced by -O-" means.

In the chemical formulas of component compounds, the symbol of terminal group R ¹ is used for a plurality of compounds. In these compounds, two groups represented by any two R ¹ may be identical 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 other end groups. In the formula (2), when the index 'b' is 2, two rings C are present. In this compound, two rings represented by two rings C may be identical or different. This rule applies to any two rings C when the index 'b' is greater than two. This rule also applies to symbols such as Z ³ and ring E. This rule also applies when the compounds have identical substituents.

Symbols such as A, B, C and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C and ring D, respectively, and have a three-, four-, five-, six-membered ring And a ring such as a fused ring. In the compound (4), the oblique lines crossing one side of this hexagon indicate that any hydrogen on the ring may be replaced by a group such as -Sp ¹ -P ¹ . A subscript such as 'f' indicates the number of groups replaced. There is no such substitution when the subscript 'f' is 0 (zero). When the subscript 'f' is 2 or more, a plurality of -Sp ¹ -P ¹ is present on ring I. The plurality of groups represented by -Sp ¹ -P ¹ may be identical or different. The expression "ring A and ring B are independently X, Y or Z" means that ring A and ring B are independently selected from the group of X, Y and Z . When the subject is "ring A", "independent" is not used because the subject is singular. This rule also applies to other symbols.

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 left-right asymmetric divalent groups generated by removing two hydrogens from the ring such as tetrahydropyran-2,5-diyl. This rule also applies to divalent linking groups such as carbonyloxy (-COO- or -OCO-).

または

であり、好ましくは

である。 The alkyl of the liquid crystal compound is linear or branched and does not contain cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same is true for end groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

  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、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ａは１，２−シクロプロピレン、１，３−シクロブチレン、１，３−シクロペンチレン、１，３−シクロペンテニレン、１，４−シクロペンテニレン、または３、５−シクロペンテニレンであり、これらの基において、少なくとも１つの−ＣＨ_２−は−Ｏ−で置き換えられてもよく；環Ｂは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルであり；Ｘ^１およびＸ^２は独立して、水素、フッ素、またはトリフルオロメチルであり；Ｚ^１およびＺ^２は独立して、酸素、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ａは、０、１、２、または３である。 Item 1. A liquid crystal composition comprising at least one compound selected from compounds represented by formula (1) as a first component, and having a nematic phase and negative dielectric anisotropy.

In formula (1), R ¹ and R ² independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons Or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring A is 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1 , 3-cyclopentenylene, 1,4-cyclopentenylene, or 3, 5-cyclopentenylene, and in these groups, at least one -CH ₂ -may be replaced by -O- Ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen Fluorine- or chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or X ¹ and X ² are independently hydrogen, fluorine, or trifluoromethyl; and Z ¹ and Z ² are independent, at least one hydrogen being chroman- ² , 6-diyl, wherein fluorine or chlorine is replaced; And oxygen, a single bond, ethylene, carbonyloxy or methyleneoxy; a is 0, 1, 2 or 3.

式（１−１）から式（１−５）において、Ｒ^１およびＲ^２は独立して、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；Ｘ^１およびＸ^２は独立して、水素、フッ素、またはトリフルオロメチルである。 Item 2. Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from the compounds represented by formulas (1-1) to (1-5) as a first component.

In formulas (1-1) to (1-5), R ¹ and R ² independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , Alkenyloxy having 2 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; X ¹ and X ² independently represent hydrogen, fluorine, or trifluoro. It is methyl.

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, wherein the proportion of the first component is in the range of 3% by mass to 20% by mass.

式（２）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｃおよび環Ｄ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２，５−ジフルオロ−１，４−フェニレンであり；Ｚ^３は、単結合、エチレン、またはカルボニルオキシであり；ｂは、１、２、または３である。 Item 4. 4. The liquid crystal composition according to any one of items 1 to 3, containing at least one compound selected from the compounds represented by formula (2) as a second component.

In formula (2), R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine. C 1 to C 12 alkyl, or C 2 to C 12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene or carbonyloxy; b is 1 , 2 or 3.

式（２−１）から式（２−１３）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。 Item 5. 5. The liquid crystal composition according to any one of items 1 to 4, containing at least one compound selected from the compounds represented by formulas (2-1) to (2-13) as a second component.

In formulas (2-1) to (2-13), R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is an alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 6. Item 6. The liquid crystal composition according to item 4 or 5, wherein the proportion of the second component is in the range of 15% by mass to 80% by mass.

式（３）において、Ｒ^５およびＲ^６は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または水素であり；環Ｅおよび環Ｇ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、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルであり；環Ｆは、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、２，３−ジフルオロ−５−メチル−１，４−フェニレン、３，４，５−トリフルオロナフタレン−２，６−ジイル、７，８−ジフルオロクロマン−２，６−ジイル、３，４，５，６−テトラフルオロフルオレン−２，７−ジイル、４，６−ジフルオロジベンゾフラン−３，７−ジイル、または１，１，６，７−テトラフルオロインダン−２，５−ジイルでありであり；Ｚ^４およびＺ^５は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ｃは、１、２、または３であり；ｄは、０または１であり；ｃとｄとの和は３以下である。 Item 7. 7. The liquid crystal composition according to any one of items 1 to 6, containing at least one compound selected from the compounds represented by formula (3) as a third component.

In formula (3), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, or At least one hydrogen is an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine, or hydrogen; ring E and ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, Tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen is fluorine or chlorine Substituted naphthalene-2,6-diyl, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine Ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5 substituted chroman-2,6-diyl; -Methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ⁴ and Z ⁵ are independently C is 1, 2 or 3; d is 0 or 1; and the sum of c and d is 3 or less.

式（３−１）から式（３−３３）において、Ｒ^５およびＲ^６は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルである。 Item 8. 8. The liquid crystal composition according to any one of items 1 to 7, containing at least one compound selected from the compounds represented by formula (3-1) to formula (3-33) as a third component.

In formulas (3-1) to (3-33), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is an alkenyloxy of the number 2 to 12 or an alkyl of the number 1 to 12 carbon in which at least one hydrogen is replaced by fluorine or chlorine.

Item 9. Item 9. The liquid crystal composition according to item 7 or 8, wherein the proportion of the third component is in the range of 10% by mass to 80% by mass.

式（４）において、環Ｉおよび環Ｋは独立して、シクロヘキシル、シクロヘキセニル、フェニル、１−ナフチル、２−ナフチル、テトラヒドロピラン−２−イル、１，３−ジオキサン−２−イル、ピリミジン−２−イル、またはピリジン−２−イルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｊは、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、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、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、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ^６およびＺ^７は独立して、単結合または炭素数１から１０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−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−、−Ｃ（ＣＨ_３）＝ＣＨ−、−ＣＨ＝Ｃ（ＣＨ_３）−、または−Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）−で置き換えられてもよく、これらの基において、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；Ｐ^１、Ｐ^２、およびＰ^３は独立して、重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、単結合、または炭素数１から１０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−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、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；ｅは、０、１、または２であり；ｆ、ｇ、およびｈは独立して、０、１、２、３、または４であり；そしてｆ、ｇ、およびｈの和は、１以上である。 Item 10. Item 10. The liquid crystal composition according to any one of items 1 to 9, containing at least one compound selected from polymerizable compounds represented by formula (4) as a first additive.

