JP2018123296A - 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 demands for characteristic such as a high maximum temperature, a low minimum temperature, small viscosity, appropriate optical anisotropy and negatively large dielectric anisotropy, or having an appropriate balance in at least two of the above characteristics, and an AM element comprising the above composition.SOLUTION: The liquid crystal composition may contain a polymerizable compound as a first additive and may contain a specific compound having negatively large dielectric anisotropy as a first component or a specific compound having a high maximum temperature or small viscosity as a second component.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 and multiplex, and AM is classified into thin film transistor (TFT), metal insulator metal (MIM), and the like. TFTs are classified into amorphous silicon and polycrystalline silicon depending on the material. The latter is further 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 relationship between the two characteristics is 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 not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferable. A composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after being used for a long time is preferable. 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 for a liquid crystal monitor, a liquid crystal television, and the like.

  In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. 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. A composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode, an FFS mode, or an FPA mode. Examples of compositions for polymer-supported orientation type elements are disclosed in Patent Documents 1 to 4.

International Publication No. 2015/004954 JP 2003-307720 A JP 2004-131704 A European Patent Application Publication No. 1898894

  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）において、環Ａおよび環Ｃ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Ｂ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、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；ａは、１または２であり；ｂ、ｃ、およびｄは独立して、０、１、２、３、または４であり；そしてｂ、ｃ、およびｄの和は、２以上である。 It contains at least one compound selected from the polymerizable compounds represented by formula (1) as an additive, and the proportion of the additive is 0.7% by weight or more, and has a negative dielectric anisotropy The present invention relates to a liquid crystal composition and a liquid crystal display device containing the composition.

In formula (1), ring A and ring C 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 B 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, C 1 to C 12 alkoxy, C 2 to C 12 alkenyloxy, or at least one hydrogen substituted with fluorine or chlorine may be substituted with C 1 to C 12 alkyl; P ¹ , P ² , and P ³ are independently polymerizable groups; a is 1 or 2; b, c, and d are independently 0, 1, 2, 3 or 4; and the sum of b, c, and d is 2 or greater.

  The advantages of the present invention are 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, the high stability to ultraviolet rays, the heat It is to provide a liquid crystal composition satisfying at least one of the characteristics such as high stability against. 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, and 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. The characteristics of the composition and the device may be examined by a aging 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.

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 (2-1) is ethyl and R ¹ of the compound (2-2) is ethyl. In some cases, R ^{1 of} compound (2-1) is ethyl and R ¹ of compound (2-2) is propyl. This rule also applies to symbols such as other end groups. In the formula (2), when the subscript “e” 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 'e' is greater than 2. This rule also applies to symbols such as Z ¹ and ring G. This rule also applies to the case that the two -P ⁵ in the compound (1-12).

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 the compound (1), the hatched across one side of the hexagon represents that any hydrogen on the ring may be substituted with groups such as -P ^1. A subscript such as 'b' indicates the number of groups replaced. When the subscript 'b' is 0 (zero), there is no such replacement. When the subscript 'b' is 2 or more, there are a plurality of -P ¹ on the ring A. In this case, a plurality of groups -P ¹ represents 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.

式（１）において、環Ａおよび環Ｃ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Ｂ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、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；ａは、１または２であり；ｂ、ｃ、およびｄは独立して、０、１、２、３、または４であり；そしてｂ、ｃ、およびｄの和は、２以上である。 The present invention includes the following items.
Item 1. It contains at least one compound selected from the polymerizable compounds represented by formula (1) as an additive, and the proportion of the additive is 0.7% by weight or more, and has a negative dielectric anisotropy Liquid crystal composition.

In formula (1), ring A and ring C 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 B 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, C 1 to C 12 alkoxy, C 2 to C 12 alkenyloxy, or at least one hydrogen substituted with fluorine or chlorine may be substituted with C 1 to C 12 alkyl; P ¹ , P ² , and P ³ are independently polymerizable groups; a is 1 or 2; b, c, and d are independently 0, 1, 2, 3 or 4; and the sum of b, c, and d is 2 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 2. In formula (1), 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). 2. The liquid crystal composition according to 1.

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（１−１）から式（１−１３）において、Ｐ^４、Ｐ^５、およびＰ^６は独立して、式（Ｐ−１）から式（Ｐ−３）で表される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のアルキルである。

Item 3. Item 3. The liquid crystal composition according to item 1 or 2, comprising at least one compound selected from the group of polymerizable compounds represented by formula (1-1) to formula (1-13).

In Formula (1-1) to Formula (1-13), P ⁴ , P ⁵ , and P ⁶ are each independently a polymerizable group represented by Formula (P-1) to Formula (P-3). A group selected from the group, wherein M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl of 1 to 5 carbons, or at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 5 carbon atoms.

