JPWO2018235662A1 - Liquid crystal display device and liquid crystal composition - Google Patents

Abstract

A liquid crystal composition in which the alignment of liquid crystal molecules of a liquid crystal display device having no alignment film is controlled by using an alignment monomer having a specific structure with no coloration, and the alignment monomer having no coloration shows good compatibility. It is to provide things. In the liquid crystal display device having no alignment film of the present invention, a liquid crystal composition having a positive dielectric anisotropy containing a cinnamate group or a chalcone group, and an alignment monomer having a hydroxyl group as a first additive is added to the liquid crystal composition. When polarized light exposure is performed while heating at a temperature higher than the upper limit temperature of the object, the alignment of liquid crystal molecules can be controlled.

Description

  The present invention relates to a liquid crystal display device and a liquid crystal composition containing a liquid crystal composition having a positive dielectric anisotropy. In particular, the present invention relates to a liquid crystal display device using a liquid crystal composition containing an aligning monomer and capable of achieving alignment of liquid crystal molecules by the action of this compound without using an alignment film such as polyimide.

  In a liquid crystal display device, classification based on the operation mode of liquid crystal molecules is performed by PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), and IPS. The modes include (in-plane switching), VA (vertical alignment), FFS (fringe field switching), and FPA (field-induced photo-reactive alignment). The classification based on the drive system of the element is PM (passive matrix) and AM (active matrix). PM is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal). TFTs are classified into amorphous silicon and polycrystal 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 is a reflective type that uses natural light, a transmissive type that uses a backlight, and a transflective type that uses both natural light and a backlight.

  The liquid crystal display device contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM device having good properties can be obtained. The relationship between the two properties 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. The preferred maximum temperature of the nematic phase is about 70 ° C or higher, and the preferred minimum temperature of the nematic phase is about -10 ° C or lower. The viscosity of the composition is related to the response time of the device. A short response time is preferable for displaying a moving image on the device. Response times as short as 1 millisecond are desirable. Therefore, a low viscosity in the composition is preferred. Small viscosities at low temperatures are 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, large optical anisotropy or small optical anisotropy, that is, 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 product value depends on the mode of operation. This value is in the range of about 0.30 μm to about 0.40 μm for VA mode devices and about 0.20 μm to about 0.30 μm for IPS mode or FFS mode devices. 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, large dielectric anisotropy is preferable. The 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 preferable. The stability of the composition against UV and heat is related to the lifetime of the device. When this stability is high, the life 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.

  A composition having a positive dielectric anisotropy is used in an AM device having a TN mode. 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 or an FFS mode. In a polymer sustained alignment (PSA) type AM device, a composition having a positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type liquid crystal display device, a liquid crystal composition containing a polymer is used. First, a composition containing a small amount of a polymerizable compound 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, the orientation of liquid crystal molecules can be controlled by the polymer, so that the response time of the device is shortened and image sticking is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

  Instead of an alignment film such as polyimide, there is a method of controlling the alignment of liquid crystal by using a low molecular compound having a cinnamate group, polyvinyl cinnamate, a low molecular compound having a chalcone structure, a low molecular compound having an azobenzene structure or a dendrimer. It has been reported (Patent Document 1). In the method of Patent Document 1, first, the low molecular weight compound or polymer is dissolved in the liquid crystal composition as an additive. Next, the additive is phase-separated to form a thin film of the low-molecular compound or polymer on the substrate. Finally, the substrate is irradiated with linearly polarized light at a temperature higher than the upper limit temperature of the liquid crystal composition. When the low molecular weight compound or polymer is dimerized or isomerized by this linearly polarized light, the molecules are arranged in a certain direction. In this method, it is possible to manufacture a device of horizontal alignment mode such as IPS and FFS and a device of vertical alignment mode such as VA by selecting the kind of low molecular weight compound or polymer. In this method, it is important that the low molecular weight compound or polymer is easily dissolved at a temperature higher than the maximum temperature of the liquid crystal composition, and when the temperature is returned to room temperature, the compound is easily phase-separated from the liquid crystal composition. However, it was difficult to ensure compatibility between the low molecular weight compound or polymer and the liquid crystal composition.

