JP2018009140A - Liquid crystal composition, and liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition satisfying at least one of characteristics such as a high maximum temperature, a low minimum temperature, a small viscosity, a suitable optical anisotropy and a negatively large dielectric anisotropy, or having a suitable balance between 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 a negatively large dielectric anisotropy as a first component and a specific compound having a small viscosity as a second component; and the composition may contain a specific compound having a negative dielectric anisotropy as a third component, a specific compound having a high maximum temperature or a small viscosity as a fourth component, or a specific compound having a polymerizable group as an additive.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal composition, a liquid crystal display device 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 element containing the composition and having a mode such as IPS, VA, FFS, and FPA. The present invention also relates to a polymer-supported alignment type liquid crystal display element.

  In the liquid crystal display element, the classification based on the operation mode of liquid crystal molecules is as follows: PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. 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 element driving method is PM (passive matrix) and AM (active matrix). PM is classified into static, multiplex, etc., and AM is classified into TFT (thin film transistor), MIM (metal insulator metal), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type according to the manufacturing process. The classification based on the light source includes a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

  The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationships in these properties are summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the device can be used. A preferred maximum temperature of the nematic phase is about 70 ° C. or more, and a preferred minimum temperature of the nematic phase is about −10 ° C. or less. The viscosity of the composition is related to the response time of the device. A short response time is preferred for displaying moving images on the device. A shorter response time is desirable even at 1 millisecond. Therefore, a small viscosity in the composition is preferred. A small viscosity at low temperatures is even 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 optical anisotropy or a small optical anisotropy, ie an appropriate 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 for 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 for the VA mode element and in the range of about 0.20 μm to about 0.30 μm for the IPS mode or FFS mode element. In these cases, a composition having a large optical anisotropy is preferable for a device having a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric anisotropy is preferable. A large specific resistance 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 in the initial stage is preferable. A composition having a large specific resistance after being used for a long time is preferred. The stability of the composition against ultraviolet rays 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 device used in a liquid crystal projector, a liquid crystal television, and the like.

  In a general-purpose liquid crystal display element, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display element, 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 rays while applying a voltage between the substrates of the device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, since the alignment of liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened, and image burn-in is improved. Such an effect of the polymer can be expected for a device having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  In an AM device having a TN mode, a composition having a positive dielectric anisotropy is used. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. In an AM device having an IPS mode or an FFS mode, a composition having a positive or negative dielectric anisotropy is used. In a polymer-supported orientation type AM device, a composition having positive or negative dielectric anisotropy is used. The compound contained in the first component of the present invention is disclosed in the following Patent Document 1.

JP 2001-115161 A

  One object of the present invention is to provide a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, and a high stability to ultraviolet light. It is to provide a liquid crystal composition satisfying at least one of characteristics such as high stability to heat. Another object is to provide a liquid crystal composition having an appropriate 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 a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

式（１）および式（２）において、Ｒ^１およびＲ^２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のアルキルであり；Ｒ^３は、エチル、ビニル、または１−プロペニルであり；環Ａは、テトラヒドロピラン−２，５−ジイルであり；環Ｂおよび環Ｃは独立して、２−フルオロ−１，４−フェニレンまたは２，３−ジフルオロ−１，４−フェニレンであり；Ｚ^１、Ｚ^２、およびＺ^３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；ａおよびｂの一方は０であり、他方は１である。 The present invention provides at least one compound selected from the group of compounds represented by formula (1) as the first component and at least one selected from the group of compounds represented by formula (2) as the second component The present invention relates to a liquid crystal composition containing a compound and having negative dielectric anisotropy, and a liquid crystal display device containing the composition.

In Formula (1) and Formula (2), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons. Or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; R ³ is ethyl, vinyl, or 1-propenyl; ring A is tetrahydropyran-2 Ring B and Ring C are independently 2-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene; Z ¹ , Z ² , and Z ³ Are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; one of a and b is 0 and the other is 1.

  One advantage of the present invention is that the upper limit temperature of the nematic phase, the lower limit temperature of the nematic phase, the small viscosity, the appropriate optical anisotropy, the negative dielectric constant anisotropy, the large specific resistance, and the high stability to ultraviolet rays. It is to provide a liquid crystal composition satisfying at least one of characteristics such as high stability to heat. Another advantage is to provide a liquid crystal composition having an appropriate 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 a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

  Terms used in this specification are 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 general term for liquid crystal display panels and liquid crystal display modules. “Liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a liquid crystal phase, but has a composition for the purpose of adjusting characteristics such as temperature range, viscosity, dielectric anisotropy of the nematic phase. It is a general term for compounds mixed with products. This compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and its molecular structure is rod-like. The “polymerizable compound” is a compound added for the purpose of forming a polymer in the composition. A liquid crystalline compound having alkenyl is not polymerizable in that sense.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to this liquid crystal composition as necessary. The The ratio of the liquid crystal compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive even when the additive is added. The ratio of the additive is expressed as a percentage by weight (% by weight) based on the weight of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or additive is calculated based on the total weight of the liquid crystal compound. Weight parts per million (ppm) may be used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

  “Maximum temperature of nematic phase” may be abbreviated as “maximum temperature”. “Lower limit temperature of nematic phase” may be abbreviated as “lower limit temperature”. “High specific resistance” means that the composition has a large specific resistance in the initial stage and a large specific resistance after long-term use. "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 temperature in the initial stage, and a large voltage not only at room temperature but also at a temperature close to the upper limit temperature after long-term use. It means having a retention rate. In a composition or device, characteristics may be examined before and after a aging test (including an accelerated deterioration test). The expression “increasing dielectric anisotropy” means that when the composition has a positive dielectric anisotropy, the value increases positively, and the composition having a negative dielectric anisotropy When it is a thing, it means that the value increases negatively.

  The compound represented by the formula (1) may be abbreviated as “compound (1)”. At least one compound selected from the group of compounds represented by formula (1) may be abbreviated as “compound (1)”. “Compound (1)” means one compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression “at least one‘ A ’” means that the number of ‘A’ is arbitrary. The expression “at least one 'A' may be replaced by 'B'” means that when the number of 'A' is one, the position of 'A' is arbitrary and the number of 'A' is 2 Even when there are more than two, their positions can be selected without restriction. This rule also applies to the expression “at least one 'A' is 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, the expression includes both “one —CH ₂ — may be replaced with —O—” and “at least two non-adjacent —CH ₂ — may be replaced with —O—”. means. This rule applies not only to replacement with —O— but also to replacement with a divalent group such as —CH═CH— or —COO—.

In the chemical formulas of the component compounds, the symbol of the terminal group R ¹ is used for a plurality of compounds. In these compounds, two groups represented by two arbitrary R ¹ may be the same or different. For example, there is a case where R ^{1 of} the compound (1-1) is ethyl and R ¹ of the compound (1-2) is ethyl. In some cases, R ^{1 of} compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to symbols such as other end groups. In the formula (3), when the subscript 'c' is 2, there are two rings D. In this compound, the two rings represented by the two rings D may be the same or different. This rule also applies to any two rings D when the subscript 'c' is greater than 2. This rule also applies to symbols such as Z ⁴ and ring G. This rule also applies to the case where the compound (5-27) in such a two ^-Sp 2 -P ^2.