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；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、またはテトラヒドロピラン−２，５−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^１およびＺ^２は独立して、単結合、エチレン、メチレンオキシ、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、ｆは０または１であり；そしてｅとｆ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 compounds represented by formula (2) as a first component.

In 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, 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 in which at least one hydrogen is replaced by fluorine or chlorine, or tetrahydropyran-2,5-diyl; 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-be difluorochroman-2,6-diyl,; ^{Z 1} and ^{Z 2} are each independently a single bond, ethylene, methyleneoxy or carbonyloxy,; e is 1, 2 or 3, f is 0 or 1, and the sum of e and f is 3 or less.

式（２−１）から式（２−２７）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 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 (2-1) to (2-27) as a first component: object.

In formulas (2-1) to (2-27), 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 6. Item 6. The liquid crystal composition according to item 4 or 5, wherein the ratio of the first component is in the range of 10 wt% to 90 wt%.

式（３）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、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^３は、単結合、エチレン、またはカルボニルオキシであり；ｇは１、２、または３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 compounds represented by formula (3) as the second component.

In Formula (3), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is fluorine or chlorine. Substituted alkenyl having 2 to 12 carbons; 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 ³ is a single bond, ethylene, or carbonyloxy; g is 1, 2, or 3.

式（３−１）から式（３−１３）において、Ｒ^３およびＲ^４は独立して、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、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, containing at least one compound selected from the group of compounds represented by formulas (3-1) to (3-13) as a second component: object.

In Formula (3-1) to Formula (3-13), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine.

Item 9. Item 9. The liquid crystal composition according to item 7 or 8, wherein the ratio of the second component is in the range of 10% by weight to 90% by weight.

Item 10. Item 10. A liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 9.

Item 11. Item 11. The liquid crystal display element according to item 10, 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 12. Item 10. A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 9, or a polymerizable compound in the liquid crystal composition being polymerized.

Item 13. Item 10. Use of the liquid crystal composition according to any one of items 1 to 9 in a liquid crystal display device.

Item 14. Item 10. Use of the liquid crystal composition according to any one of items 1 to 9 in a polymer supported alignment type liquid crystal display device.

  The present invention also includes the following items. (A) The liquid crystal composition described above is placed between two substrates, and light is applied to the composition in a state where a voltage is applied to polymerize a polar compound having a polymerizable group contained in the composition. A method for producing the liquid crystal display element described above. (B) The upper limit temperature of the nematic phase is 70 ° C or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C) is 0.08 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C) ) Is −2 or less.

  The present invention also includes the following items. (A) One compound selected from the group of additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, two compounds Or a composition as described above containing three or more compounds. (B) An AM device containing the above composition. (C) The above-mentioned composition further containing a polymerizable compound, and a polymer-supported orientation (PSA) type AM device containing this composition. (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 constitution of component compounds in 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. This composition contains a plurality of liquid crystal compounds. The composition may contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into a composition A and a composition B from the viewpoint of a liquid crystal compound. The composition A may further contain other liquid crystal compounds, additives and the like in addition to the liquid crystal compound selected from the compound (2) and the compound (3). The “other liquid crystal compound” is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

  Composition B consists essentially of a liquid crystalline compound selected from compound (2) and compound (3). “Substantially” means that the composition B may contain an additive but does not contain any 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 and the device will be described. 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 extremely small.

  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) gives a polymer by polymerization, and this polymer shortens the response time of the device and improves image burn-in. Compound (2) increases the dielectric anisotropy and decreases the minimum temperature. Compound (3) decreases the viscosity or increases the maximum temperature.

  Third, the combination of components in the composition, the preferred ratio of the component compounds, and the basis thereof will be described. A preferred combination of components in the composition is compound (1) + compound (2), compound (1) + compound (3), or compound (1) + compound (2) + compound (3). A more preferred combination is compound (1) + compound (2) + compound (3).

  A polymerizable compound such as compound (1) is added to the composition for the purpose of adapting it to a polymer-supported orientation type device. A desirable ratio of the polymerizable compound is approximately 0.7% by weight or more for shortening the response time, and approximately 10% by weight or less for preventing a display defect of the device. A more desirable ratio is in the range of approximately 1% by weight to approximately 5% by weight. A particularly preferred ratio is in the range of approximately 1.5% by weight to approximately 2% by weight.

  A desirable ratio of compound (2) is approximately 10% by weight or more for increasing the dielectric anisotropy, and approximately 90% by weight or less for decreasing the minimum temperature. A more desirable ratio is in the range of approximately 20% by weight to approximately 80% by weight. A particularly desirable ratio is in the range of approximately 30% by weight to approximately 70% by weight.