In the methods of Patent Documents 2 and 3, a dendrimer having azobenzene as a partial structure is dissolved in a liquid crystal composition as an additive. A thin film of this compound is then formed on the substrate by phase separating the compound. At this time, the liquid crystal composition is aligned vertically to the substrate. Next, the substrate is irradiated with linearly polarized light without being heated. When the linearly polarized light causes the dendrimer to dimerize or isomerize, the molecules are aligned in a direction horizontal to the substrate. A device of horizontal alignment mode such as IPS or FFS can be manufactured. Also in this method, the dendrimer and the liquid crystal composition must be appropriately combined so that the dendrimer can easily undergo dissolution and phase separation. When a dendrimer having azobenzene as a partial structure is used, there is a problem that azobenzene-derived coloring occurs.
Further, Patent Document 4 discloses a combination of a liquid crystal compound having a positive dielectric anisotropy and a polymerizable compound. Here, it is disclosed that a response time and electro-optical characteristics of a liquid crystal cell are improved by imparting a pretilt angle by polymerizing a polymerizable compound contained in a liquid crystal medium while applying a voltage. In this method, it was difficult to obtain the horizontal alignment of the liquid crystal compound by polarized light irradiation even if the disclosed polymerizable compound was used. Further, there is no suggestion or description that a specific polymerizable compound can control the horizontal alignment of a liquid crystal compound by polarized light irradiation.
Patent Documents 5 to 7 disclose combinations of a liquid crystal compound having a positive dielectric anisotropy and a polymerizable compound having a polar group. Here, the polymerizable compound having a polar group contained in the liquid crystal medium is intended to vertically control the alignment of the liquid crystal. Even with the method described here, it was difficult to control the alignment of the liquid crystal compound horizontally. Further, there is no suggestion or description that the polymerizable compound having a polar group can control the horizontal alignment of the liquid crystal compound by polarized light irradiation.

International Publication No. 2015/146369 JP, 2005-64465, A JP, 2005-125151, A International Publication No. 2009/156118 International Publication No. 2012/038026 JP-A-2005-168826 International Publication No. 2016/015803

  The problem to be solved by the present invention is to control the orientation of liquid crystal molecules of a liquid crystal display device having no alignment film by using an alignment monomer having no coloring, and an alignment monomer having no coloring is good. To provide a liquid crystal composition exhibiting excellent compatibility.

  In the liquid crystal display device having no alignment film of the present invention, a liquid crystal composition having a positive dielectric anisotropy containing a cinnamate group or chalcone group, and an aligning monomer having a hydroxyl group as a first additive is added to the liquid crystal composition. When the polarized light exposure is performed while heating at a temperature higher than the upper limit temperature of the object, the alignment of the liquid crystal molecules can be controlled.

By using the liquid crystal composition containing the aligning monomer of the present invention, the step of forming the alignment film is unnecessary, so that a liquid crystal display element with reduced manufacturing cost can be obtained.
Further, a liquid crystal composition having a positive dielectric constant anisotropy that is compatible with the orienting monomer can be obtained.

  The usage of terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display device" may be abbreviated as "composition" and "device", respectively. “Liquid crystal display element” is a generic term for a liquid crystal display panel and a liquid crystal display module. The “liquid crystal compound” is a compound having a liquid crystal phase such as a nematic phase or a smectic phase and a liquid crystal phase, but is a composition for the purpose of controlling properties such as temperature range, viscosity and dielectric anisotropy of the nematic phase. It is a general term for the compounds mixed in the product. This compound has a 6-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 crystal compound having an alkenyl is not polymerizable in that sense.

  The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are added to this composition as needed. . The proportion of the liquid crystal compound is represented by a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive even when the additive is added. The ratio of the additive is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the 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.

  The "maximum temperature of the nematic phase" may be abbreviated as "maximum temperature". The "minimum temperature of the nematic phase" may be abbreviated as "minimum temperature". "High resistivity" means that the composition has a high resistivity in the initial stage and a high resistivity after long-term use. “High voltage retention” means that the device has a large voltage retention not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after a long time use, it has a large voltage not only at room temperature but also at a temperature close to the upper limit temperature. Means to have a retention rate. Aging tests are sometimes used to study the properties of compositions and devices. The expression “increasing the dielectric anisotropy” means that, in the case of a composition having a positive dielectric anisotropy, that value increases positively, and a composition having a negative dielectric anisotropy. When it is a thing, it means that its 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 the 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's 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 two. When there are more than one, those positions can be selected without limitation. This rule also applies to the expression "at least one'A 'has been replaced by'B'."