In formula (4), ring I and ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Fluorine or chlorine may be substituted by alkyl having 1 to 12 carbon atoms; ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1, -Diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 to 12 alkyl, C 1 to C 12 alkoxy, or at least one hydrogen may be replaced by C 1 to C 12 alkyl substituted with fluorine or chlorine; Z ⁶ and Z ⁷ are independently is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - OO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{1, P} 2, And P ³ independently represent a polymerizable group; Sp ¹ , Sp ² and Sp ^{3 each} independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one of- CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ -is -CH = CH- or -C≡C Replaced by- Well, in these groups, at least one hydrogen may be replaced by fluorine or chlorine; e is 0, 1 or 2; f, g and h are independently 0, 1, 0, 1 And 2, 3 or 4; and the sum of f, g and h is 1 or more.

式（Ｐ−１）から式（Ｐ−５）において、Ｍ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 11. Item 10, wherein P ¹ , P ² and P ³ in Formula (4) are independently a group selected from the polymerizable groups represented by Formula (P-1) to Formula (P-6) The liquid crystal composition as described.

In formulas (P-1) to (P-5), M ¹ , M ² and M ³ independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by

式（４−１）から式（４−２９）において、Ｐ^４、Ｐ^５、およびＰ^６は独立して、式（Ｐ−１）から式（Ｐ−３）で表される基から選択された重合性基であり；

ここで、Ｍ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルであり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は独立して、単結合、または炭素数１から１０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−、−ＣＯＯ−、−ＯＣＯ−、または−ＯＣＯＯ−で置き換えられてもよく、少なくとも１つの−ＣＨ_２−ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、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い。 Item 12. Item 12. The liquid crystal according to any one of items 1 to 11, containing at least one polymerizable compound selected from the compounds represented by formulas (4-1) to (4-29) as the first additive: Composition.

In formulas (4-1) to (4-29), P ⁴ , P ⁵ and P ⁶ are independently selected from groups represented by formulas (P-1) to (P-3) A polymerizable group;

Here, M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Sp ¹ , Sp ² and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— And —OCO— or —OCOO—, and at least one —CH ₂ —CH ₂ — may be replaced by —CH = CH— or —C≡C— in these groups , At least one hydrogen may be replaced by fluorine or chlorine.

Item 13. Item 13. The liquid crystal composition according to any one of items 10 to 12, wherein the proportion of the first additive is in the range of 0.03% by mass to 10% by mass.

Item 14. Item 14. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 13.

Item 15. Item 15. The liquid crystal display element according to item 14, wherein an operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and a driving method of the liquid crystal display element is an active matrix method.

Item 16. Item 14. A polymer supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 13 or in which a polymerizable compound in the liquid crystal composition is polymerized.

Item 17. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a liquid crystal display device.

Item 18. Item 14. Use of the liquid crystal composition according to any one of items 1 to 13 in a polymer supported alignment type liquid crystal display device.

  The present invention also includes the following items. (A) The liquid crystal composition described above is disposed between two substrates, light is irradiated to the composition under voltage application, and the polar compound having a polymerizable group contained in the composition is polymerized. A method of manufacturing the above liquid crystal display device by (B) The upper limit temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy (measured at 25 ° C.) at a wavelength of 589 nm is 0.08 or more, and the dielectric anisotropy (measured at 25 ° C. at a frequency of 1 kHz) The above liquid crystal composition, wherein

  The present invention also includes the following items. (C) As a second additive, such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, a polymerizable compound different from the compound (4), a polymerization initiator, a polymerization inhibitor, a polar compound The above composition further comprising at least one of the following: (D) AM element containing the above composition. (E) AM element of polymer supported orientation (PSA) type containing the above composition further containing a polymerizable compound. (F) An AM element of the polymer supported orientation (PSA) type, containing the composition described above, wherein the polymerizable compound in the composition is polymerized. (G) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (H) A transmission type device containing the above composition. (I) Use of the above composition as a composition having a nematic phase. (J) Use as an optically active composition by adding an optically active compound to the above composition.

  The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main properties of the component compounds and the main effects of the compounds on the composition are explained. Third, the combination of components in the composition, the preferred ratio of the components and the basis thereof will be described. Fourth, the preferred embodiments of the component compounds are described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, the synthesis methods of the component compounds will be described. Finally, the application of the composition is described.

  First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. The composition may contain an additive. The additive is an optically active compound, an antioxidant, an ultraviolet light absorber, a quencher, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound and the like. This composition is classified into the composition A and the composition B from the viewpoint of the liquid crystal compound. Composition A may further contain other liquid crystal compounds, additives, and the like, in addition to the liquid crystal compound selected from compound (1), compound (2), and compound (3). The “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2) and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

  Composition B consists essentially of the liquid crystal compound selected from compound (1), compound (2), and compound (3). The term "substantially" means that composition B may contain an additive, but does not contain any other liquid crystal compound. Composition B has a smaller number of components than composition A. Composition B is preferable to composition A in terms of cost reduction. Composition A is preferable to composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

  Second, the main properties of the component compounds and the main effects of the compounds on the composition are explained. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols of Table 2, L means large or high, M medium, and S small or low. The symbols L, M, S are classifications based on qualitative comparisons among the component compounds, and the symbol 0 (zero) means smaller than S (small).

  When the component compounds are mixed into the composition, the main effects of the component compounds on the properties of the composition are as follows. The compound (1) raises the dielectric anisotropy. The compound (2) raises the upper limit temperature or lowers the viscosity. Compound (3) lowers the lower limit temperature and raises the dielectric anisotropy. Compound (4) gives a polymer by polymerization, which shortens the response time of the device and improves the image sticking.

  Third, the combination of the component compounds in the composition, the preferable ratio and the basis thereof will be described. Preferred combinations of the components in the composition are compound (1) + compound (2), compound (1) + compound (2) + compound (3), compound (1) + compound (2) + first additive, compound (1) + compound (2) + compound (3) + first additive. A further preferable combination is compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (3) + first additive.

  The preferred proportion of the compound (1) is about 3% by mass or more in order to increase the dielectric anisotropy, and about 20% by mass or less in order to lower the lower limit temperature. A further preferred ratio is in the range of about 3% by weight to about 18% by weight. An especially desirable ratio is in the range of about 4% by weight to about 15% by weight.

  The preferred proportion of the compound (2) is about 15% by mass or more to lower the viscosity, and about 80% by mass or less to lower the lower limit temperature. A further preferred ratio is in the range of about 25% by weight to about 65% by weight. An especially desirable ratio is in the range of about 30% by weight to about 60% by weight.