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 represent rings such as six-membered rings and condensed rings. In compound (5), the diagonal line across one side of the hexagon represents that any hydrogen on the ring may be replaced with a group such as -Sp ¹ -P ¹ . A subscript such as 'g' indicates the number of groups replaced. When the subscript 'g' is 0 (zero), there is no such replacement. When the subscript 'g' is 2 or more, a plurality of -Sp ¹ -P ¹ exists on the ring J. The plurality of groups represented by -Sp ¹ -P ¹ may be the same or different. In the expression “ring A and ring B are independently X, Y, or Z”, since there are plural subjects, “independently” is used. When the subject is “ring A”, since the subject is singular, “independently” is not used.

2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric bivalent groups generated by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent linking groups such as carbonyloxy (—COO— or —OCO—).

  The alkyl of the liquid crystal compound is linear or branched and does not include cyclic alkyl. Linear alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis for increasing the maximum temperature.

  The present invention includes the following items.

式（１）および式（２）において、Ｒ^１およびＲ^２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のアルキルであり；Ｒ^３は、エチル、ビニル、または１−プロペニルであり；環Ａは、テトラヒドロピラン−２，５−ジイルであり；環Ｂおよび環Ｃは独立して、２−フルオロ−１，４−フェニレンまたは２，３−ジフルオロ−１，４−フェニレンであり；Ｚ^１、Ｚ^２、およびＺ^３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；ａおよびｂの一方は０であり、他方は１である。 Item 1. Containing at least one compound selected from the group of compounds represented by formula (1) as the first component and at least one compound selected from the group of compounds represented by formula (2) as the second component And a liquid crystal composition having negative dielectric anisotropy.

In Formula (1) and Formula (2), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons. Or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; R ³ is ethyl, vinyl, or 1-propenyl; ring A is tetrahydropyran-2 Ring B and Ring C are independently 2-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene; Z ¹ , Z ² , and Z ³ Are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; one of a and b is 0 and the other is 1.

式（１−１）から式（１−６）において、Ｒ^１およびＲ^２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 2. Item 2. The liquid crystal composition according to item 1, comprising at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-6) as a first component.

In formula (1-1) to formula (1-6), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.

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 5 wt% to 25 wt%, and the proportion of the second component is in the range of 15 wt% to 70 wt%.

式（３）において、Ｒ^４およびＲ^５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のアルキルであり；環Ｄおよび環Ｆは独立して、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、少なくとも１つの水素がフッ素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Ｅ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、または７，８−ジフルオロクロマン−２，６−ジイルであり；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、そしてｃとｄの和は３以下である。 Item 4. Item 4. The liquid crystal composition according to any one of items 1 to 3, comprising at least one compound selected from the group of compounds represented by formula (3) as a third component.

In Formula (3), R ⁴ and R ⁵ are independently 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 1 to 12 carbon alkyls in which at least one hydrogen is replaced by fluorine or chlorine; ring D and ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4 -Phenylene, 1,4-phenylene, naphthalene-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, chroman -2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; E represents 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5 - There trifluoroacetic naphthalene-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 4} and ^{Z 5} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy, 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（３−２０）において、Ｒ^４およびＲ^５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 5. Item 5. The liquid crystal composition according to any one of items 1 to 4, comprising at least one compound selected from the group of compounds represented by formulas (3-1) to (3-20) as a third component: object.

In formula (3-1) to formula (3-20), R ⁴ and R ⁵ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms 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 ratio of the third component is in the range of 20% by weight to 75% by weight.

式（４）において、Ｒ^６およびＲ^７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Ｇおよび環Ｉ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^６は、単結合、エチレン、またはカルボニルオキシであり；ｅは、１、２、または３であり；ｅが１のとき、環Ｉは、１，４−フェニレンである。 Item 7. Item 7. The liquid crystal composition according to any one of items 1 to 6, comprising at least one compound selected from the group of compounds represented by formula (4) as a fourth component.

In Formula (4), R ⁶ and R ⁷ are independently 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 Or alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, ethylene, or carbonyloxy; e is 1 2 or 3; when e is 1, ring I is 1,4-phenylene.

式（４−１）から式（４−１２）において、Ｒ^６およびＲ^７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 8. Item 8. The liquid crystal composition according to any one of items 1 to 7, comprising at least one compound selected from the group of compounds represented by formulas (4-1) to (4-12) as a fourth component: object.

In formulas (4-1) to (4-12), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.

Item 9. Item 9. The liquid crystal composition according to item 7 or 8, wherein the ratio of the fourth component is in the range of 2% by weight to 30% by weight.

式（５）において、環Ｊおよび環Ｌ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Ｋ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^７およびＺ^８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；ｆは、０、１、または２であり；ｇ、ｈ、およびｉは独立して、０、１、２、３、または４であり、そしてｇ、ｈ、およびｉ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, comprising at least one compound selected from the group of polymerizable compounds represented by formula (5) as an additive.

In formula (5), ring J and ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and 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. C 1-12 alkyl substituted with fluorine or chlorine may be substituted; ring K may be 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, in which at least one hydrogen is fluorine, chlorine, carbon number 1 to 12 alkyl, 1 to 12 carbon alkoxy, or at least one hydrogen may be replaced with 1 to 12 carbon alkyl substituted with fluorine or chlorine; Z ⁷ and Z ⁸ 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 are independently a polymerizable group; Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, at least one — CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, wherein 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; f is 0, 1, or 2; g, h, and i are independently 0, 1, 1, 2, 3, or 4 and the sum of g, h, and i is 1 or greater.

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. In Formula (5), P ¹ , P ² , and P ³ are groups independently selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-5). Item 11. The liquid crystal composition according to item 10.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with

式（５−１）から式（５−２７）において、Ｐ^１、Ｐ^２、およびＰ^３は独立して、式（Ｐ−１）から式（Ｐ−３）で表される重合性基の群から選択された基であり：

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 compound selected from the group of polymerizable compounds represented by formulas (5-1) to (5-27) as an additive: Composition.

In Formula (5-1) to Formula (5-27), P ¹ , P ² , and P ³ are each independently a polymerizable group represented by Formula (P-1) to Formula (P-3). A group selected from the 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. Yes; Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is —O—, —COO— , —OCO—, or —OCOO—, and at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C— , 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 a ratio of the additive is in the range of 0.03% by weight to 10% by weight.

Item 14. Item 14. A liquid crystal display device comprising 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 the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 16. Item 14. A liquid crystal display element of a polymer-supported alignment type, comprising the liquid crystal composition according to any one of items 1 to 13, wherein an additive contained 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 above-mentioned further containing at least one of an additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound Composition. (B) An AM device containing the above composition. (C) A polymer-supported orientation (PSA) type AM device containing the above composition further containing a polymerizable compound. (D) A polymer-supported orientation (PSA) type AM device comprising the above-described composition, wherein the polymerizable compound in the composition is polymerized. (E) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive device containing the above composition. (G) Use of the above composition as a composition having a nematic phase. (H) 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 characteristics of the component compounds and the main effects of the compounds on the composition will be explained. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.

  First, the composition of the composition will be described. The composition of the present invention is classified into Composition A and Composition B. The composition A further contains other liquid crystal compounds, additives and the like in addition to the liquid crystal compounds selected from the compound (1), the compound (2), the compound (3), and the compound (4). Also good. The “other liquid crystal compound” is a liquid crystal compound different from the compound (1), the compound (2), the compound (3), and the compound (4). Such compounds are mixed into the composition for the purpose of further adjusting the properties. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like.

  Composition B consists essentially of a liquid crystalline compound selected from compound (1), compound (2), compound (3), and compound (4). The term “substantially” means that the composition may contain an additive but no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of reducing the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds.

  Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be explained. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means moderate, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison among the component compounds, and 0 (zero) means that the value is close to zero.