Expressions such as “at least one —CH ₂ — may be replaced with —O—” are used herein. In this _case, -CH ₂ -CH ₂ -CH ₂ - it is, -CH ₂ nonadjacent - may be converted _-O-CH 2 -O- to by is replaced by -O-. However, adjacent -CH ₂ - is not replaced by -O-. This is because this replacement produces —O—O—CH ₂ — (peroxide). In other words, this representation, and both _{- -} "may be replaced by -O- -CH 2 nonadjacent least two,""one -CH 2 is -O- in may be replaced" with means. This rule applies not only to replacement with -O-, but also replacement with divalent groups such as -CH = CH- and -COO-.

In the chemical formulas of component compounds, the symbol of the terminal group R ¹ is used for a plurality of compounds. In these compounds, the two groups represented by any two R ¹ 's 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 (1), when the subscript'a 'is 2, two rings A exist. In this compound, the two rings represented by the two rings A may be the same or different. This rule also applies to any two rings A when the subscript'a 'is greater than 2. This rule also applies to symbols such as Z ¹ , ring D, etc.

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, and represent rings such as six-membered ring and condensed ring. In the formula (4), a diagonal line crossing one side of the hexagon represents that any hydrogen on the ring may be replaced with a group such as —Sp ¹ —P ¹ . Subscripts such as'e 'indicate the number of groups replaced. When the subscript'e 'is 0 (zero), there is no such replacement. When the subscript'e 'is 2 or more, there are a plurality of -Sp ¹ -P ¹ on the ring F. The plurality of groups represented by —Sp ¹ —P ¹ may be the same or different.

2-Fluoro-1,4-phenylene means the following two divalent groups. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric divalent groups created by removing two hydrogens from a 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. Straight-chain alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis for increasing the maximum temperature.

  The present invention includes the following items.

式（Ａ−１）および式（Ａ−２）において、Ｐ^１０は独立して、式（Ｑ−１）から式（Ｑ−５）で表される基から選択された基であり；
式（Ｑ−１）から式（Ｑ−５）において、Ｍ^１０、Ｍ^２０、およびＭ^３０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；
式（Ａ−１）および式（Ａ−２）において、
Ｓｐ^１０およびＳｐ^１１は独立して、単結合または炭素数１から１２のアルキレンであり、このアルキレンの少なくとも１つの水素はフッ素、塩素または式（Ｑ−６）で置き換えられていてもよく、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−または−Ｃ≡Ｃ−で置き換えられてもよく；

式（Ｑ−６）において、Ｍ^１１、Ｍ^２１、およびＭ^３１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^４１は独立して、単結合または炭素数１から１２のアルキレンであり、このアルキレンの少なくとも１つの水素はフッ素または塩素で置き換えられていてもよく、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；
式（Ａ−１）、式（Ａ−２）、式（Ｂ−１）および式（Ｂ−２）において、
環Ａ^１０、環Ａ^２０、環Ａ^３０、環Ａ^４０および環Ａ^５０は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、４，４’−ビフェニレン、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、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、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−ジイル、ペルヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイル、または２，３，４，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７−テトラデカヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイルであるが、隣接する構造が−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−の場合は、１，４−フェニレン、４，４’−ビフェニレン、ナフタレン−２，６−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−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、ヒドロキシ、塩素、炭素数１から１２のアルキル、炭素数２から１２のアルケニル、炭素数１から１１のアルコキシ、または炭素数２から１１のアルケニルオキシ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；
式（Ａ−１）および式（Ａ−２）において、Ｚ^１０は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
式（Ａ−２）において、Ｚ^１１は−ＣＨ＝ＣＨ−ＣＯ−または−ＣＯ−ＣＨ＝ＣＨ−であり；
式（Ａ−１）および式（Ａ−２）において、ｎ^１０は０から４の整数であり；
式（Ｂ−１）および式（Ｂ−２）において、
Ｒ^２０は水素、フッ素、塩素、ヒドロキシ、シアノ、ニトロ、トリフルオロメチル、炭素数１から１０のアルキルまたは炭素数１から１０のアルコキシであり；
Ｓｐ^２０およびＳｐ^２１は独立して単結合または炭素数１から１２のアルキレンであり、このアルキレンの少なくとも１つの水素はフッ素で置き換えられていてもよく、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−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−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ｚ^２０は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
ｎ^２０は０から３の整数である。Item 1. The liquid crystal layer is sandwiched between a pair of substrates which are arranged facing each other and are bonded to each other via a sealant.
Between the pair of substrates and the liquid crystal layer, an alignment control layer that controls the alignment of liquid crystal molecules,
The liquid crystal layer is composed of a liquid crystal composition having a positive dielectric anisotropy,
The liquid crystal composition is a group of compounds represented by the formula (A-1), the formula (A-2), the formula (B-1) and the formula (B-2) as an aligning monomer which is a first additive. Containing at least one compound selected from and a liquid crystal compound,
The said orientation control layer is a liquid crystal display element which consists of the polymer produced by superposing | polymerizing the said 1st additive.