  The preferred proportion of the compound (3) is about 10% by mass or more to increase the dielectric anisotropy or to raise the upper limit temperature, and is about 80% by mass or less to lower the lower limit temperature. A further preferred ratio is in the range of about 15% by weight to about 70% by weight. An especially desirable ratio is in the range of about 20% by weight to about 60% by weight.

  The first additive is added to the composition as a first additive for the purpose of being adapted to a polymer-supported oriented device. The preferred proportion of the first additive is about 0.03% by mass or more for aligning liquid crystal molecules, and about 10% by mass or less for preventing display defects of the device. A further preferred ratio is in the range of about 0.1% by weight to about 2% by weight. An especially desirable ratio is in the range of about 0.2% by mass to about 1.0% by mass.

Fourth, the preferred embodiments of the component compounds are described. First, three liquid crystal compounds will be described collectively. Next, the first additive and the second additive will be described in order.
(A) Liquid Crystalline Compounds In the formulas (1), (2) and (3), R ¹ and R ² are independently hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, It is an alkenyl having 2 to 12 carbons, an alkenyloxy having 2 to 12 carbons, or an alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ¹ or R ² is hydrogen to lower the viscosity, alkyl having 1 to 12 carbon atoms to increase the stability to ultraviolet light and heat, and 1 to carbon atoms to increase the dielectric anisotropy. 12 alkoxy. R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 1 having carbons in which at least one hydrogen is replaced by fluorine or chlorine. 12 alkyl, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ³ or R ⁴ is alkenyl having 2 to 12 carbons to lower the viscosity, and alkyl having 1 to 12 carbons to increase the stability to ultraviolet light and heat. R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, at least one hydrogen is fluorine or It is a C1-C12 alkyl substituted by chlorine or hydrogen. Desirable R ⁵ or R ⁶ is alkyl having 1 to 12 carbons in order to increase the stability to ultraviolet light and heat, and alkoxy having 1 to 12 carbons in order to increase the dielectric anisotropy.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl or pentyl to lower the viscosity.

  Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More desirable alkoxy is methoxy or ethoxy for decreasing the viscosity.

  Preferred alkenyl is vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl to lower the viscosity. The preferred configuration of -CH = CH- in these alkenyls depends on the position of the double bond. Trans is preferable in the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity and the like. Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

  Preferred examples of the alkyl in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl Or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl or 5-fluoropentyl to increase dielectric anisotropy.

  Preferred examples of the alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are: 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro -4-pentenyl or 6,6-difluoro-5-hexenyl. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for decreasing the viscosity.

好ましい環Ｆは、誘電率異方性を上げるために２，３−ジフルオロ−１，４−フェニレンである。 Ring A is 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3-cyclopentenylene, 1,4-cyclopentenylene or 3,5-cyclo And pentenylene, in which at least one -CH _2- may be replaced by -O-. Preferred ring A is 1,3-cyclopentylene to increase the maximum temperature. Ring B, ring E and ring G are each independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine Or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least Chroman-2,6-diyl in which one hydrogen is replaced by fluorine or chlorine. Preferred ring B, ring E or ring G is 1,4-cyclohexylene to lower the viscosity or to raise the upper limit temperature, 1,4-phenylene to lower the lower limit temperature, and the dielectric constant It is 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine to increase anisotropy. Ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene. Preferred ring C or ring D is 1,4-cyclohexylene to lower the viscosity or to raise the upper limit temperature, and 1,4-phenylene to increase the optical anisotropy. Ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,4, 5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF 4), 4,6- Difluorodibenzofuran-3,7-diyl (BFF2) or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4).

Preferred ring F is 2,3-difluoro-1,4-phenylene to increase the dielectric anisotropy.

X ¹ and X ² are independently hydrogen, fluorine or trifluoromethyl. Desirable X ¹ or X ² is fluorine for increasing dielectric anisotropy.

Z ¹ and Z ² are independently oxygen, a single bond, ethylene, carbonyloxy or methyleneoxy. Preferred Z ¹ or Z ² is a single bond to lower the viscosity, and oxygen or methyleneoxy to lower the upper temperature limit. Z ³ is a single bond, ethylene or carbonyloxy. Preferred Z ³ is a single bond to lower the viscosity. Z ⁴ and Z ⁵ are independently a single bond, ethylene, carbonyloxy or methyleneoxy. Desirable Z ⁴ or Z ⁵ is a single bond to lower the viscosity, and methyleneoxy to raise the dielectric anisotropy.

  a is 0, 1, 2 or 3. Preferred a is 0 to reduce the viscosity. b is 1, 2 or 3; Preferred b is 1 to lower the viscosity and 2 to raise the upper temperature limit. c is 1, 2 or 3; d is 0 or 1; and the sum of c and d is 3 or less. Preferred c is 1 to lower the viscosity and 2 to raise the upper temperature limit. Preferred d is 0 to lower the viscosity and 1 to raise the upper temperature limit.

(B) First additive In the formula (4), P ¹ , P ² and P ³ are independently a polymerizable group. Preferred P ¹ , P ² or P ³ is a group selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-5). Further preferable P ¹ , P ² or P ³ is a group represented by formula (P-1), formula (P-2) or formula (P-3). Particularly preferred P ¹ , P ² or P ³ is a group represented by formula (P-1) or formula (P-2). Most preferable P ¹ , P ² or P ³ is a group represented by formula (P-1). Preferred groups represented by the formula (P-1) is, -OCO-CH = CH ₂ or _{-OCO-C (CH} 3) a = CH _2. The wavy lines in Formula (P-1) to Formula (P-5) indicate the binding site.

In formulas (P-1) to (P-5), M ¹ , M ² and M ³ independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by Preferred M ¹ , M ² or M ³ is hydrogen or methyl to increase the reactivity. Further preferred M ¹ is hydrogen or methyl, and further preferred M ² or M ³ is hydrogen.

Sp ¹ , Sp ² and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, —OCO -Or -OCOO-, and at least one -CH ₂ -CH ₂ -may be replaced by -CH = CH- or -C≡C-; One hydrogen may be replaced by fluorine or chlorine. Preferred Sp ¹ , Sp ² or Sp ³ is a single bond, -CH ₂ -CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, Or -CH = CH-CO-. Further preferred Sp ¹ , Sp ² or Sp ³ is a single bond.

  Ring I and ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl or pyridine -2-yl, in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is replaced by fluorine or chlorine May be substituted with alkyl having 1 to 12 carbon atoms. Preferred ring I and ring K are phenyl. Ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene 1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2 , 7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl in these rings, At least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine. From the obtained 1 carbon atoms may be replaced by alkyl of 12. Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁶ and Z ⁷ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO—, or — OCO- may be replaced and at least one -CH ₂ -CH ₂ -is -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ ) — may be replaced, and in these groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z ⁶ or Z ⁷ is a single bond, -CH ₂ -CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Further preferred Z ⁶ or Z ⁷ is a single bond.

  e is 0, 1 or 2; Preferred e is 0 or 1. f, g and h are independently 0, 1, 2, 3 or 4 and the sum of f, g and h is 1 or more. Preferred f, g or h is 1 or 2.