  When component compounds are mixed into the composition, the main effects of the component compounds on the properties of the composition are as follows. Compound (1) increases the dielectric anisotropy. Compound (2) decreases the viscosity. Compound (3) increases the dielectric anisotropy and decreases the minimum temperature. Compound (4) increases the maximum temperature or decreases the viscosity. Compound (5) gives a polymer by polymerization, and this polymer shortens the response time of the device and improves image burn-in.

  Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Preferred combinations of the components in the composition are: first component + second component, first component + second component + third component, first component + second component + fourth component, first component + second component + addition First component + second component + third component + fourth component, first component + second component + third component + additive, first component + second component + fourth component + additive, first Component + second component + third component + fourth component + additive. Further preferred combinations are first component + second component + third component + fourth component, first component + second component + third component + fourth component + additive.

  A desirable ratio of the first component is approximately 5% by weight or more for increasing the dielectric anisotropy, and approximately 25% by weight or less for decreasing the viscosity. A more desirable ratio is in the range of approximately 5% by weight to approximately 20% by weight. A particularly desirable ratio is in the range of approximately 5% by weight to approximately 15% by weight.

  A desirable ratio of the second component is approximately 15% by weight or more for decreasing the viscosity, and approximately 70% by weight or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 15% by weight to approximately 60% by weight. A particularly desirable ratio is in the range of approximately 20% by weight to approximately 50% by weight.

  A desirable ratio of the third component is approximately 20% by weight or more for increasing the dielectric anisotropy, and approximately 75% by weight or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 25% by weight to approximately 70% by weight. A particularly preferred ratio is in the range of approximately 30% by weight to approximately 65% by weight.

  A desirable ratio of the fourth component is approximately 2% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 30% by weight or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 4% by weight to approximately 25% by weight. A particularly preferred ratio is in the range of approximately 4% by weight to approximately 20% by weight.

  The additive is added to the composition for the purpose of adapting to the polymer-supported orientation type device. A desirable ratio of the additive is approximately 0.03% by weight or more for aligning liquid crystal molecules, and approximately 10% by weight or less for preventing display defects of the device. A more desirable ratio is in the range of approximately 0.1% by weight to approximately 2% by weight. A particularly preferred ratio is in the range of approximately 0.2% by weight to approximately 1.0% by weight.

Fourth, a preferred form of the component compound will be described. In Formula (1), Formula (2), Formula (3), and Formula (4), R ¹ , R ² , R ⁴ , and R ⁵ are independently alkyl having 1 to 12 carbons, 1 carbon To C12 alkoxy, C2 to C12 alkenyl, C2 to C12 alkenyloxy, or C1 to C12 alkyl in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ¹ , R ² , R ⁴ , or R ⁵ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat, and 1 to 12 carbons for increasing the dielectric anisotropy. Alkoxy. R ³ is ethyl, vinyl, or 1-propenyl. Preferred R ³ is vinyl for decreasing the viscosity. R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 1 to carbon having at least one hydrogen replaced by fluorine or chlorine. 12 alkyls or alkenyls having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Desirable R ⁶ or R ⁷ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet light or heat.

  Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More desirable alkyl is methyl, ethyl, propyl, butyl or pentyl for decreasing 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 desirable alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for decreasing the viscosity. The preferred configuration of —CH═CH— in these alkenyls depends on the position of the double bond. Trans is preferable in alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl.

  Preferred examples of 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 for increasing the dielectric anisotropy.

  Preferred examples of 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.

  Ring A is tetrahydropyran-2,5-diyl. Ring B and ring C are independently 2-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene.

  Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene 2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine, or chroman in which at least one hydrogen is replaced with fluorine or chlorine 2,6-diyl. Desirable ring D or ring F is 1,4-cyclohexylene for decreasing the viscosity, and 1,4-phenylene for increasing the optical anisotropy. Ring E 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 or 7,8-difluorochroman-2,6-diyl. Preferred ring E is 2,3-difluoro-1,4-phenylene for decreasing the viscosity and 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy. In order to increase anisotropy, it is 7,8-difluorochroman-2,6-diyl.

  Ring G and ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring G or ring I is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature. The configuration of 1,4-cyclohexylene is preferably trans rather than cis for increasing the maximum temperature.

Z ¹ , Z ² , Z ³ , Z ⁴ , and Z ⁵ are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ¹ , Z ² , Z ³ , Z ⁴ , or Z ⁵ is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy. . Z ⁶ is a single bond, ethylene or carbonyloxy. Desirable Z ⁶ is a single bond for increasing the stability to ultraviolet light and heat.

  One of a and b is 0 and the other is 1. 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 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Preferred d is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature. e is 1, 2 or 3. Preferred e is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

In formula (5), 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 preferred P ¹ , P ² or P ³ is a group represented by the formula (P-1), the formula (P-2) or the formula (P-3). Particularly preferred P ¹ , P ² , or P ³ is a group represented by the formula (P-1) or the formula (P-2). Most preferred P ¹ , P ² or P ³ is a group represented by the formula (P-1). A preferred group represented by the formula (P-1) is —OCO—CH═CH ₂ or —OCO—C (CH ₃ ) ═CH ₂ . The wavy line from formula (P-1) to formula (P-5) indicates the site to be bound.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with Preferred M ¹ , M ² or M ³ is hydrogen or methyl for increasing the reactivity. More preferred M ¹ is hydrogen or methyl, and more preferred M ² or M ³ is hydrogen.

Sp ¹ , Sp ² , and Sp ³ are each 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 it may be replaced by -OCOO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least 1 One hydrogen may be replaced with fluorine or chlorine. Preferred Sp ¹ , Sp ² , or Sp ³ are 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 J and Ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridine -2-yl, and 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. Further, it may be substituted with alkyl having 1 to 12 carbons. Preferred ring J or ring L is phenyl. Ring K 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, 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 K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁷ and Z ⁸ are each independently a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — is —O—, —CO—, —COO—, 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, and in these groups at least one hydrogen may be replaced with fluorine or chlorine. Preferred Z ⁷ or Z ⁸ is a single bond, —CH ₂ —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. Further preferred Z ⁷ or Z ⁸ is a single bond.

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

  Fifth, preferred component compounds are shown. Desirable compounds (1) are the compounds (1-1) to (1-6) described in item 2. In these compounds, it is preferable that at least one of the first components is the compound (1-1), the compound (1-2), or the compound (1-3). It is preferable that at least two of the first components are a combination of the compound (1-1) and the compound (1-3).

  Desirable compound (3) is the compound (3-1) to the compound (3-20) according to item 5. In these compounds, at least one of the third components is compound (3-1), compound (3-2), compound (3-3), compound (3-4), compound (3-6), compound ( 3-7), compound (3-8), or compound (3-10) is preferable. At least two of the third components are compound (3-1) and compound (3-6), compound (3-1) and compound (3-10), compound (3-3) and compound (3-6), The compound (3-3) and the compound (3-10), the compound (3-4) and the compound (3-6), or a combination of the compound (3-4) and the compound (3-10) is preferable.

  Desirable compounds (4) are the compounds (4-1) to (4-12) according to item 8. In these compounds, it is preferable that at least one of the fourth components is the compound (4-2), the compound (4-4), the compound (4-5), or the compound (4-6). It is preferable that at least two of the fourth components are a combination of the compound (4-2), the compound (4-4), the compound (4-2), and the compound (4-6).