  A desirable ratio of compound (3) is approximately 10% by weight or more for increasing the maximum temperature or decreasing the viscosity, and approximately 90% by weight or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of approximately 20% by weight to approximately 80% by weight. A particularly desirable ratio is in the range of approximately 30% by weight to approximately 70% by weight.

  Fourth, a preferred form of the component compound will be described. In formula (1), ring A and ring C 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. It may be replaced by alkyl having 1 to 12 carbon atoms replaced by fluorine or chlorine. Preferred ring A or ring C is phenyl. Ring B 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, alkenyloxy having 2 to 12 carbons, or at least May be replaced by one of hydrogen from 1 carbon atoms are replaced by fluorine or chlorine 12 alkyl. Preferred ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene.

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). P ⁴ , P ⁵ , and P ⁶ are independently a group selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3). Preferred P ⁴ , P ⁵ , or P ⁶ is a group selected from a polymerizable group represented by formula (P-1). 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.

  a is 1 or 2. Preferred a is 1. b, c, and d are independently 0, 1, 2, 3, or 4, and the sum of b, c, and d is 2 or more. Preferred b, c, or d is 1 or 2. Preferred sum of b, c, and d is 3 or more.

In Formula (2) and Formula (3), 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. Desirable R ¹ or R ² is alkyl having 1 to 12 carbons for increasing the stability, and alkoxy having 1 to 12 carbons for increasing the dielectric anisotropy. R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or carbon 2 having at least one hydrogen replaced with fluorine or chlorine. To 12 alkenyl. Desirable R ³ or R ⁴ is alkenyl having 2 to 12 carbons for decreasing the viscosity, and alkyl having 1 to 12 carbons for increasing the stability.

  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 alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferable alkenyloxy is allyloxy or 3-butenyloxy for decreasing the viscosity.

  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.

または

であり、好ましくは

である。 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, or Tetrahydropyran-2,5-diyl. Preferred examples of “1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine” are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- 3-Fluoro-1,4-phenylene. Preferred ring D or ring F is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and for increasing the optical anisotropy. 1,4-phenylene. Tetrahydropyran-2,5-diyl is

Or

And preferably

It is.

  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.
Desirable ring G or ring I is 1,4-cyclohexylene for decreasing the viscosity or increasing the maximum temperature, and 1,4-phenylene for increasing the optical anisotropy.

Z ¹ and Z ² are independently a single bond, ethylene, methyleneoxy, or carbonyloxy. Desirable Z ¹ or Z ² is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy. Z ³ is a single bond, ethylene, or carbonyloxy. Desirable Z ³ is a single bond for decreasing the viscosity.

  e is 1, 2 or 3, f is 0 or 1, and the sum of e and f is 3 or less. Preferred e is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Preferred f is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature. g is 1, 2 or 3. Preferred g is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature.

  Fifth, preferred component compounds are shown. Desirable compounds (1) are the compounds (1-1) to (1-13) described in item 3. More desirable compound (1) is compound (1-7), compound (1-9), compound (1-10), compound (1-11), or compound (1-13).

  Desirable compound (2) is the compound (2-1) to the compound (2-27) according to item 5. In these compounds, at least one of the first components is a compound (2-1), a compound (2-3), a compound (2-6), a compound (2-8), a compound (2-10), a compound ( 2-14) or compound (2-17) is preferable. At least two of the first components are compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8), Compound (2-3) and Compound (2-14), Compound (2-3) and Compound (2-17), Compound (2-6) and Compound (2-8), Compound (2-6) and Compound A combination of (2-10), compound (2-6) and compound (2-17), compound (2-10) and compound (2-17) is preferred.

  Desirable compound (3) is the compound (3-1) to the compound (3-13) according to item 8. In these compounds, at least one of the second components is the compound (3-1), the compound (3-3), the compound (3-5), the compound (3-6), the compound (3-8), or the compound (3-9) is preferred. At least two of the second components are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3-6). It is preferable that it is the combination of these.

  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, and the like. An optically active compound is added to the composition for the purpose of inducing a helical structure of liquid crystal molecules to give a twist angle. Examples of such compounds are compounds (4-1) to (4-5). 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 (5) wherein n is an integer of 1 to 9.