In formulas (A-1) and (A-2), P ¹⁰ is independently a group selected from the groups represented by formulas (Q-1) to (Q-5);
In formulas (Q-1) to (Q-5), M ¹⁰ , M ²⁰ , and M ³⁰ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine. An alkyl having 1 to 5 carbons replaced by
In formula (A-1) and formula (A-2),
Sp ¹⁰ and Sp ¹¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or formula (Q-6), and at least one of _-CH 2 -, -O -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or - May be replaced by C≡C-;

In formula (Q-6), M ¹¹ , M ²¹ , and M ³¹ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine. To 5 alkyls;
Sp ⁴¹ is independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine or chlorine, and at least one —CH ₂ — is —O. -, -CO-, -COO-, or -OCO- may be substituted;
In formula (A-1), formula (A-2), formula (B-1) and formula (B-2),
Ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , ring A ⁴⁰ and ring A ⁵⁰ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 4,4 ′. -Biphenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3 -Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, per Hydrocyclopenta [a] phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclo And the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO-C≡C-. , -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl. , Pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, in which at least one hydrogen is fluorine, hydroxy, It may be replaced by chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons. There are, at least one hydrogen may be replaced by fluorine or chlorine;
In formulas (A-1) and (A-2), Z ¹⁰ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —. _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O-, _{-OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡ C-;
In formula (A-2), Z ¹¹ is —CH═CH—CO— or —CO—CH═CH—;
In the formula (A-1) and the formula (A-2), n ¹⁰ is an integer of 0 to 4;
In formula (B-1) and formula (B-2),
R ²⁰ is hydrogen, fluorine, chlorine, hydroxy, cyano, nitro, trifluoromethyl, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons;
Sp ²⁰ and Sp ²¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, and at least one —CH ₂ — is —O. -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-;
Z ²⁰ is independently a single bond, -COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - ( _{CH 2) 4 -, - CH} 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or a -C≡C-;
n ²⁰ is an integer of 0 to 3.

Item 2. In the formula (A-1) and the formula (A-2) described in item 1,
P ¹⁰ is independently formula (Q-1);
In formula (Q-1),
M ¹⁰ is independently hydrogen, fluorine, methyl, or trifluoromethyl;
M ²⁰ and M ³⁰ are hydrogen;
Sp ¹⁰ and Sp ¹¹ are independently a single bond or alkylene having 2 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or formula (Q-6), and one of _-CH 2 -, -O -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or - May be replaced by C≡C-;
In formula (Q-6), M ¹¹ is independently hydrogen, fluorine, methyl, or trifluoromethyl; M ²¹ and M ³¹ are hydrogen;
Sp ⁴¹ is independently a single bond or alkylene having 1 to 12 carbons, at least one hydrogen of this alkylene may be replaced by fluorine, and at least one —CH ₂ — is —O—, May be replaced with -CO-, -COO-, or -OCO-;
In formula (A-1), formula (A-2), formula (B-1) and formula (B-2),
Ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , ring A ⁴⁰ and ring A ⁵⁰ are independently 1,4-cyclohexylene, 1,4-phenylene, 4,4′-biphenylene, naphthalene-2,6. -Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, but adjacent structures are -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-. , -OCO-C [identical to] C-, -CH = CH-, -CF = CF- or -C [identical to] C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl. And in these rings at least one hydrogen may be replaced by fluorine, hydroxy, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons;
In formulas (A-1) and (A-2), Z ¹⁰ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —. _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O-, _{-OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡ C-;
In formula (A-2), Z ¹¹ is —CH═CH—CO— or —CO—CH═CH—;
In the formula (A-1) and the formula (A-2), n ¹⁰ is an integer of 0 to 4;
In formula (B-1) and formula (B-2),
R ²⁰ is hydrogen, fluorine, hydroxy, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Sp ²⁰ and Sp ²¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH ₂ — of this alkylene may be replaced by —O—;
Item ^20. The liquid crystal display device according to item 1, wherein n ²⁰ is an integer of 0 to 3.