  Desirable compound (5) is the compound (5-1) to the compound (5-27) according to item 12. In these compounds, at least one of the additives is compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26), or compound ( 5-27) is preferred. At least two of the additives are compound (5-1) and compound (5-2), compound (5-1) and compound (5-18), compound (5-2) and compound (5-24), compound (5-2) and compound (5-25), compound (5-2) and compound (5-26), compound (5-25) and compound (5-26), or compound (5-18) and compound A combination of (5-24) is preferred.

  Sixth, additives that may be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, 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 compound (6-1) to compound (6-5). A desirable ratio of the optically active compound is approximately 5% by weight or less. A more desirable ratio is in the range of approximately 0.01% by weight to approximately 2% by weight.

In order to prevent a decrease in specific resistance due to heating in the atmosphere or 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, an antioxidant is composed. Added to the product. A preferred example of the antioxidant is a compound (7) wherein n is an integer of 1 to 9.

  In the compound (7), preferred n is 1, 3, 5, 7, or 9. Further preferred n is 7. Since the compound (7) in which n is 7 has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device has been used for a long time. A desirable ratio of the antioxidant is approximately 50 ppm or more for achieving its effect, and is approximately 600 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

  Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Also preferred are light stabilizers such as sterically hindered amines. A desirable ratio of these absorbers and stabilizers is approximately 50 ppm or more for achieving the effect thereof, and approximately 10,000 ppm or less for avoiding a decrease in the maximum temperature or avoiding an increase in the minimum temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 10,000 ppm.

  A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to adapt to a GH (guest host) mode device. A preferred ratio of the dye is in the range of approximately 0.01% by weight to approximately 10% by weight. In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition. A desirable ratio of the antifoaming agent is approximately 1 ppm or more for obtaining the effect thereof, and approximately 1000 ppm or less for preventing a display defect. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

  A polymerizable compound is used to adapt to a polymer support alignment (PSA) type device. Compound (5) is suitable for this purpose. A polymerizable compound different from the compound (5) may be added to the composition together with the compound (5). Instead of the compound (5), a polymerizable compound different from the compound (5) may be added to the composition. Preferable examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. Further preferred examples are acrylate or methacrylate derivatives. By changing the type of compound (5) or combining compound (5) with a polymerizable compound different from compound (5) in an appropriate ratio, the reactivity of polymerization and the pretilt angle of liquid crystal molecules are adjusted. can do. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long lifetime can be achieved.

  The polymerizable compound is polymerized by ultraviolet irradiation. The polymerization may be performed in the presence of an initiator such as a photopolymerization initiator. Appropriate conditions for polymerization and the appropriate type and amount of initiator are known to the person 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. A desirable ratio of the photopolymerization initiator is in the range of approximately 0.1% by weight to approximately 5% by weight based on the weight of the polymerizable compound. A more desirable ratio is in the range of approximately 1% by weight to approximately 3% by weight.

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

The polar compound is an organic compound having polarity. Here, a compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen are more electronegative and tend to have partial negative charges. Carbon and hydrogen tend to be neutral or have a partial positive charge. Polarity arises from the fact that partial charges are not evenly distributed among different types of atoms in a compound. For example, the polar compound has at least one of partial structures such as —OH, —COOH, —SH, —NH ₂ ,> NH, and> N—.

  Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. The method for synthesizing compound (1) is described in the Examples section. Compound (2) is synthesized by the method described in JP-A-59-176221. Compound (3-6) is synthesized by the method described in JP 2000-53602 A. Compound (4-2) is synthesized by the method described in JP-A-52-53783. Compound (5-18) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compounds of formula (7) where n is 1 are available from Sigma-Aldrich Corporation. Compound (7) etc. in which n is 7 is synthesized by the method described in US Pat. No. 3,660,505.

  Compounds that have not been described as synthetic methods include Organic Synthesis (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis ( Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. The composition is prepared from the compound thus obtained by known methods. For example, the component compounds are mixed and dissolved in each other by heating.

  Finally, the use of the composition will be described. Most compositions have a minimum temperature of about −10 ° C. or lower, a maximum temperature 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 ratio of the component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. A device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. This composition can be used as a composition having a nematic phase or can be used as an optically active composition by adding an optically active compound.

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

  An example of a method for producing a polymer-supported orientation type element 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 prepared by mixing a liquid crystal compound. A polymerizable compound is added to the composition. You may add an additive further as needed. This composition is injected into the device. The device is irradiated with light with a voltage applied. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. By this polymerization, a composition containing a polymer is generated. The polymer-supported orientation type element is manufactured by such a procedure.

  In this procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. According to this orientation, the molecules of the polymerizable compound are also oriented. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer maintaining this orientation is formed. The effect of this polymer shortens the response time of the device. Since image sticking is a malfunction of the liquid crystal molecules, the effect of this polymer also improves the image sticking. It is also possible to polymerize a polymerizable compound in the composition in advance and place the composition between the substrates of the liquid crystal display element.

  The invention is explained in more detail by means of examples. The invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The invention also includes a mixture of at least two of the example compositions. The synthesized compound was identified by a method such as NMR analysis. The characteristics of the compound, composition and device were measured by the methods described below.

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

  Gas chromatographic analysis: A GC-14B gas chromatograph manufactured 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 column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used. The column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./min. A sample was prepared in an acetone solution (0.1% by weight), and 1 μL thereof was injected into the sample vaporization chamber. The recorder is a C-R5A type Chromatopac manufactured by Shimadzu Corporation or an equivalent thereof. The obtained gas chromatogram showed the peak retention time and peak area corresponding to the component compounds.

  As a solvent for diluting the sample, chloroform, hexane or the like may be used. In order to separate the component compounds, the following capillary column may be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, BP-1 made by SGE International Pty. Ltd (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm). In order to prevent compound peaks from overlapping, 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.

  The ratio 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 ratio (weight ratio) of liquid crystal compounds. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the ratio (% by weight) of the liquid crystal compound can be calculated from the peak area ratio.

  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 characteristics of the compound, a sample for measurement was prepared by mixing this compound (15% by weight) with mother liquid crystals (85% by weight). The characteristic value of the compound was calculated from the value obtained by the measurement by extrapolation. (Extrapolated value) = {(Measured value of sample) −0.85 × (Measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) is precipitated at 25 ° C. at this ratio, the ratio of the compound and the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight in this order. changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were determined.

The following mother liquid crystals were used. The ratio of the component compounds is shown by weight%.

  Measuring method: The characteristics were measured by the following method. Many of these are the methods described in the JEITA standard (JEITA ED-2521B) established by the Japan Electronics and Information Technology Industries Association (JEITA), or a modified method thereof. Met. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Maximum temperature of nematic phase (NI; ° C.): A sample was placed on a hot plate of a melting point measuring apparatus equipped with a polarizing microscope and heated at a rate of 1 ° C./min. The temperature was measured when a part of the sample changed from a nematic phase to an isotropic liquid. 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, when the sample remained in the nematic phase at −20 ° C. and changed to a crystalline or smectic phase at −30 ° C., the _TC was described as <−20 ° C. The lower limit temperature of the nematic phase may be abbreviated as “lower limit temperature”.

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C .; mPa · s): The measurement was performed according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I followed. A sample was put in a VA device having a distance (cell gap) between two glass substrates of 20 μm. This element was applied stepwise in increments of 1 volt within a range of 39 to 50 volts. After no application for 0.2 seconds, the application was repeated under the condition of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and peak time of the transient current generated by this application were measured. These measurements and M.I. The value of rotational viscosity was obtained from the paper by Imai et al., Calculation formula (8) on page 40. The dielectric anisotropy necessary for this calculation was measured in the item (6).