  In the compound (5), preferable n is 1, 3, 5, 7, or 9. Further preferred n is 7. Since the compound (5) 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 in these absorbents and stabilizers is approximately 50 ppm or more for obtaining 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 added to the composition in order to adapt it to a polymer supported alignment (PSA) type device. Compound (1) is suitable for this purpose. Other polymerizable compounds different from these compounds may be added to the composition together with the compound (1). Preferable examples of other polymerizable compounds 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. When other polymerizable compounds are added, a preferred ratio of compound (1) is about 10% by weight or more based on the total weight of the polymerizable compounds. A more desirable ratio is about 50% by weight or more. A particularly desirable ratio is approximately 80% by weight or more. A particularly desirable ratio is also 100% by weight.

  A polymerizable compound such as compound (1) is polymerized by ultraviolet irradiation. The polymerization may be performed in the presence of a suitable polymerization initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark; BASF), which are photoinitiators, are suitable for radical polymerization. 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 a polymerizable compound such as compound (1), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone derivatives such as hydroquinone and methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

  Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. The synthesis method is illustrated. Compound (1-7) is synthesized by the method described in International Publication No. 2015/004947. Compound (2-1) is synthesized by the method described in JP-A No. 2000-053602. Compound (3-1) is synthesized by the method described in JP-A-59-176221. Antioxidants are commercially available. Compounds of formula (5) where n is 1 are available from Sigma-Aldrich Corporation. Compound (5) etc. in which n is 7 are 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 mode such as TN, OCB, IPS, or FFS 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 conventional polymer-supported orientation type device is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal compound is 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 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 following methods.

NMR analysis: For measurement, DRX-500 manufactured by Bruker BioSpin Corporation was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and 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. A mixture of liquid crystal compounds is detected by a gas chromatograph (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 injected into 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 by the method described in measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C.): The 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 injected into 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 by ultraviolet rays after the sample was injected. 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 LCD5200 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter (Low-pass filter) was set to 500 Hz.
A distance (cell gap) between two glass substrates was 3.2 μm, and a sample was put in a normally black mode PSA element. The device was irradiated with 76 mW / cm ² of ultraviolet light while applying a voltage of 15 V, and the pretilt angle was set to 0.9 ± 0.2 °. A metal halide lamp (US4-X0401FKTN) manufactured by Eye Graphic Co., Ltd. was used for ultraviolet irradiation. Next, ultraviolet rays of 3.8 mW / cm ² were irradiated for 60 minutes without applying a voltage. A black light (F40T10) manufactured by Eye Graphic Co., Ltd. was used for ultraviolet irradiation. A rectangular wave (30 Hz, 7.5 V, 1 second) 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.
(Specific resistance) = {(Voltage) × (Capacity of vessel)} / {(DC current) × (Dielectric constant of vacuum)}

  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.

測定方法（１２）に記載した方法で、応答時間を測定した。τ＝４．９ｍｓ． [Comparative Example 1]
In the examples described in WO2015 / 004954, the compound (1-3) and the compound (1-9) were contained, and the example 3 with the shortest response time was taken as the comparative example 1.
3-BB (2F, 3F) -O2 (2-6) 9%
2O-BB (2F, 3F) -O2 (2-6) 3%
2-HH1OB (2F, 3F) -O2 (2-10) 10%
3-HH1OB (2F, 3F) -O2 (2-10) 20%
2-BB (2F, 3F) B-4 (2-19) 3%
2-HH-3 (3-1) 19%
3-HH-4 (3-1) 4%
3-HH-V (3-1) 8%
V2-BB-1 (3-3) 3%
1-BB-3 (3-3) 6%
V-HHB-3 (3-5) 5%
3-HBB-2 (3-6) 4%
5-B (F) BB-2 (3-7) 3%
5-HBBH-3 (3) 3%
NI = 83.6 ° C .; Tc <−20 ° C .; Δn = 0.108; Δε = −2.8; Vth = 2.34V.
To this composition, 0.2% by weight of compound (1-3) and 0.2% by weight of compound (1-9) were added.

The response time was measured by the method described in measurement method (12). τ = 4.9 ms.

測定方法（１２）に記載した方法で、応答時間を測定した。τ＝４．４ｍｓ． [Example 1]
3-BB (2F, 3F) -O2 (2-6) 9%
2O-BB (2F, 3F) -O2 (2-6) 3%
2-HH1OB (2F, 3F) -O2 (2-10) 10%
3-HH1OB (2F, 3F) -O2 (2-10) 20%
2-BB (2F, 3F) B-4 (2-19) 3%
2-HH-3 (3-1) 19%
3-HH-4 (3-1) 4%
3-HH-V (3-1) 8%
V2-BB-1 (3-3) 3%
1-BB-3 (3-3) 6%
V-HHB-3 (3-5) 5%
3-HBB-2 (3-6) 4%
5-B (F) BB-2 (3-7) 3%
5-HBBH-3 (3) 3%
Compound (1-3) was added to this composition at a ratio of 0.5 wt% and compound (1-9) was added at a ratio of 0.5 wt%.