  Fifth, preferred component compounds are shown. The preferred compound (1) is the compound (1-1) to the compound (1-5) described in item 2. In these compounds, it is preferable that at least one of the first components is a compound (1-1), a compound (1-2), a compound (1-3), or a compound (1-4). At least two of the first components are a compound (1-1) and a compound (1-2), a compound (1-1) and a compound (1-3), a compound (1-2) and a compound (1-3), It is preferable that it is a combination of a compound (1-3) and a compound (1-4).

  The preferred compound (2) is the compound (2-1) to the compound (2-13) described in item 5. In these compounds, at least one of the second components is a compound (2-1), a compound (2-2), a compound (2-3), a compound (2-4) a compound (2-5), a compound (2) -6), the compound (2-7), the compound (2-11) or the compound (2-13). It is preferable that at least two of the second components be a combination of the compound (2-1) and the compound (2-3), the compound (2-1) and the compound (2-5).

  The preferred compound (3) is a compound (3-1) to a compound (3-33) described in item 8. In these compounds, at least one of the third components is a compound (3-1), a compound (3-3), a compound (3-6), a compound (3-8), a compound (3-10), a compound (3-10) It is preferable that it is 3-13), a compound (3-14), or a compound (3-16). At least two of the third components are the compound (3-1) and the compound (3-8), the compound (3-1) and the compound (3-14), the compound (3-3) and the compound (3-8), Compound (3-3) and Compound (3-10), Compound (3-3) and Compound (3-14), Compound (3-6) and Compound (3-8), Compound (3-6) and Compound It is preferable that it is a combination of (3-10), a compound (3-6) and a compound (3-16), or a compound (3-10) and a compound (3-14).

  The preferred compound (4) is a compound (4-1) to a compound (4-29) described in Item 12. In these compounds, at least one of the first additives is a compound (4-1), a compound (4-2), a compound (4-24), a compound (4-25), a compound (4-26), or It is preferable that it is a compound (4-27). At least two of the first additives are the compound (4-1) and the compound (4-2), the compound (4-1) and the compound (4-18), the compound (4-2) and the compound (4-24) A compound (4-2) and a compound (4-25), a compound (4-2) and a compound (4-26), a compound (4-25) and a compound (4-26), or a compound (4-18) It is preferable that it is a combination of and a compound (4-24).

  Sixth, additives that may be added to the composition will be described. Such additives include optically active compounds, antioxidants, ultraviolet light absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compounds (5-1) to (5-5). The preferred proportion of the optically active compound is about 5% by mass or less. A further preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

In order to prevent the decrease in specific resistance due to heating in the atmosphere, or after using the device for a long time, in order to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature, Is added to the Preferred examples of the antioxidant include compound (6-1) to compound (6-3).

  Since the compound (6-2) has low volatility, it is effective to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. The preferred proportion of the antioxidant is about 50 ppm or more to obtain its effect, and is about 600 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. Preferred examples of the light stabilizer include compound (7-1) to compound (7-16). The preferred proportion of these absorbents and stabilizers is about 50 ppm or more to obtain the effect, and about 10000 ppm or less so as not to lower the upper temperature limit or to raise the lower temperature limit. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

A quencher is a compound which receives the light energy absorbed by the liquid crystal compound and converts it into heat energy to prevent the decomposition of the liquid crystal compound. Preferred examples of the quencher include compound (8-1) to compound (8-7). The preferred proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less to lower the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

  In order to conform to a guest host (GH) mode device, a dichroic dye such as an azo dye or an anthraquinone dye is added to the composition. The preferred proportion of dye is in the range of about 0.01% by weight to about 10% by weight. In order to prevent foaming, an antifoam agent such as dimethyl silicone oil, methylphenyl silicone oil or the like is added to the composition. The preferable proportion of the antifoaming agent is about 1 ppm or more in order to obtain the effect, and is about 1000 ppm or less in order to prevent display defects. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

  Polymerizable compounds are used to make them compatible with polymer-supported oriented (PSA) type devices. Compound (4) is suitable for this purpose. Along with the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Preferred examples of other polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl ketones and the like. Further preferred examples are acrylate and methacrylate. By changing the type of the compound (4) or by combining the compound (4) with a polymerizable compound different from the compound (4) in an appropriate ratio, the reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecule Can be adjusted. By optimizing the pretilt angle, short response times of the device can be achieved. Since the alignment of liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.

  The polymerizable compound such as the compound (4) is polymerized by ultraviolet irradiation. It may be polymerized in the presence of a suitable initiator such as a photoinitiator. Appropriate conditions for polymerization, appropriate types of initiators, and appropriate amounts are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. The preferred proportion of the photoinitiator is in the range of about 0.1 wt% to about 5 wt% based on the weight of the polymerizable compound. A further preferred ratio is in the range of about 1% by weight to about 3% by weight.

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

Polar compounds are organic compounds with polarity. Here, compounds having an ionic bond are not included. Atoms such as oxygen, sulfur and nitrogen are more electronegative and tend to have a partial negative charge. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity results from the inhomogeneous distribution of partial charges among different types of atoms in the compound. For example, polar compounds have _{-OH, -COOH, -SH, -NH 2} ,> NH, at least one of the> N-moiety like.

  Seventh, the synthesis methods of the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. Examples of the synthesis of compound (1) are described in the section of Examples. The compound (2-5) is synthesized by the method described in JP-A-59-176221. The compound (3-8) is synthesized by the method described in JP-A-2-503441. The compound (4-19) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compound (6-1) is available from Aldrich (Sigma-Aldrich Corporation). Compounds (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

  Compounds that did not describe the method of synthesis were organic syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), complementary organic syntheses ( It can be synthesized by the method described in the book of Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Lecture (Maruzen) and the like. The compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved together by heating.

  Finally, the application of the composition is described. Most compositions have a lower temperature limit of about -10 ° C. or lower, an upper temperature limit of about 70 ° C. or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the component compounds, or by mixing other liquid crystal compounds. Furthermore, compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. Devices containing this composition have a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for transmissive AM devices. This composition can be used as a composition having a nematic phase or as an optically active composition by adding an optically active compound.

  This composition can be used for an AM device. Furthermore, the use to PM element is also possible. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA. The use for an AM device having a TN, OCB, IPS mode or FFS mode is particularly preferred. In an AM device having an IPS mode or an FFS mode, the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate when no voltage is applied. These elements may be reflective, transmissive or semi-transmissive. Its use for transmission type devices is preferred. The use for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements is also possible. The composition can be used for an element of NCAP (nematic curvilinear aligned phase) type prepared by microencapsulation or a element of PD (polymer dispersed) type in which a three-dimensional network polymer is formed in the composition.

  An example of the method for producing a polymer-supported oriented device is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additives may be further added as needed. The composition is injected into the device. Light is irradiated in a state where a voltage is applied to this element. UV light is preferred. The polymerizable compound is polymerized by light irradiation. This polymerization produces a composition containing a polymer. A polymer-supported oriented device is manufactured by such a procedure.