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

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

(7) Threshold voltage (Vth; measured at 25 ° C .; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures the element with ultraviolet rays is used. And sealed. The voltage (60 Hz, rectangular wave) applied to this element was increased stepwise from 0V to 20V by 0.02V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was created in which the transmittance was 100% when the light amount reached the maximum and the transmittance was 0% when the light amount was the minimum. The threshold voltage was expressed as a voltage when the transmittance reached 10%.

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

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

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

(11) Voltage holding ratio (VHR-4; measured at 25 ° C .;%): The TN device into which the sample was injected was heated in a thermostatic bath at 80 ° C. for 500 hours, and then the voltage holding ratio was measured and stability against heat. Evaluated. In the measurement of VHR-4, a decaying voltage was measured for 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

(12) Response time (τ; measured at 25 ° C .; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. A sample was put in a normally black mode VA device in which the distance between two glass substrates (cell gap) was 4 μm and the rubbing direction was anti-parallel. The device was sealed using an adhesive that was cured 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 the maximum, and the transmittance was 0% when the light amount was the minimum. The response time was expressed as the time required to change the transmittance from 90% to 10% (fall time; millisecond).

(13) Specific resistance (ρ; measured at 25 ° C .; Ωcm): A sample (1.0 mL) was injected into a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance was calculated from the following equation. (Resistivity) = {(Voltage) × (Capacity of container)} / {(DC current) × (Dielectric constant of vacuum)}.

  Compound (1-4) was synthesized by the method described below. Solmix A-11 was a mixture of ethanol (85.5%), methanol (13.4%) and 2-propanol (1.1%), and was obtained from Nippon Alcohol Sales Co., Ltd.

First step:
Compound (T-1) was synthesized by a known method. Compound (T-1) (4.89 g, 22.3 mmol), Compound (T-2) (4.81 g, 20.3 mmol), potassium carbonate (5.61 g, 40.6 mmol), tetrabutylammonium bromide (1 .31 g, 4.06 mmol), palladium on carbon (0.179 g), toluene (20 ml), a mixture of Solmix (20 ml) and water (20 ml) was refluxed for 5 hours. The reaction mixture was cooled to room temperature and palladium on carbon was filtered off. The product was subjected to ordinary post-treatment and purified by silica gel chromatography to obtain compound (T-3) (6.72 g, 20.3 mmol; 99%).

Second step:
A solution of compound (T-3) (6.72 g, 20.3 mmol) in THF (50 ml) was cooled to −70 ° C., and a solution of i-PrMgCl·LiCl in THF (1.3 M; 17.17 ml, 22.3 mmol). ) Was added dropwise. After stirring at −70 ° C. for 2.5 hours, a solution of N, N-dimethylformamide (2.04 ml, 26.4 mmol) in THF (10 ml) was added dropwise. After stirring at −70 ° C. for 1 hour, the reaction mixture was returned to room temperature and poured into an aqueous sodium thiosulfate solution. The product was subjected to ordinary post-treatment and purified by silica gel chromatography to obtain compound (T-4) (4.55 g, 16.2 mmol; 80%).

Third step:
A solution of vinylmagnesium bromide in THF (1.31M; 13.3 ml, 17.0 mmol) was added dropwise to a solution of lithium chloride (0.722 g, 17.0 mmol) in THF (45 ml), and the mixture was stirred at room temperature for 1 hour. The reaction mixture was cooled to 0 ° C., and a solution of compound (T-4) (4.55 g, 16.2 mmol) in THF (15 ml) was added dropwise. The reaction mixture was returned to room temperature, stirred for 8 hours, and poured into 1M hydrochloric acid. The product was subjected to ordinary post-treatment and purified by silica gel chromatography to obtain compound (T-5) (5.00 g, 16.2 mmol; quantitative).

Fourth step:
To a solution of 2-iodoxybenzoic acid (63%; 9.02 g, 20.3 mmol) in DMSO (40 ml), a solution of compound (T-5) (5.00 g, 16.2 mmol) in DMSO (15 ml) was added dropwise, Stir at room temperature for 3 hours. Water and toluene were added to the reaction mixture, the residue was removed by filtration, and an aqueous sodium sulfite solution was added to the filtrate. The product was subjected to ordinary post-treatment and purified by silica gel chromatography to obtain compound (T-6) (4.97 g, 16.2 mmol; quantitative).

5th step:
A solution of dibutylamine (3.31 ml, 19.5 mmol) in DMF (10 ml) was added dropwise to a solution of valeraldehyde (1.75 ml, 16.2 mmol) in DMF (40 ml) and refluxed for 10 hours. The reaction mixture was cooled to room temperature and subjected to normal workup. The crude product was dissolved in DMF (50 ml), a solution of compound (T-6) (4.97 g, 16.2 mmol) in DMF (15 ml) was added, heated to 50 ° C., and stirred for 10 hours. The reaction mixture was cooled to room temperature and acetic acid was added. The product was subjected to ordinary post-treatment and purified by silica gel chromatography to obtain compound (T-7) (5.35 g, 13.6 mmol; 84%).

Step 6:
To a mixture of compound (T-7) (5.35 g, 13.6 mmol), toluene (20 ml), formic acid (15 ml) and acetic acid (15 ml), zinc chloride (1.86 g, 13.6 mmol) and 1,1,1, 3,3-Tetramethyldisiloxane (11.5 ml, 75.0 mmol) was added and stirred at room temperature for 10 hours. The reaction mixture was poured into water, subjected to ordinary work-up, and purified by silica gel chromatography and recrystallization to obtain compound (1-4) (2.84 g, 7.50 mmol; 55%).

¹ H-NMR (CDCl ₃ ; δ ppm): 7.03 (1H, t, J = 7.6 Hz), 7.18 (2H, d, J = 9.4 Hz), 7.02 (1H, ddd, J = 2.2 Hz, 8.1 Hz, 8.1 Hz), 6.79 (1 H, ddd, J = 1.8 Hz, 8.0 Hz, 8.1 Hz), 4.30 (1 H, dd, J = 2.1) , 11.4 Hz), 4.16 (2H, q, J = 7.1 Hz), 4.12-4.08 (1H, m), 3.22 (1H, t, J = 11.2 Hz), 2 .03-1.99 (1H, m), 1.94-1.89 (1H, m), 1.73-1.65 (1H, m), 1.64-1.56 (1H, m) , 1.48 (3H, t, J = 7.0 Hz), 1.41-1.24 (3H, m), 1.22-1.09 (2H, m), 0.92 (3H, t, J = 7. Hz).

  Examples of the compositions are shown below. The component compounds were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration regarding 1,4-cyclohexylene is trans. The number in parentheses after the symbolized compound represents the chemical formula to which the compound belongs. The symbol (−) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. Finally, the characteristic values of the composition are summarized.

[Comparative Example 1]
Example 10 was selected from the compositions disclosed in JP-A-2001-115161. This is because the composition contains the compound (1-3) as the first component.
5-DhB (2F, 3F) -O1 (-) 5%
3-HDhB (2F, 3F) -1 (-) 5%
3-HDhB (2F, 3F) -3 (-) 5%
3-HDhB (2F, 3F) -O1 (-) 10%
5-HDhB (2F, 3F) -O1 (-) 11%
3-HDhB (2F, 3F) -O2 (-) 11%
5-HDhB (2F, 3F) -O2 (-) 11%
5-BDhB (2F, 3F) -O1 (-) 5%
5-BDhB (2F, 3F) -O2 (-) 3%
3-DhB (2F, 3F) B (2F, 3F) -O2 (1-3) 3%
3-HH-4 (-) 5%
3-HB-O2 (4-1) 4%
3-HH-EMe (-) 4%
3-HHB-1 (4-4) 3%
3-HHB-O1 (4-4) 4%
4-HEB-O2 (4) 5%
5-HEB-O2 (4) 6%
NI = 94.7 ° C .; Tc <−20 ° C .; η = 43.8 mPa · s; Δn = 0.094; Δε = −3.8.