The response time was measured by the method described in measurement method (12). τ = 4.4 ms.

ＮＩ＝７８．１℃；Ｔｃ＜−２０℃；Δｎ＝０．１０５；Δε＝−３．４；Ｖｔｈ＝２．１３Ｖ；τ＝４．４ｍｓ． [Example 2]
2-H1OB (2F, 3F) -O2 (2-3) 8%
3-H1OB (2F, 3F) -O2 (2-3) 9%
2-HHB (2F, 3F) -O2 (2-8) 3%
3-HHB (2F, 3F) -O2 (2-8) 3.5%
2-HBB (2F, 3F) -O2 (2-14) 5%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
5-HBB (2F, 3F) -O2 (2-14) 10.5%
2-HH-3 (3-1) 20%
3-HH-4 (3-1) 4%
3-HB-O2 (3-2) 14%
3-HBB-2 (3-6) 7%
Compound (1-7) was added to the composition at a ratio of 0.8% by weight.

NI = 78.1 ° C .; Tc <−20 ° C .; Δn = 0.105; Δε = −3.4; Vth = 2.13 V; τ = 4.4 ms.

ＮＩ＝７６．８℃；Ｔｃ＜−２０℃；η＝１５．５ｍＰａ・ｓ；Δｎ＝０．１０５；Δε＝−３．２；Ｖｔｈ＝２．６６Ｖ；τ＝４．５ｍｓ． [Example 3]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 3.5%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 13%
5-HB-O2 (3-2) 7.5%
3-HHB-3 (3-5) 2%
3-HBB-2 (3-6) 14%
Compound (1-10) was added to this composition in a proportion of 0.7% by weight.

NI = 76.8 ° C .; Tc <−20 ° C .; η = 15.5 mPa · s; Δn = 0.105; Δε = −3.2; Vth = 2.66 V; τ = 4.5 ms.

ＮＩ＝７８．４℃；Ｔｃ＜−２０℃；η＝１６．２ｍＰａ・ｓ；Δｎ＝０．１０５；Δε＝−２．７；Ｖｔｈ＝２．４３Ｖ；τ＝４．４ｍｓ． [Example 4]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 8%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
2-HH-5 (3-1) 2%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 17%
3-HBB-2 (3-6) 10%
Compound (1-11) was added to the composition at a ratio of 0.8% by weight.

NI = 78.4 ° C .; Tc <−20 ° C .; η = 16.2 mPa · s; Δn = 0.105; Δε = −2.7; Vth = 2.43 V; τ = 4.4 ms.

ＮＩ＝７５．６℃；η＝１８．４ｍＰａ・ｓ；Δｎ＝０．１０５；Δε＝−３．３；Ｖｔｈ＝２．１３Ｖ；τ＝４．３ｍｓ． [Example 5]
2-H1OB (2F, 3F) -O2 (2-3) 7%
3-H1OB (2F, 3F) -O2 (2-3) 7%
3-DhB (2F, 3F) -O2 (2-4) 5%
3-HHB (2F, 3F) -O2 (2-8) 4.5%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 9%
4-HBB (2F, 3F) -O2 (2-14) 4%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-dhBB (2F, 3F) -O2 (2-16) 4%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 3%
3-HH-5 (3-1) 3%
3-HB-O2 (3-2) 13%
3-HBB-2 (3-6) 9.5%
Compound (1-13) was added to the composition at a ratio of 0.9% by weight.

NI = 75.6 ° C .; η = 18.4 mPa · s; Δn = 0.105; Δε = −3.3; Vth = 2.13 V; τ = 4.3 ms.

ＮＩ＝７４．４℃；Ｔｃ＜−２０℃；Δｎ＝０．０９８；Δε＝−３．０；Ｖｔｈ＝２．１７Ｖ；τ＝４．４ｍｓ． [Example 6]
2-H1OB (2F, 3F) -O2 (2-3) 8%
3-H1OB (2F, 3F) -O2 (2-3) 8%
2O-B (2F) B (2F, 3F) -O2 (2-7) 4%
2O-B (2F) B (2F, 3F) -O4 (2-7) 6%
3-HHB (2F, 3F) -O2 (2-8) 7%
2-HBB (2F, 3F) -O2 (2-14) 3%
3-HBB (2F, 3F) -O2 (2-14) 10%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 5%
3-HH-5 (3-1) 5%
3-HB-O2 (3-2) 7%
3-HHB-1 (3-5) 5%
3-HHB-3 (3-5) 6%
3-HBB-2 (3-6) 8%
Compound (1-7) was added to this composition in a proportion of 0.7% by weight.