  In this procedure, when a voltage is applied, liquid crystal molecules are aligned by the action of an alignment film and an electric field. The molecules of the polymerizable compound are also oriented according to this orientation. In this state, since the polymerizable compound is polymerized by ultraviolet light, a polymer maintaining this orientation is formed. The effect of the polymer reduces the response time of the device. Since image sticking is a malfunction of liquid crystal molecules, the effect of the polymer is to simultaneously improve the sticking. In addition, it is also possible to pre-polymerize the polymerizable compound in the composition and arrange this composition between the substrates of the liquid crystal display element.

  The invention will be further described by way of examples. The invention is not limited by these examples. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the compositions of the Examples. The compound synthesized was identified by a method such as NMR analysis. The properties of the compounds, compositions and devices were measured by the methods described below.

NMR analysis: For measurement, DRX-500 manufactured by Bruker Biospin Ltd. was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature under conditions of 500 MHz and 16 integrations. Tetramethylsilane was used as an internal standard. ^{In 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the number of integrations was 24 times. In the description of nuclear magnetic resonance spectrum, s is singlet, d is doublet, t is triplet, q is quartet, quin is quintet, sex is sextet, m is multiplet, br is broad.

  Gas Chromatographic Analysis: A GC-14B gas chromatograph made by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set at 280 ° C. and the detector (FID) was set at 300 ° C. For separation of the component compounds, capillary columns DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; fixed liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. were used. The column was kept at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./minute. The sample was prepared in an acetone solution (0.1% by mass), and 1 μL thereof was injected into the sample vaporization chamber. The recorder is Model C-R5A Chromatopac manufactured by Shimadzu Corporation, or its equivalent. The obtained gas chromatogram showed the retention time of the peak corresponding to the component compound and the area of the peak.

  As a solvent for diluting the sample, chloroform, hexane or the like may be used. The following capillary column may be used to separate the component compounds. HP-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in thickness) manufactured by Agilent Technologies Inc., Rtx-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in film thickness) manufactured by Restek Corporation, BP-1 (30 m in length, 0.32 mm in inner diameter, 0.25 μm in film thickness) manufactured by SGE International Pty. Ltd. A capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used for the purpose of preventing overlapping of compound peaks.

  The proportion of the liquid crystal compound contained in the composition may be calculated by the following method. The mixture of liquid crystalline compounds is analyzed by gas chromatography (FID). The area ratio of peaks in the gas chromatogram corresponds to the proportion (mass ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (mass%) of the liquid crystal compound can be calculated from the area ratio of the peaks.

  Measurement sample: When measuring the characteristics of the composition and the device, the composition was used as it was as a sample. When measuring the properties of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with the mother liquid crystal (85% by mass). The characteristic values of the compound were calculated by extrapolation from the values obtained by the measurement. (Extrapolated value) = {(measured value of sample) −0.85 × (measured value of base liquid crystal)} / 0.15. When a smectic phase (or crystal) precipitates at 25 ° C. in this proportion, the proportion of the compound and the base liquid crystal is 10 mass%: 90 mass%, 5 mass%: 95 mass%, 1 mass%: 99 mass% in this order. changed. The values of the upper limit temperature, the optical anisotropy, the viscosity, and the dielectric anisotropy of the compound were determined by this extrapolation method.

The following mother liquid crystals were used. The proportions of the component compounds are indicated by mass%.

  Measurement method: The measurement of the characteristics was performed by the following method. Many of these are modified methods or methods described in the JEITA standard (JEITA ED-2521B), which is deliberately established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA). It was a method. A thin film transistor (TFT) was not attached to the TN device used for the measurement.

(1) Upper limit temperature of nematic phase (NI; ° C.): The sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarization microscope and heated at a rate of 1 ° C./min. The temperature was measured when part of the sample changed from the nematic phase to the isotropic liquid. The upper limit temperature of the nematic phase may be abbreviated as "upper limit temperature".

(2) 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, the sample remained in the -20 ° C. in a nematic phase, when changed to -30 ° C. At crystals or a smectic phase was described as <-20 ° C. The T _C. The lower limit temperature of the nematic phase may be abbreviated as "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s): For measurement, a rotational viscosity measurement system LCM-2 type manufactured by Toyo Technica Co., Ltd. was used. The sample was injected into a VA device in which the distance between two glass substrates (cell gap) was 10 μm. A rectangular wave (55 V, 1 ms) was applied to this element. The peak current and peak time of transient current generated by this application were measured. The values of rotational viscosity were obtained using these measured values and dielectric anisotropy. The dielectric anisotropy was measured by the method described in the measurement (6).

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

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

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

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

(9) Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured in the same procedure as described above except that measurement was performed at 80 ° C. instead of 25 ° C. The obtained value was expressed as VHR-2.

(10) Voltage holding ratio (VHR-3; measured at 25 ° C .;%): After irradiation with ultraviolet light, the voltage holding ratio was measured to evaluate the stability to ultraviolet light. The TN device used for the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into the device and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Inc.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, the decaying voltage was measured for 16.7 milliseconds. Compositions with large VHR-3 have high stability to ultraviolet light. 90% or more is preferable and 95% or more of VHR-3 is more preferable.

(11) Voltage holding ratio (VHR-4; measured at 25 ° C .;%): The TN device injected with the sample is heated in a thermostatic chamber at 80 ° C. for 500 hours, and then the voltage holding ratio is measured and stability to heat Was evaluated. In the measurement of VHR-4, the decaying voltage was measured for 16.7 milliseconds. Compositions having large VHR-4 have great stability to heat.

(12) Response time (τ; measured at 25 ° C .; ms): For measurement, LCD Evaluation System Model LCD-5100 made by Otsuka Electronics Co., Ltd. was used. The light source was a halogen lamp. The low pass filter (Low-pass filter) was set to 5 kHz. The sample was placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was antiparallel. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The response time is represented by the time (fall time; milliseconds) taken to change from 90% transmittance to 10% transmittance.

(13) Elastic constant (K; measured at 25 ° C .; pN): For measurement, HP4284A LCR meter manufactured by Yokogawa-Hewlett-Packard Co. was used. The sample was placed in a horizontal alignment device in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 0 to 20 volts was applied to the device, and the capacitance and the applied voltage were measured. The values of the measured capacitance (C) and the applied voltage (V) can be found in the formula of “Liquid crystal device handbook” (Nippon Kogyo Shimbun Ltd.), page 75
2.98), fitting was performed using equation (2.101), and values of K11 and K33 were obtained from equation (2.99). Next, K22 was calculated using the values of K11 and K33 previously obtained in the equation (3.18) on page 171 in the same. The elastic constant is determined in this way, K11,
It represented by the average value of K22 and K33.

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

Synthesis example 1
The compound (1-2-1) was synthesized by the following route.