[Example 1]
3-DhB (F) B (2F, 3F) -O2 (1-1) 6%
3-DhB (2F, 3F) B (2F, 3F) -O2 (1-3) 7%
3-HH-V (2) 29%
V-HB (2F, 3F) -O2 (3-1) 7%
3-BB (2F, 3F) -O2 (3-4) 7%
V2-BB (2F, 3F) -O2 (3-4) 7%
2-HHB (2F, 3F) -O2 (3-6) 3%
3-HHB (2F, 3F) -O2 (3-6) 8%
V-HHB (2F, 3F) -O2 (3-6) 10%
V-HHB (2F, 3F) -O4 (3-6) 5%
3-HBB (2F, 3F) -O2 (3-10) 7%
V-HHB-1 (4-4) 4% NI = 75.2 ° C .; Tc <−20 ° C .; η = 20.0 mPa · s; Δn = 0.106; Δε = −4.4.

[Example 2]
3-dhB (F) B (2F, 3F) -O2 (1-4) 5%
3-dhB (2F, 3F) B (2F, 3F) -O2 (1-6) 5%
3-HH-V (2) 30%
3-H2B (2F, 3F) -O2 (3-2) 7%
3-BB (2F, 3F) -O2 (3-4) 4%
5-BB (2F, 3F) -O2 (3-4) 3%
3-HHB (2F, 3F) -O2 (3-6) 5%
V-HHB (2F, 3F) -O2 (3-6) 5%
3-HH2B (2F, 3F) -O2 (3-7) 3%
5-HH2B (2F, 3F) -O2 (3-7) 4%
V-HH1OB (2F, 3F) -O2 (3-8) 3%
2-HBB (2F, 3F) -O2 (3-10) 5%
3-HHB (2F, 3Cl) -O2 (3-12) 2%
5-HHB (2F, 3Cl) -O2 (3-12) 3%
3-HchB (2F, 3F) -O2 (3-17) 2%
3-BB (2F) B (2F, 3F) -O2 (3-18) 4%
3-BB (F) B (2F, 3F) -O2 (3-19) 2%
5-HB-O2 (4-1) 2%
V2-BB-1 (4-2) 2%
3-HBB-2 (4-5) 4%
NI = 82.9 ° C .; Tc <−20 ° C .; η = 16.3 mPa · s; Δn = 0.111; Δε = −3.7.

[Example 3]
3-DhB (F) B (2F, 3F) -O2 (1-1) 5%
3-dhB (F) B (2F, 3F) -O2 (1-4) 5%
3-HH-V (2) 30%
3-HH-V1 (2) 5%
V-HB (2F, 3F) -O2 (3-1) 5%
3-H1OB (2F, 3F) -O2 (3-3) 3%
3-B (2F, 3F) B (2F, 3F) -O2 (3-5) 3%
3-HHB (2F, 3F) -O2 (3-6) 9%
4-HHB (2F, 3F) -O2 (3-6) 4%
3-HH1OB (2F, 3F) -O2 (3-8) 4%
2-BB (2F, 3F) B-3 (3-9) 3%
3-HBB (2F, 3Cl) -O2 (3-13) 2%
5-HBB (2F, 3Cl) -O2 (3-13) 3%
3-HH1OCro (7F, 8F) -5 (3-15) 4%
3-B (2F) B (2F, 3F) -O2 (3-20) 2%
V2-HHB-1 (4-4) 2%
1-BB (F) B-2V (4-6) 3%
V2-BB2B-1 (4-8) 3%
3-HH-VFF (-) 5%
NI = 76.6 ° C .; Tc <−20 ° C .; η = 15.4 mPa · s; Δn = 0.102; Δε = −3.4.

[Example 4]
3-DhB (2F) B (2F, 3F) -O2 (1-2) 7%
3-dhB (2F, 3F) B (2F, 3F) -O4 (1-6) 5%
3-HH-V (2) 25%
3-HH-2 (2) 10%
3-HB (2F, 3F) -O2 (3-1) 5%
5-HB (2F, 3F) -O2 (3-1) 5%
2-HHB (2F, 3F) -O2 (3-6) 3%
3-HHB (2F, 3F) -O2 (3-6) 5%
2-HBB (2F, 3F) -O2 (3-10) 3%
3-HBB (2F, 3F) -O2 (3-10) 8%
3-HEB (2F, 3F) B (2F, 3F) -O2 (3-11) 3%
3-H1OCro (7F, 8F) -5 (3-14) 3%
3-chB (2F, 3F) -O2 (3-16) 3%
V-chB (2F, 3F) -O2 (3-16) 3%
3-HHEH-3 (4-3) 3%
5-B (F) BB-3 (4-7) 3%
5-HB (F) BH-3 (4-11) 3%
1O1-HBBH-5 (-) 3%
NI = 80.1 ° C .; Tc <−20 ° C .; η = 19.0 mPa · s; Δn = 0.102; Δε = −3.5.

[Example 5]
3-DhB (F) B (2F, 3F) -O2 (1-1) 5%
3-dhB (2F) B (2F, 3F) -O2 (1-5) 5%
3-HH-V (2) 20%
3-HH-V1 (2) 5%
3-HH-2 (2) 5%
3-HB (2F, 3F) -O2 (3-1) 5%
3-BB (2F, 3F) -O2 (3-4) 3%
5-BB (2F, 3F) -O2 (3-4) 3%
2-HHB (2F, 3F) -O2 (3-6) 5%
3-HHB (2F, 3F) -O2 (3-6) 12%
V-HHB (2F, 3F) -O2 (3-6) 3%
V-HH1OB (2F, 3F) -O2 (3-8) 3%
2-HBB (2F, 3F) -O2 (3-10) 5%
3-HBB (2F, 3F) -O2 (3-10) 8%
1-BB-3 (4-2) 4%
1-BB-5 (4-2) 3%
3-HHB-1 (4-4) 3%
3-HHEBH-3 (4-10) 3%
NI = 87.7 ° C .; Tc <−20 ° C .; η = 15.1 mPa · s; Δn = 0.110; Δε = −3.6.

[Example 6]
3-DhB (2F) B (2F, 3F) -O2 (1-2) 7%
4-DhB (2F, 3F) B (2F, 3F) -O2 (1-3) 5%
3-HH-V (2) 28%
3-HH-V1 (2) 5%
3-HH-2 (2) 5%
3-HB (2F, 3F) -O2 (3-1) 5%
3-BB (2F, 3F) -O2 (3-4) 5%
2-HHB (2F, 3F) -O2 (3-6) 5%
3-HHB (2F, 3F) -O2 (3-6) 7%
2-HBB (2F, 3F) -O2 (3-10) 5%
3-HBB (2F, 3F) -O2 (3-10) 10%
5-BB (2F) B (2F, 3F) -O2 (3-18) 2%
3-BB (F) B (2F, 3F) -O2 (3-19) 2%
3-HB-O2 (4-1) 3%
3-HB (F) HH-2 (4-9) 3%
3-HBB (F) B-2 (4-12) 3%
NI = 85.8 ° C .; Tc <−20 ° C .; η = 17.8 mPa · s; Δn = 0.111; Δε = −3.5.