NI = 74.4 ° C .; Tc <−20 ° C .; Δn = 0.098; Δε = −3.0; Vth = 2.17 V; τ = 4.4 ms.

ＮＩ＝７５．４℃；Ｔｃ＜−２０℃；Δｎ＝０．１０６；Δε＝−２．５；τ＝３．７ｍｓ． [Example 7]
3-HB (2F, 3F) -O2 (2-1) 13%
3-HHB (2F, 3F) -O2 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-V (3-1) 36%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
Compound (1-7) was added to this composition in a proportion of 0.7% by weight.

NI = 75.4 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.5; τ = 3.7 ms.

ＮＩ＝７４．７℃；Ｔｃ＜−２０℃；Δｎ＝０．１０６；Δε＝−２．７；τ＝４．０ｍｓ． [Example 8]
3-HB (2F, 3F) -O2 (2-1) 3%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 12%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HBB (2F, 3F) -O2 (2-14) 8%
3-dhBB (2F, 3F) -O2 (2-16) 8%
3-HH-V (3-1) 33%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 8%
Compound (1-9) was added to the composition at a ratio of 0.8% by weight.

NI = 74.7 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.7; τ = 4.0 ms.

ＮＩ＝７５．３℃；Ｔｃ＜−２０℃；Δｎ＝０．１０６；Δε＝−２．７；τ＝３．８ｍｓ． [Example 9]
2O-B (2F) B (2F, 3F) -O2 (2-7) 6%
2O-B (2F) B (2F, 3F) -O4 (2-7) 13%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
3-dhBB (2F, 3F) -O2 (2-16) 5%
3-HB (2F) B (2F, 3F) -O2 (2-18) 7%
3-H2BBB (2F, 3F) -O2 (2-25) 5%
3-HH-V (3-1) 42%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 3%
V-HHB-1 (3-5) 2%
Compound (1-7) was added to this composition at a ratio of 1.0% by weight.

NI = 75.3 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.7; τ = 3.8 ms.

ＮＩ＝７６．１℃；Ｔｃ＜−２０℃；η＝１７．８ｍＰａ・ｓ；Δｎ＝０．０９３；Δε＝−２．９；τ＝４．３ｍｓ． [Example 10]
3-H2B (2F, 3F) -O2 (2-2) 15%
5-H2B (2F, 3F) -O2 (2-2) 6%
3-HDhB (2F, 3F) -O2 (2-13) 7%
3-HBB (2F, 3F) -O2 (2-14) 10%
4-HBB (2F, 3F) -O2 (2-14) 7%
5-HBB (2F, 3F) -O2 (2-14) 7%
2-HH-3 (3-1) 18%
3-HH-4 (3-1) 8%
3-HB-O2 (3-2) 10%
5-HB-O2 (3-2) 3%
3-HHB-1 (3-5) 3%
3-HHB-3 (3-5) 3%
3-HHB-O1 (3-5) 3%
Compound (1-7) was added to the composition at a ratio of 0.9% by weight.

NI = 76.1 ° C .; Tc <−20 ° C .; η = 17.8 mPa · s; Δn = 0.093; Δε = −2.9; τ = 4.3 ms.

ＮＩ＝７４．８℃；Ｔｃ＜−２０℃；η＝１３．８ｍＰａ・ｓ；Δｎ＝０．１０２；Δε＝−２．６；τ＝４．０ｍｓ． [Example 11]
3-BB (2F, 3F) -O2 (2-6) 10%
V2-BB (2F, 3F) -O2 (2-6) 9%
V-HHB (2F, 3F) -O1 (2-8) 4%
V-HHB (2F, 3F) -O2 (2-8) 12%
V-HHB (2F, 3F) -O4 (2-8) 10%
3-HH2B (2F, 3F) -O2 (2-9) 8%
3-HH-V (3-1) 29%
3-HB-O2 (3-2) 1%
1-BB-3 (3-3) 4%
1-BB-5 (3-3) 2%
V-HHB-1 (3-5) 11%
Compound (1-7) was added to the composition at a ratio of 0.8% by weight.

NI = 74.8 ° C .; Tc <−20 ° C .; η = 13.8 mPa · s; Δn = 0.102; Δε = −2.6; τ = 4.0 ms.