Step 1: Synthesis of Compound (T-2) Compound (T-1) (16.0 g), cyclopentylmethanol (8.39 g), triphenylphosphine (26.4 g), and tetrahydrofuran (THF,) under a nitrogen atmosphere 150 mL) was charged into the reactor and cooled on an ice bath. Diethyl azodicarboxylate (DEAD, 2.2 M; toluene solution; 45.7 ml) was added and stirred at room temperature for 8 hours. After completion of the reaction, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The extract was washed with brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 1: 4) to give compound (T-2) (19.8 g; 86%).

Second Step: Synthesis of Compound (T-3) In a nitrogen atmosphere, compound (T-2) (19.8 g) and tetrahydrofuran (THF, 200 mL) were put in a reactor and cooled to -70 ° C. Lithium diisopropylamide (LDA, 1.1 M; n-hexane-tetrahydrofuran solution; 73.0 ml) was added and stirred for 1 hour. Triisopropyl borate (8.9 ml) was added, and the mixture was returned to room temperature and stirred for 12 hours. Acetic acid (8.3 ml) was added at room temperature and stirred for 30 minutes, then aqueous hydrogen peroxide (50 wt%; 8.9 ml) was added and stirred for 1 hour. After completion of the reaction, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The extract was washed with water, saturated aqueous sodium thiosulfate solution and brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, ethyl acetate: heptane = 1: 4) to give compound (T-3) (12.5 g; 59%).

Step 3: Synthesis of Compound (T-5) Compound (T-3) (12.5 g), Compound (T-4) (9.1 g), toluene (125 ml), ethanol (125 ml), under a nitrogen atmosphere Water (125 ml), PdCl ₂ (Amphos) ₂ (Pd-132, 0.03 g), potassium carbonate (11.9 g), and tetrabutylammonium bromide (TBAB, 3.5 g) are charged to the reactor and Stir for 4 hours. The reaction mixture was poured into water and extracted with toluene. The extract was washed with water and brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, ethyl acetate: heptane = 1: 2) to give compound (T-5) (13.0 g; 78%).

Step 4: Synthesis of Compound (1-2-1) Compound (T-5) (13.0 g), sodium hydride (1.7 g), dimethyl sulfoxide (DMSO, 130 ml) in a reactor under a nitrogen atmosphere Then, it was stirred at 120 ° C. for 4 hours. The reaction mixture was poured into water and extracted with toluene. The extract was washed with brine, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography (volume ratio, toluene: heptane = 2: 1). Further, purification was performed by recrystallization from a mixed solvent (volume ratio, 1: 1) of Solmix (registered trademark) A-11 and heptane to obtain compound (1-2-1) (6.0 g; 48%) .

¹ H-NMR (CDCl ₃ ; δ ppm): 7.48-7.45 (m, 2H), 6.99-6.96 (m, 2H), 4.20 (q, J = 7.0 Hz, 2H) ), 4.00 (d, J = 7.0 Hz, 2 H), 2.48-2.39 (m, 1 H), 1.91-1. 85 (m, 2 H), 1.70-1.58 (M, 4H), 1.49 (t, J = 7.0 Hz, 3 H), 1.45-1.36 (m, 2 H). ¹⁹ F-NMR (δ ppm; CDCl ₃ ): −157.91 (d, J = 7.3 Hz, 1 F), −158.10 (d, J = 7.0 Hz, 1 F).

  The compounds in the examples are represented by symbols based on the definition of Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The numbers in parentheses after the symbols correspond to the compound numbers. The symbol (-) means other liquid crystal compounds. The proportion (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition were summarized.

Compounds A to J shown below were used as the first component.

Example 6 was chosen from the composition disclosed by Unexamined-Japanese-Patent No. 2016-506434 as a comparative example. This composition contains a compound K having a cyclopentyl group and a compound L, and has negative dielectric anisotropy.

Comparative Example 1
5-HH-O1 (2-1) 9%
5-HH-3 (2-1) 10%
5-HB-3 (2-2) 14%
2-HHB-3 (2-5) 4%
3-HHB (2F, 3F) -1 (3-8) 14%
5-HHB (2F, 3F) -O2 (3-8) 7%
3-HHB (2F, 3F) -O2 (3-8) 8%
3-HH1OB (2F, 3F) -1 (3-10) 4%
2-HBB (2F, 3F) -O2 (3-14) 12%
Compound K (-) 10%
Compound L (-) 8%
NI = 77.8 ° C .; Δn = 0.092; Δε = −3.8; K33 = 15.2 pN; γ1 = 138 mPa · s.

Example 1
A composition in which the compound K and the compound L are replaced with the compound I and the compound B, respectively, in the composition of Comparative Example 1 is referred to as Example 1.
Compound B (1-1) 8%
Compound I (1-3) 10%
5-HH-O1 (2-1) 9%
5-HH-3 (2-1) 10%
5-HB-3 (2-2) 14%
2-HHB-3 (2-5) 4%
3-HHB (2F, 3F) -1 (3-8) 14%
5-HHB (2F, 3F) -O2 (3-8) 7%
3-HHB (2F, 3F) -O2 (3-8) 8%
3-HH1OB (2F, 3F) -1 (3-10) 4%
2-HBB (2F, 3F) -O2 (3-14) 12%
NI = 73.9 ° C .; Δn = 0.105; Δε = −5.1; K33 = 12.3 pN; γ1 = 160.8 mPa · s.

Example 2
Compound G (1-3) 3%
3-HH-V (2-1) 20%
1-BB-3 (2-3) 1%
V-HHB-1 (2-5) 1%
3-HBB-2 (2-6) 3%
V-HBB-2 (2-6) 4%
3-HB (F) HH-2 (2-10) 2%
3-DhB (2F, 3F) -O2 (3-4) 4%
3-BB (2F, 3F)-O2 (3-6) 8%
5-BB (2F, 3F)-O2 (3-6) 9%
2-HHB (2F, 3F) -O2 (3-8) 3%
3-HHB (2F, 3F) -O2 (3-8) 4%
V-HHB (2F, 3F)-O1 (3-8) 4%
V-HHB (2F, 3F) -O2 (3-8) 10%
V-HHB (2F, 3F) -O4 (3-8) 9%
3-HD h B (2F, 3F)-O2 (3-13) 10%
3-BB (F) B (2F, 3F)-O2 (3-21) 3%
V-HH2BB (2F, 3F)-O2 (3-24) 2%
NI = 93.7 ° C .; Tc <−20 ° C .; Δn = 0.125; Δε = −4.4.