Item 3. In the formula (A-1) and the formula (A-2) described in item 1,
P ¹⁰ is independently formula (Q-1);
In formula (Q-1),
M ¹⁰ is independently hydrogen or methyl;
M ²⁰ and M ³⁰ are hydrogen;
Sp ¹⁰ and Sp ¹¹ are independently a single bond or alkylene having 2 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by the formula (Q-6), and at least one —CH. ₂ -, -O -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or -C≡C- May be replaced with;
In formulas (A-1) and (A-2), Z ¹⁰ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —. _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O-, _{-OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡ C-;
In formula (A-2), Z ¹¹ is —CH═CH—CO— or —CO—CH═CH—;
Ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , ring A ⁴⁰ and ring A ⁵⁰ are independently 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl, or tetrahydronaphthalene-2. , 6-diyl, but the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO-C≡C-, -CH = CH-, In the case of -CF = CF- or -C≡C-, it is 1,4-phenylene or naphthalene-2,6-diyl, and in this 1,4-phenylene, any hydrogen is fluorine, hydroxy or trifluoromethyl. , Alkyl having 1 to 3 carbons, or alkoxy having 1 to 3 carbons;
In formula (A-1) and formula (A-2), n ¹⁰ is an integer of 0 to 2;
In formula (B-1) and formula (B-2),
R ²⁰ is hydrogen, fluorine, hydroxy, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Sp ²⁰ and Sp ²¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH ₂ — of this alkylene may be replaced by —O—;
n ²⁰ is an integer from 0 to 3,
Item 3. The liquid crystal display device according to item 1 or 2.

Item 4. Any one of Items 1 to 3, wherein the ratio of the orientational monomer that is the first additive is in the range of 0.1 parts by weight to 10 parts by weight when the total amount of the liquid crystal compounds is 100 parts by weight. The liquid crystal display element according to item 1.

式（１）において、Ｒ^１は炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または炭素数２から１２のアルケニルであり；環Ａは、１，４−シクロヘキシレン、１，４−フェニレン、２−フルオロ−１，４−フェニレン、２，３−ジフルオロ−１，４−フェニレン、２，６−ジフルオロ−１，４−フェニレン、ピリミジン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、またはテトラヒドロピラン−２，５−ジイルであり；Ｚ^１は、単結合、エチレン、カルボニルオキシ、−ＣH＝ＣＦ−、−ＣＦ＝ＣＦ−、ジフルオロメチレンオキシ、−ＣH＝ＣＦ−ＣＦ_２Ｏ−または−ＣＦ＝ＣＦ−ＣＦ_２Ｏ−であり；Ｘ^１およびＸ^２は独立して、水素またはフッ素であり；Ｙ^１は、フッ素、塩素、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、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２から１２のアルケニルオキシであり；ａは、１、２、３、または４である。Item 5. Item 5. The liquid crystal display element according to any one of items 1 to 4, which contains at least one compound selected from the group of compounds represented by formula (1) as a first component.

In the formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring A is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane 2,5-diyl or tetrahydropyran-2,5-diyl,; ^{Z 1} is a single bond, ethylene, carbonyloxy, -CH = CF -, - CF = CF-, difluoromethyleneoxy, -CH = _CF-CF 2 O- or -CF = _CF-CF 2 O- and is; ^{X 1} and ^{X 2} are each independently hydrogen or fluorine; ^{Y 1} is fluorine, chlorine, at least one hydrogen Alkyl having 1 to 12 carbons replaced with fluorine or chlorine, alkoxy having 1 to 12 carbons having at least one hydrogen replaced with fluorine or chlorine, or carbon having at least one hydrogen replaced with fluorine or chlorine. Is an alkenyloxy of the number 2 to 12; a is 1, 2, 3, or 4.