ＮＩ＝７０．１℃；Ｔｃ＜−２０℃；η＝１６．４ｍＰａ・ｓ；Δｎ＝０．０９２；Δε＝−２．６；τ＝４．０ｍｓ． [Example 12]
3-H2B (2F, 3F) -O2 (2-2) 20%
5-H2B (2F, 3F) -O2 (2-2) 20%
3-HHB (2F, 3Cl) -O2 (2-11) 2%
3-HBB (2F, 3Cl) -O2 (2-15) 8%
5-HBB (2F, 3Cl) -O2 (2-15) 7%
3-HH-V (3-1) 26%
V-HHB-1 (3-5) 6%
2-BB (F) B-3 (3-8) 4%
3-HHEBH-3 (3-11) 4%
3-HHEBH-4 (3-11) 3%
Compound (1-7) was added to the composition at a ratio of 0.8% by weight.

NI = 70.1 ° C .; Tc <−20 ° C .; η = 16.4 mPa · s; Δn = 0.092; Δε = −2.6; τ = 4.0 ms.

ＮＩ＝７５．１℃；Ｔｃ＜−２０℃；η＝１７．１ｍＰａ・ｓ；Δｎ＝０．１０３；Δε＝−２．５；τ＝４．２ｍｓ． [Example 13]
3-HB (2F, 3F) -O2 (2-1) 8%
V-HB (2F, 3F) -O2 (2-1) 12%
V-HB (2F, 3F) -O4 (2-1) 3%
3-HBB (2F, 3F) -O2 (2-14) 10%
5-HBB (2F, 3F) -O2 (2-14) 9%
3-HH1OCro (7F, 8F) -O2 (2-27) 5%
2-HH-3 (3-1) 22%
3-HH-VFF (3-1) 9%
3-HB-O2 (3-2) 10%
5-HBB (F) B-2 (3-13) 6%
5-HBB (F) B-3 (3-13) 6%
Compound (1-7) was added to this composition in a proportion of 0.7% by weight.

NI = 75.1 ° C .; Tc <−20 ° C .; η = 17.1 mPa · s; Δn = 0.103; Δε = −2.5; τ = 4.2 ms.

ＮＩ＝７３．５℃；Ｔｃ＜−２０℃；η＝１７．０ｍＰａ・ｓ；Δｎ＝０．１０６；Δε＝−２．７；τ＝３．７ｍｓ． [Example 14]
3-HB (2F, 3F) -O2 (2-1) 5%
V2-BB (2F, 3F) -O2 (2-6) 8%
3-HHB (2F, 3F) -O2 (2-8) 6%
V-HHB (2F, 3F) -O2 (2-8) 7%
V-HHB (2F, 3F) -O4 (2-8) 4%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 6%
V-HBB (2F, 3F) -O2 (2-14) 7%
V-HBB (2F, 3F) -O4 (2-14) 6%
2-BB (2F, 3F) B-3 (2-19) 5%
V-HH-V (3-1) 24%
V-HH-V1 (3-1) 20%
Compound (1-9) was added to this composition in a proportion of 1.0% by weight.

NI = 73.5 ° C .; Tc <−20 ° C .; η = 17.0 mPa · s; Δn = 0.106; Δε = −2.7; τ = 3.7 ms.

ＮＩ＝７３．６℃；Ｔｃ＜−２０℃；Δｎ＝０．１０６；Δε＝−２．４；τ＝３．７ｍｓ． [Example 15]
3-HB (2F, 3F) -O2 (2-1) 13%
3-HHB (2F, 3F) -1 (2-8) 2%
3-HHB (2F, 3F) -2 (2-8) 2%
2-HBB (2F, 3F) -O2 (2-14) 4%
3-HBB (2F, 3F) -O2 (2-14) 11%
4-HBB (2F, 3F) -O2 (2-14) 5%
V-HBB (2F, 3F) -O2 (2-14) 8%
V-HBB (2F, 3F) -O4 (2-14) 8%
3-HH-V (3-1) 36%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
Compound (1-10) was added to the composition at a ratio of 0.9% by weight.

NI = 73.6 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.4; τ = 3.7 ms.

ＮＩ＝７２．５℃；Ｔｃ＜−２０℃；Δｎ＝０．１０６；Δε＝−２．６；τ＝３．９ｍｓ． [Example 16]
3-HB (2F, 3F) -O2 (2-1) 3%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 12%
2-HHB (2F, 3F) -O2 (2-8) 4%
3-HHB (2F, 3F) -O2 (2-8) 8%
5-HBB (2F, 3F) -O2 (2-14) 4%
3-dhBB (2F, 3F) -O2 (2-16) 8%
3-HB (2F, 3F) B-2 (2-17) 4%
3-HH-V (3-1) 33%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 8%
Compound (1-9) was added to the composition at a ratio of 0.8% by weight.

NI = 72.5 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = −2.6; τ = 3.9 ms.