[Example 3]
Compound F (1-3) 3%
3-HH-V (2-1) 14%
1-BB-3 (2-3) 2%
V-HHB-1 (2-5) 2%
V2-HHB-1 (2-5) 2%
3-HBB (F) B-2 (2-13) 4%
3-HB (2F, 3F)-O2 (3-1) 3%
V1O-chB (2F, 3F) -O2 (3-5) 5%
2-BB (2F, 3F)-O2 (3-6) 7%
V2-BB (2F, 3F) -O2 (3-6) 8%
2O-B (2F) B (2F, 3F) -O2 (3-7) 6%
2-HHB (2F, 3F) -O2 (3-8) 7%
3-HHB (2F, 3F) -O2 (3-8) 6%
5-HHB (2F, 3F) -O2 (3-8) 3%
V-HHB (2F, 3F)-O1 (3-8) 4%
V-HHB (2F, 3F) -O2 (3-8) 6%
V-HHB (2F, 3F)-O4 (3-8) 4%
3-HH2B (2F, 3F)-O2 (3-9) 9%
3-BB (2F) B (2F, 3F)-O2 (3-20) 2%
2-BB2B (2F, 3F) -3 (3-23) 3%
NI = 83.6 ° C .; Tc <−20 ° C .; Δn = 0.125; Δε = −4.4.

Example 4
Compound I (1-3) 4%
3-HH-V (2-1) 31%
3-HB (2F, 3F)-O2 (3-1) 10%
2-BB (2F, 3F)-O2 (3-6) 6%
3-BB (2F, 3F)-O2 (3-6) 8%
3-HHB (2F, 3F) -O2 (3-8) 8%
5-HHB (2F, 3F) -O2 (3-8) 8%
V-HHB (2F, 3F) -O2 (3-8) 2%
3-HH2B (2F, 3F)-O2 (3-9) 8%
2-HBB (2F, 3F) -O2 (3-14) 3%
3-HBB (2F, 3F) -O2 (3-14) 8%
4-HBB (2F, 3F) -O2 (3-14) 4%
Tc <−20 ° C .; Δn = 0.103; Δε = −4.1; K33 = 11.4 pN; γ1 = 97.1 mPa · s; = 1 = 17.0 mPa · s.

[Example 5]
Compound A (1-1) 2%
Compound E (1-2) 1%
Compound G (1-3) 3%
2-HH-3 (2-1) 4%
3-HH-4 (2-1) 3%
3-HH-5 (2-1) 5%
3-HB-O2 (2-2) 3%
1-BB-3 (2-3) 4%
1-BB-5 (2-3) 3%
3-HHB-1 (2-5) 1%
3-HBB-2 (2-6) 3%
5-B (F) BB-2 (2-8) 3%
3-HHEBH-3 (2-11) 5%
3-HB (2F, 3F)-O2 (3-1) 4%
2-H1OB (2F, 3F) -O2 (3-3) 6%
2-HH1OB (2F, 3F) -O2 (3-10) 16%
3-HH1OB (2F, 3F) -O2 (3-10) 12%
V-HchB (2F, 3F)-O2 (3-12) 6%
3-HB (2F, 3F) B-O2 (3-17) 4%
3-HB (2F) B (2F, 3F) -O2 (3-18) 6%
2-B2BB (2F, 3F) -O2 (3-22) 4%
3-H 2 BBB (2F, 3F) -O 2 (3-25) 2%
NI = 97.5 ° C .; Tc <−20 ° C .; Δn = 0.126; Δε = −4.3; = 1 = 18.9 mPa · s.

[Example 6]
Compound H (1-3) 7%
3-HH-V (2-1) 28%
3-HH-V1 (2-1) 5%
1-BB-3 (2-3) 3%
3-HB (2F, 3F)-O2 (3-1) 2%
3-BB (2F, 3F)-O2 (3-6) 7%
2-HHB (2F, 3F) -O2 (3-8) 5%
3-HHB (2F, 3F) -O2 (3-8) 8%
5-HHB (2F, 3F) -O2 (3-8) 4%
V-HHB (2F, 3F)-O1 (3-8) 4%
V-HHB (2F, 3F) -O2 (3-8) 5%
3-HH2B (2F, 3F)-O2 (3-9) 10%
3-HD h B (2F, 3F)-O2 (3-13) 7%
3-dhBB (2F, 3F) -O2 (3-16) 5%
Tc <−20 ° C .; Δn = 0.100; Δε = −4.3; K33 = 13.9 pN; γ1 = 125.0 mPa · s; = 2 = 20.6 mPa · s.

[Example 7]
Compound I (1-3) 4%
Compound J (1-4) 1%
2-HH-3 (2-1) 15%
3-HH-V1 (2-1) 3%
1V2-HH-3 (2-1) 4%
5-HB-O2 (2-2) 2%
3-HHEH-3 (2-4) 2%
3-HHB-O1 (2-5) 4%
V-HHB-1 (2-5) 3%
V2-HHB-1 (2-5) 5%
3-BB (2F, 3F)-O2 (3-6) 11%
V2-BB (2F, 3F) -O2 (3-6) 10%
V-HHB (2F, 3F) -O2 (3-8) 7%
3-HH1OB (2F, 3F) -O2 (3-10) 14%
3-HD h B (2F, 3F)-O2 (3-13) 8%
2-BB (2F, 3F) B-3 (3-19) 7%
Tc <−20 ° C .; Δn = 0.115; Δε = −4.4; K33 = 13.5 pN; γ1 = 140.9 mPa · s; = 2 = 22.7 mPa · s.

[Example 8]
Compound E (1-2) 3%
2-HH-3 (2-1) 10%
2-BB (F) B-3 (2-7) 4%
5-B (F) BB-2 (2-8) 10%
2-BB 2 B-3 (2-9) 5%
5-HB (F) BH-5 (2-12) 4%
3-H1OB (2F, 3F) -O2 (3-3) 3%
3-BB (2F, 3F)-O2 (3-6) 9%
5-BB (2F, 3F)-O2 (3-6) 9%
3-HD h B (2F, 3F)-O2 (3-13) 7%
2-HBB (2F, 3F) -O2 (3-14) 3%
3-HBB (2F, 3F) -O2 (3-14) 9%
5-HBB (2F, 3F) -O2 (3-14) 9%
3-dhBB (2F, 3F) -O2 (3-16) 10%
3-H1OCro (7F, 8F) -5 (3-26) 2%
3-HH1OCro (7F, 8F) -5 (3-27) 3%
Tc <−20 ° C .; Δn = 0.171; Δε = −5.1; = 4 = 46.3 mPa · s.

[Example 9]
Compound C (1-2) 1%
Compound D (1-2) 1%
3-HH-V (2-1) 12%
V-HHB-1 (2-5) 3%
5-HBB (F) B-2 (2-13) 3%
3-H 2 B (2F, 3F) -O 2 (3-2) 21%
5-H2B (2F, 3F)-O2 (3-2) 20%
3-DhB (2F, 3F) -O2 (3-4) 4%
3-HHB (2F, 3Cl) -O2 (3-11) 2%
4-HHB (2F, 3Cl) -O2 (3-11) 2%
5-HHB (2F, 3Cl) -O2 (3-11) 2%
3-HBB (2F, 3F) -O2 (3-14) 6%
3-HBB (2F, 3Cl) -O2 (3-15) 9%
4-HBB (2F, 3Cl) -O2 (3-15) 6%
5-HBB (2F, 3Cl) -O2 (3-15) 8%
Tc <−20 ° C .; Δn = 0.108; Δε = −4.4; = 3 = 31.2 mPa · s.