式（１−１）から式（１−３９）において、Ｒ^１は、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、または炭素数２から１２のアルケニルである。Item 6. Item 6. The liquid crystal display according to any one of items 1 to 5, containing at least one compound selected from the group of compounds represented by formulas (1-1) to (1-39) as a first component. element.

In the formulas (1-1) to (1-39), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.

Item 7. Item 7. The liquid crystal display device according to item 5 or 6, wherein the ratio of the first component is in the range of 10% by weight to 85% by weight with respect to the total amount of the liquid crystal compounds.

式（２）において、Ｒ^２およびＲ^３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Ｂおよび環Ｃ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^２は、単結合、エチレン、またはカルボニルオキシであり；ｂは、１、２、または３である。Item 8. Item 8. The liquid crystal display device according to any one of items 1 to 7, containing at least one compound selected from the group of compounds represented by formula (2) as the second component.

In the formula (2), R ² and R ³ 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. A substituted alkenyl having 2 to 12 carbons; ring B and ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 - be-difluoro-1,4-phenylene; ^{Z 2} is a single bond, ethylene or carbonyloxy,; b is 1, 2 or 3.

式（２−１）から式（２−１３）において、Ｒ^２およびＲ^３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 9. Item 9. The liquid crystal display according to any one of items 1 to 8, which contains at least one compound selected from the group of compounds represented by formulas (2-1) to (2-13) as a second component. element.

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

Item 10. Item 10. The liquid crystal display element according to item 8 or 9, wherein the ratio of the second component is in the range of 10% by weight to 85% by weight with respect to the total amount of the liquid crystal compounds.

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、または炭素数２から１２のアルケニルオキシであり；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、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルであり；環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^３およびＺ^４は独立して、単結合、エチレン、カルボニルオキシ、またはメチレンオキシであり；ｃは、１、２、または３であり、ｄは、０または１であり；ｃとｄとの和は３以下である。Item 11. Item 11. The liquid crystal display device according to any one of items 1 to 10, containing 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, or alkenyloxy having 2 to 12 carbons. Yes; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen being fluorine or chlorine. 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one Chroman-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; 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 3} and ^{Z 4} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy,; c is 1, 2, or 3,, d is , 0 or 1; the sum of c and d is 3 or less.

式（３−１）から式（３−２２）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、または炭素数２から１２のアルケニルオキシである。Item 12. Item 12. The liquid crystal display according to any one of items 1 to 11, containing at least one compound selected from the group of compounds represented by formulas (3-1) to (3-22) as a third component. element.

In formulas (3-1) to (3-22), 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, or It is an alkenyloxy having 2 to 12 carbon atoms.

Item 13. Item 13. The liquid crystal display element according to item 11 or 12, wherein the ratio of the third component is in the range of 3% by weight to 25% by weight with respect to the total amount of the liquid crystal compounds.

式（４）において、環Ｆ^３および環Ｉ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Ｇは、１，４−シクロヘキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、ナフタレン−１，２−ジイル、ナフタレン−１，３−ジイル、ナフタレン−１，４−ジイル、ナフタレン−１，５−ジイル、ナフタレン−１，６−ジイル、ナフタレン−１，７−ジイル、ナフタレン−１，８−ジイル、ナフタレン−２，３−ジイル、ナフタレン−２，６−ジイル、ナフタレン−２，７−ジイル、テトラヒドロピラン−２，５−ジイル、１，３−ジオキサン−２，５−ジイル、ピリミジン−２，５−ジイル、またはピリジン−２，５−ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ^６およびＺ^７は独立して、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＣＯＯ−、または−ＯＣＯ−で置き換えられてもよく、そして少なくとも１つの−ＣＨ_２ＣＨ_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、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、そして少なくとも１つの−ＣＨ_２ＣＨ_２−は、−ＣＨ＝ＣＨ−または−Ｃ≡Ｃ−で置き換えられてもよく、これらの基において、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；ｈは０、１、または２であり；ｅ、ｆ、およびｇは独立して、０、１、２、３、または４であり、そしてｅ、ｆ、およびｇの和は、１以上である。Item 14. Item 14. The liquid crystal display element according to any one of items 1 to 13, further containing at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive.