[Example 7]
3-DhB (F) B (2F, 3F) -O2 (1-1) 4%
4-DhB (F) B (2F, 3F) -O2 (1-1) 4%
3-dhB (2F) B (2F, 3F) -O2 (1-5) 7%
3-HH-V (2) 25%
3-HH-2 (2) 8%
V-HB (2F, 3F) -O2 (3-1) 3%
5-HB (2F, 3F) -O2 (3-1) 5%
5-H2B (2F, 3F) -O2 (3-2) 3%
2-H1OB (2F, 3F) -O2 (3-3) 3%
3-HHB (2F, 3F) -O2 (3-6) 10%
4-HHB (2F, 3F) -O2 (3-6) 2%
2-HH1OB (2F, 3F) -O2 (3-8) 3%
3-HBB (2F, 3F) -O2 (3-10) 6%
3-HH1OCro (7F, 8F) -5 (3-15) 3%
3-HchB (2F, 3F) -O2 (3-17) 3%
V-HBB-3 (4-5) 5%
2-BB (F) B-2V (4-6) 3%
3-BB (F) B-2V (4-6) 3%
NI = 81.4 ° C .; Tc <−20 ° C .; η = 18.4 mPa · s; Δn = 0.107; Δε = −3.7.

[Example 8]
3-dhB (F) B (2F, 3F) -O2 (1-4) 5%
3-dhB (2F, 3F) B (2F, 3F) -O2 (1-6) 5%
3-HH-V (2) 30%
V-HB (2F, 3F) -O2 (3-1) 5%
3-HB (2F, 3F) -O2 (3-1) 8%
3-HHB (2F, 3F) -O2 (3-6) 8%
4-HHB (2F, 3F) -O2 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 3%
3-HBB (2F, 3F) -O2 (3-10) 5%
5-HBB (2F, 3F) -O2 (3-10) 5%
3-H1OCro (7F, 8F) -5 (3-14) 3%
5-HchB (2F, 3F) -O2 (3-17) 3%
3-HBB-2 (4-5) 8%
F3-HH-V (-) 3%
3-HDhB (2F, 3F) -O2 (-) 3%
3-dhBB (2F, 3F) -O2 (-) 3%
NI = 84.5 ° C .; Tc <−20 ° C .; η = 17.4 mPa · s; Δn = 0.102; Δε = −3.7.

[Example 9]
3-DhB (F) B (2F, 3F) -O4 (1-1) 5%
3-dhB (2F) B (2F, 3F) -O2 (1-5) 4%
5-dhB (2F) B (2F, 3F) -O2 (1-5) 4%
3-HH-V (2) 20%
3-HH-V1 (2) 5%
5-HB (2F, 3F) -O2 (3-1) 5%
3-H1OB (2F, 3F) -O2 (3-3) 5%
3-BB (2F, 3F) -O2 (3-4) 6%
2O-BB (2F, 3F) -O2 (3-4) 5%
4-HHB (2F, 3F) -O2 (3-6) 3%
V-HHB (2F, 3F) -O2 (3-6) 10%
3-HBB (2F, 3F) -O2 (3-10) 5%
4-HBB (2F, 3F) -O2 (3-10) 5%
1V2-BB-1 (4-2) 3%
3-HHEBH-4 (4-10) 3%
5-HBB (F) B-3 (4-12) 3%
5-HH-V (-) 3%
2-HH-5 (-) 3%
3-HH-4 (-) 3%
NI = 84.3 ° C .; Tc <−20 ° C .; η = 16.9 mPa · s; Δn = 0.112; Δε = −3.9.

[Example 10]
5-DhB (2F) B (2F, 3F) -O2 (1-2) 5%
3-DhB (2F, 3F) B (2F, 3F) -O2 (1-3) 5%
3-HH-V (2) 31%
3-HB (2F, 3F) -O2 (3-1) 10%
3-H2B (2F, 3F) -O2 (3-2) 4%
2O-BB (2F, 3F) -O2 (3-4) 5%
3-HHB (2F, 3F) -O2 (3-6) 12%
2-BB (2F, 3F) B-3 (3-9) 3%
2-BB (2F, 3F) B-4 (3-9) 3%
V-HBB (2F, 3F) -O2 (3-10) 5%
3-HEB (2F, 3F) B (2F, 3F) -O2 (3-11) 5%
V2-HchB (2F, 3F) -O2 (3-17) 3%
5-B (F) BB-2 (4-7) 3%
3-HHEBH-5 (4-10) 3%
5-HH-O1 (-) 3%
NI = 81.2 ° C .; Tc <−20 ° C .; η = 17.8 mPa · s; Δn = 0.111; Δε = −3.8.

[Example 11]
3-DhB (2F) B (2F, 3F) -O2 (1-2) 3%
3-DhB (2F) B (2F, 3F) -O4 (1-2) 3%
3-dhB (2F) B (2F, 3F) -O2 (1-5) 6%
3-HH-V (2) 20%
3-HH-2 (2) 10%
5-HB (2F, 3F) -O2 (3-1) 5%
3-BB (2F, 3F) -O2 (3-4) 5%
2-HHB (2F, 3F) -O2 (3-6) 5%
V-HHB (2F, 3F) -O2 (3-6) 5%
V-HHB (2F, 3F) -O4 (3-6) 5%
3-HBB (2F, 3F) -O2 (3-10) 10%
5-HBB (2F, 3F) -O2 (3-10) 5%
7-HB-1 (4-1) 3%
1-BB-3 (4-2) 3%
3-HHEH-5 (4-3) 3%
3-HHB-3 (4-4) 3%
V2-HHB-1 (4-4) 3%
2-BB (F) B-3 (4-6) 3%
NI = 84.1 ° C .; Tc <−20 ° C .; η = 15.3 mPa · s; Δn = 0.110; Δε = −3.3.

[Example 12]
3-DhB (F) B (2F, 3F) -O1 (1-1) 5%
3-dhB (2F, 3F) B (2F, 3F) -O2 (1-6) 5%
3-HH-V (2) 30%
3-HH-V1 (2) 5%
3-HB (2F, 3F) -O2 (3-1) 10%
2O-BB (2F, 3F) -O2 (3-4) 5%
3-HHB (2F, 3F) -O2 (3-6) 7%
3-HBB (2F, 3F) -O2 (3-10) 8%
V-HBB (2F, 3F) -O2 (3-10) 5%
3-H1OCro (7F, 8F) -5 (3-14) 3%
3-HH1OCro (7F, 8F) -5 (3-15) 3%
3-HHB-O1 (4-4) 3%
VFF-HHB-1 (4-4) 3%
V-HBB-3 (4-5) 5%
2-BB (F) B-5 (4-6) 3%
NI = 81.8 ° C .; Tc <−20 ° C .; η = 16.7 mPa · s; Δn = 0.110; Δε = −3.5.

[Example 13]
3-dhB (F) B (2F, 3F) -O2 (1-4) 6%
3-dhB (2F) B (2F, 3F) -O2 (1-5) 6%
3-HH-V (2) 27%
3-HH-2 (2) 5%
2-H1OB (2F, 3F) -O2 (3-3) 3%
3-H1OB (2F, 3F) -O2 (3-3) 3%
3-BB (2F, 3F) -O2 (3-4) 5%
2-HHB (2F, 3F) -O2 (3-6) 5%
3-HHB (2F, 3F) -O2 (3-6) 8%
4-HHB (2F, 3F) -O2 (3-6) 5%
2-BB (2F, 3F) B-3 (3-9) 3%
2-HBB (2F, 3F) -O2 (3-10) 5%
3-HBB (2F, 3F) -O2 (3-10) 5%
5-HBB (2F, 3F) -O2 (3-10) 5%
3-chB (2F, 3F) -O2 (3-16) 3%
3-HB-O2 (4-1) 3%
V-HBB-2 (4-5) 3%
NI = 81.1 ° C .; Tc <−20 ° C .; η = 16.1 mPa · s; Δn = 0.110; Δε = −3.8.