ＮＩ＝７４．２℃；Ｔｃ＜−２０℃；Δｎ＝０．１１５；Δε＝−２．１；τ＝３．９ｍｓ． [Example 17]
3-DhB (2F, 3F) -O2 (2-4) 2%
2O-B (2F) B (2F, 3F) -O2 (2-7) 5%
2O-B (2F) B (2F, 3F) -O4 (2-7) 14%
2-HHB (2F, 3F) -O2 (2-8) 2%
3-HHB (2F, 3F) -O2 (2-8) 5%
2-HBB (2F, 3F) -O2 (2-14) 2%
3-HBB (2F, 3F) -O2 (2-14) 9%
3-HH-V (3-1) 32%
3-HH-V1 (3-1) 5%
1-BB-3 (3-3) 5%
3-HHB-1 (3-5) 2%
3-HBB-2 (3-6) 17%
Compound (1-7) was added to this composition at a ratio of 1.0% by weight.

NI = 74.2 ° C .; Tc <−20 ° C .; Δn = 0.115; Δε = −2.1; τ = 3.9 ms.

  The composition of Comparative Example 1 in which the proportion of the polymerizable compound represented by the formula (1) is less than 0.7% by weight had a response time of 4.9 ms. On the other hand, the response time of the composition of Example 1 was 4.4 ms. From this result, it was found that the PSA element of the example had a response time shorter than that of Comparative Example 1. Therefore, it is concluded that the composition of the present invention has excellent properties.

  The liquid crystal composition of the present invention has a high maximum temperature, a low minimum temperature, a small viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, and a high stability against heat. Or the like, satisfying at least one characteristic or having an appropriate balance between at least two characteristics. A liquid crystal display element containing this composition has characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime, and thus can be used for a liquid crystal monitor, a liquid crystal television, and the like. .

Claims (14)

It contains at least one compound selected from the polymerizable compounds represented by formula (1) as an additive, and the proportion of the additive is 0.7% by weight or more, and has a negative dielectric anisotropy Liquid crystal composition.

In formula (1), ring A and ring C 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 B 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, C 1 to C 12 alkoxy, C 2 to C 12 alkenyloxy, or at least one hydrogen substituted with fluorine or chlorine may be substituted with C 1 to C 12 alkyl; P ¹ , P ² , and P ³ are independently polymerizable groups; a is 1 or 2; b, c, and d are independently 0, 1, 2, 3 or 4; and the sum of b, c, and d is 2 or greater. In formula (1), 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 2. A liquid crystal composition according to item 1.

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 liquid crystal composition according to claim 1, comprising at least one compound selected from the group of polymerizable compounds represented by formula (1-1) to formula (1-13).

In Formula (1-1) to Formula (1-13), P ⁴ , P ⁵ , and P ⁶ are each independently a polymerizable group represented by Formula (P-1) to Formula (P-3). A group selected from the group, wherein M ¹ , M ² , and M ³ are independently hydrogen, fluorine, alkyl of 1 to 5 carbons, or at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 5 carbon atoms.

The liquid crystal composition according to any one of claims 1 to 3, comprising at least one compound selected from compounds represented by formula (2) as a first component.

In 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, 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 in which at least one hydrogen is replaced by fluorine or chlorine, or tetrahydropyran-2,5-diyl; 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-be difluorochroman-2,6-diyl,; ^{Z 1} and ^{Z 2} are each independently a single bond, ethylene, methyleneoxy or carbonyloxy,; e is 1, 2 or 3, f is 0 or 1, and the sum of e and f 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 (2-1) to formula (2-27) as a first component. Composition.

In formulas (2-1) to (2-27), 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 4 or 5, wherein the proportion of the first component is in the range of 10 wt% to 90 wt%. The liquid crystal composition according to claim 1, comprising at least one compound selected from compounds represented by formula (3) as the second component.

In Formula (3), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen is fluorine or chlorine. Substituted alkenyl having 2 to 12 carbons; 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 ³ is a single bond, ethylene, or carbonyloxy; g is 1, 2, or 3. 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 (3-1) to formula (3-13) as a second component. Composition.

In Formula (3-1) to Formula (3-13), R ³ and R ⁴ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal composition according to claim 7 or 8, wherein the ratio of the second component is in the range of 10 wt% to 90 wt%.   The liquid crystal display element containing the liquid-crystal composition of any one of Claim 1 to 9.   The liquid crystal display element according to claim 10, 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.   10. A polymer-supported alignment type liquid crystal display element comprising the liquid crystal composition according to claim 1 or a polymerized compound in the liquid crystal composition.   Use of the liquid crystal composition according to any one of claims 1 to 9 in a liquid crystal display device.   Use of the liquid crystal composition according to any one of claims 1 to 9 in a polymer supported alignment type liquid crystal display element.