[Example 10]
Compound H (1-3) 6%
Compound I (1-3) 5%
3-HH-V (2-1) 29%
V-HH-V (2-1) 4%
3-HBB (F) B-2 (2-13) 2%
3-H1OB (2F, 3F) -O2 (3-3) 6%
3-BB (2F, 3F)-O2 (3-6) 5%
V-HHB (2F, 3F) -O2 (3-8) 11%
3-HH1OB (2F, 3F) -O2 (3-10) 19%
2-BB (2F, 3F) B-3 (3-19) 13%
Tc <-20 ° C; Δn = 0.113; Δε = -4.1; = 2 = 23.7 mPa · s.

  The dielectric anisotropy of the composition of Comparative Example 1 was -3.8. On the other hand, the dielectric anisotropy of the composition of Example 1 was -5.1. Thus, the composition of Example 1 had large dielectric anisotropy compared to the composition of the comparative example. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

  The liquid crystal composition of the present invention has high upper limit temperature, low lower limit temperature, small viscosity, large optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability against ultraviolet light, high stability against heat, etc. In at least one property, or in at least two properties, there is an appropriate balance. The liquid crystal display element containing this composition has characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, long life, etc., and can therefore be used for liquid crystal monitors, liquid crystal televisions, etc. .

Claims (18)

A liquid crystal composition comprising at least one compound selected from compounds represented by formula (1) as a first component, and having a nematic phase and negative dielectric anisotropy.

In formula (1), R ¹ and R ² independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons Or alkyl of 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring A is 1,2-cyclopropylene, 1,3-cyclobutylene, 1,3-cyclopentylene, 1,3-cyclopentenylene, 1,4-cyclopentenylene or 3,5-cyclopentenylene, in which at least one -CH ₂ -is replaced by -O- Ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen; 1,4-phenylene substituted with fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is substituted with fluorine or chlorine, chroman-2,6-diyl, Or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; X ¹ and X ² are independently hydrogen, fluorine or trifluoromethyl; Z ¹ and Z ² are Independently, oxygen, a single bond, ethylene, carbonyloxy or methyleneoxy; a is 0, 1, 2 or 3. The liquid crystal composition according to claim 1, containing at least one compound selected from the compounds represented by formulas (1-1) to (1-5) as a first component.

In formulas (1-1) to (1-5), R ¹ and R ² independently represent hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , Alkenyloxy having 2 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; X ¹ and X ² independently represent hydrogen, fluorine, or trifluoro. It is methyl.   The liquid crystal composition according to claim 1 or 2, wherein the proportion of the first component is in the range of 3% by mass to 20% by mass. The liquid crystal composition according to any one of claims 1 to 3, containing at least one compound selected from the compounds represented by formula (2) as a second component.

In formula (2), R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine. C 1 to C 12 alkyl, or C 2 to C 12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine; ring C and ring D are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene or carbonyloxy; b is 1 , 2 or 3. The liquid crystal composition according to any one of claims 1 to 4, containing at least one compound selected from the compounds represented by formulas (2-1) to (2-13) as a second component. .

In formulas (2-1) to (2-13), R ³ and R ⁴ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is an alkyl having 1 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine, or an alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 4 or 5, wherein the proportion of the second component is in the range of 15% by mass to 80% by mass. The liquid crystal composition according to any one of claims 1 to 6, containing at least one compound selected from the compounds represented by Formula (3) as a third component.

In formula (3), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, One hydrogen is an alkyl having 1 to 12 carbons in which hydrogen is replaced by fluorine or chlorine, or hydrogen; ring E and ring G are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydro Pyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen is replaced by fluorine or chlorine Naphthalene-2,6-diyl, chroman-2,6-diyl, or at least one hydrogen in fluorine or chlorine Ring F is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5; -Methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z ⁴ and Z ⁵ are independently C is 1, 2 or 3; d is 0 or 1; and the sum of c and d is 3 or less. The liquid crystal composition according to any one of claims 1 to 7, containing at least one compound selected from the compounds represented by formulas (3-1) to (3-33) as a third component. .

In formulas (3-1) to (3-27), R ⁵ and R ⁶ independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is an alkenyloxy of the number 2 to 12 or an alkyl of the number 1 to 12 carbon in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 7 or 8, wherein the proportion of the third component is in the range of 10% by mass to 80% by mass. The liquid crystal composition according to any one of claims 1 to 9, containing at least one compound selected from the polymerizable compounds represented by formula (4) as the first additive.

In formula (4), ring I and ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl in which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Fluorine or chlorine may be substituted by alkyl having 1 to 12 carbon atoms; ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1, 2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1, -Diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, and in these rings, at least one hydrogen is fluorine, chlorine, carbon number 1 to 12 alkyl, C 1 to C 12 alkoxy, or at least one hydrogen may be replaced by C 1 to C 12 alkyl substituted with fluorine or chlorine; Z ⁶ and Z ⁷ are independently is a single bond or alkylene having 1 to 10 carbon atoms, in the alkylene, at least one of _-CH 2 -, -O -, - CO -, - OO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P ^{1, P} 2, And P ³ independently represent a polymerizable group; Sp ¹ , Sp ² and Sp ^{3 each} independently represent a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one of- CH ₂ -may be replaced by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ -is -CH = CH- or -C≡C Replaced by- Well, in these groups, at least one hydrogen may be replaced by fluorine or chlorine; e is 0, 1 or 2; f, g and h are independently 0, 1, 0, 1 And 2, 3 or 4; and the sum of f, g and h is 1 or more. In the formula (4), P ¹ , P ² and P ³ are independently a group selected from the polymerizable groups represented by the formulas (P-1) to (P-5). The liquid crystal composition as described in.

In formulas (P-1) to (P-5), M ¹ , M ² and M ³ independently represent hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is fluorine or chlorine And C 1 -C 5 alkyl substituted by The at least 1 polymeric compound selected from the compound represented by Formula (4-1) to Formula (4-29) as a 1st additive is described in any one of Claim 1 to 11 which contains Liquid crystal composition.

In formulas (4-1) to (4-29), P ⁴ , P ⁵ and P ⁶ are independently selected from groups represented by formulas (P-1) to (P-3) A polymerizable group;

Here, M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Sp ¹ , Sp ² and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO— And —OCO— or —OCOO—, and at least one —CH ₂ —CH ₂ — may be replaced by —CH = CH— or —C≡C— in these groups , At least one hydrogen may be replaced by fluorine or chlorine.   The liquid crystal composition according to any one of claims 10 to 12, wherein the proportion of the first additive is in the range of 0.03% by mass to 10% by mass.   A liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 13.   The liquid crystal display element according to claim 14, wherein an operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and a driving method of the liquid crystal display element is an active matrix method.   A polymer supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of claims 1 to 13, or wherein a polymerizable compound in the liquid crystal composition is polymerized.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 13 in a polymer supported alignment type liquid crystal display device.