[Example 14]
3-DhB (2F) B (2F, 3F) -O1 (1-2) 5%
3-DhB (2F, 3F) B (2F, 3F) -O2 (1-3) 5%
3-HH-V (2) 22%
3-HH-V1 (2) 9%
3-HB (2F, 3F) -O2 (3-1) 10%
5-HB (2F, 3F) -O2 (3-1) 5%
5-BB (2F, 3F) -O2 (3-4) 5%
3-HHB (2F, 3F) -O2 (3-6) 8%
V-HHB (2F, 3F) -O2 (3-6) 3%
3-HBB (2F, 3F) -O2 (3-10) 8%
4-HBB (2F, 3F) -O2 (3-10) 3%
V-HBB (2F, 3F) -O2 (3-10) 5%
1-BB-3 (4-2) 3%
3-HHB-1 (4-4) 3%
VFF2-HHB-1 (4-4) 3%
3-HH-O1 (-) 3%
NI = 75.3 ° C .; Tc <−20 ° C .; η = 15.1 mPa · s; Δn = 0.105; Δε = −3.8.

[Example 15]
3-dhB (F) B (2F, 3F) -O2 (1-4) 5%
3-dhB (2F) B (2F, 3F) -O2 (1-5) 5%
3-HH-V (2) 28%
V-HB (2F, 3F) -O2 (3-1) 5%
3-H2B (2F, 3F) -O2 (3-2) 5%
2-HHB (2F, 3F) -O2 (3-6) 5%
4-HHB (2F, 3F) -O2 (3-6) 6%
2-HH1OB (2F, 3F) -O2 (3-8) 3%
3-HH1OB (2F, 3F) -O2 (3-8) 3%
2-BB (2F, 3F) B-3 (3-9) 3%
3-HBB (2F, 3F) -O2 (3-10) 7%
5-HBB (2F, 3F) -O2 (3-10) 7%
V2-HchB (2F, 3F) -O2 (3-17) 4%
3-HB-O2 (4-1) 6%
5-HB-O2 (4-1) 3%
1V2-HH-2V1 (-) 5%
NI = 84.3 ° C .; Tc <−20 ° C .; η = 14.1 mPa · s; Δn = 0.104; Δε = −3.6.

  The viscosity of the composition of Comparative Example 1 was 43.8 mPa · s. On the other hand, the viscosities of the compositions of Examples 1 to 15 were 14.1 to 20.0 mPa · s. Thus, the composition of an Example has a small viscosity compared with the composition of a comparative example. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent characteristics.

  The liquid crystal composition of the present invention can be used for a liquid crystal projector, a liquid crystal television and the like.

Claims (18)

Containing at least one compound selected from the group of compounds represented by formula (1) as the first component and at least one compound selected from the group of compounds represented by formula (2) as the second component And a liquid crystal composition having negative dielectric anisotropy.

In Formula (1) and Formula (2), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 to 12 carbons. Or an alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; R ³ is ethyl, vinyl, or 1-propenyl; ring A is tetrahydropyran-2 Ring B and Ring C are independently 2-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene; Z ¹ , Z ² , and Z ³ Are independently a single bond, ethylene, carbonyloxy, or methyleneoxy; one of a and b is 0 and the other is 1. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-6) as a first component.

In formula (1-1) to formula (1-6), R ¹ and R ² are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 1 or 2, wherein the ratio of the first component is in the range of 5 wt% to 25 wt%, and the ratio of the second component is in the range of 15 wt% to 70 wt%. The liquid crystal composition according to any one of claims 1 to 3, comprising at least one compound selected from the group of compounds represented by formula (3) as a third component.

In Formula (3), R ⁴ and R ⁵ are independently 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 1 to 12 carbon alkyls in which at least one hydrogen is replaced by fluorine or chlorine; ring D and ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4 -Phenylene, 1,4-phenylene, naphthalene-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, in which at least one hydrogen is replaced by fluorine or chlorine, chroman -2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; E represents 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5 - There trifluoroacetic naphthalene-2,6-diyl or 7,8-difluoro-chroman-2,6-diyl,; ^{Z 4} and ^{Z 5} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy, 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 according to any one of claims 1 to 4, comprising at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-20) as a third component. Composition.

In formula (3-1) to formula (3-20), R ⁴ and R ⁵ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon Alkenyloxy having 2 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 4 or 5, wherein the ratio of the third component is in the range of 20 wt% to 75 wt%. The liquid crystal composition according to any one of claims 1 to 6, comprising at least one compound selected from the group of compounds represented by formula (4) as a fourth component.

In Formula (4), R ⁶ and R ⁷ are independently 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 Or alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, ethylene, or carbonyloxy; e is 1 2 or 3; when e is 1, ring I is 1,4-phenylene. The liquid crystal according to any one of claims 1 to 7, comprising at least one compound selected from the group of compounds represented by formula (4-1) to formula (4-12) as a fourth component. Composition.

In formulas (4-1) to (4-12), R ⁶ and R ⁷ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, It is alkyl having 1 to 12 carbons in which one hydrogen is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.   The liquid crystal composition according to claim 7 or 8, wherein the ratio of the fourth component is in the range of 2 wt% to 30 wt%. 10. The liquid crystal composition according to claim 1, comprising at least one compound selected from the group of polymerizable compounds represented by formula (5) as an additive.

In formula (5), ring J and ring L are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine- 2-yl or pyridin-2-yl, and 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. C 1-12 alkyl substituted with fluorine or chlorine may be substituted; ring K may be 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, in which at least one hydrogen is fluorine, chlorine, carbon number 1 to 12 alkyl, 1 to 12 carbon alkoxy, or at least one hydrogen may be replaced with 1 to 12 carbon alkyl substituted with fluorine or chlorine; Z ⁷ and Z ⁸ 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 are independently a polymerizable group; Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and in the alkylene, at least one — CH ₂ — may be replaced by —O—, —COO—, —OCO—, or —OCOO—, wherein 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; f is 0, 1, or 2; g, h, and i are independently 0, 1, 1, 2, 3, or 4 and the sum of g, h, and i is 1 or greater. In Formula (5), P ¹ , P ² , and P ³ are groups independently selected from the group of polymerizable groups represented by Formula (P-1) to Formula (P-5). The liquid crystal composition according to claim 10.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine 1-5 alkyl substituted with The additive according to any one of claims 1 to 11, comprising at least one compound selected from the group of polymerizable compounds represented by formula (5-1) to formula (5-27) as an additive. Liquid crystal composition.

In Formula (5-1) to Formula (5-27), P ¹ , P ² , and P ³ are each independently a polymerizable group represented by Formula (P-1) to Formula (P-3). A group selected from the 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. Yes; Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or alkylene having 1 to 10 carbons, in which at least one —CH ₂ — is —O—, —COO— , —OCO—, or —OCOO—, and at least one —CH ₂ —CH ₂ — may be replaced with —CH═CH— or —C≡C— , 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 a ratio of the additive is in the range of 0.03% by weight to 10% by weight.   The liquid crystal display element containing the liquid-crystal composition of any one of Claim 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.   14. A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition according to claim 1, wherein an additive contained 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 element.