In formula (4), ring F ³ and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-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. May be replaced by an alkyl having 1 to 12 carbons which is replaced by fluorine or chlorine; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1. , 2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1 , 6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2, 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is fluorine, chlorine, It may be replaced by alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine; Z ⁶ and Z ⁷ are independent. A single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, -COO-, or may be replaced by -OCO-, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3 ) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P 1, ^{P 2} , And P ³ are polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently a single bond or an alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH ₂ — is, -O -, - COO -, - OCO-, or it may be replaced by -OCOO-, and at least one _-CH 2 CH ₂ - is replaced by -CH = CH- or -C≡C- Being Also, in these groups, at least one hydrogen may be replaced by fluorine or chlorine; h is 0, 1, or 2; e, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 1 or more.

式（Ｐ−１）から式（Ｐ−５）において、Ｍ^１、Ｍ^２、およびＭ^３は独立して、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。Item 15. In the formula (4), P ¹ , P ² , and P ³ are independently a group selected from the group of polymerizable groups represented by the formula (P-1) to the formula (P-5). 14. The liquid crystal display element according to 14.

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. Is an alkyl having 1 to 5 carbon atoms replaced by.

式（４−１）から式（４−２７）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_２ＣＨ_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 16. Item 16. The method according to any one of Items 1 to 15, containing at least one compound selected from the group of polymerizable compounds represented by Formula (4-1) to Formula (4-27) as the second additive. Liquid crystal display element.

In formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ⁶ are independently a polymerizable group represented by formulas (P-1) to (P-3). Is a group selected from the group,

Where 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 independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, -OCO-, or -OCOO- in may be replaced, at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least One hydrogen may be replaced by fluorine or chlorine.

Item 17. Item 17. The liquid crystal according to any one of items 14 to 16, wherein the ratio of the second additive is in the range of 0.03 parts by weight to 10 parts by weight when the total amount of the liquid crystal compounds is 100 parts by weight. Display element.

Item 18. The maximum temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2 18. The liquid crystal display device according to any one of items 1 to 17 above.

Item 19. The liquid crystal composition in the liquid crystal display element according to any one of items 1 to 18 and an electrode are provided between a pair of substrates, and by irradiating linearly polarized light, the liquid crystal composition in the liquid crystal composition A liquid crystal display device in which one additive has reacted.

Item 20. Item 20. The liquid crystal display element according to item 19, 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.

Item 21. Item 20. The liquid crystal display element according to item 19, wherein an operation mode of the liquid crystal display element is an IPS mode or an FFS mode, and a driving method of the liquid crystal display element is an active matrix method.

Item 22. Item 18. A polymer-supported alignment type liquid crystal display device containing the liquid crystal composition in the liquid crystal display device according to any one of items 14 to 17, and polymerizing the polymerizable compound in the liquid crystal composition.

Item 23. Item 18. Use of the liquid crystal composition in the liquid crystal display device according to any one of items 1 to 17 in a liquid crystal display device.

Item 24. Item 18. Use of the liquid crystal composition in the liquid crystal display device according to any one of items 1 to 17 in a polymer-supported alignment type liquid crystal display device.

Item 25. 4. Alignment control of compounds represented by formula (A-1), formula (A-2), formula (B-1) and formula (B-2) in the liquid crystal display device according to any one of items 1 to 3. Use as a monomer for forming a layer.

Item 26. Item 18. The liquid crystal composition in the liquid crystal display device according to any one of items 1 to 17.

  The present invention also includes the following items. (A) The above composition further containing at least one 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. object. (B) An AM device containing the above composition. (C) A polymer-supported alignment (PSA) type AM device containing the above composition further containing a polymerizable compound. (D) A polymer-supported alignment (PSA) type AM device containing the above composition, in which 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 element 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 aligning monomer having a cinnamate group or a chalcone group and a hydroxyl group, which is contained in the liquid crystal composition used in the liquid crystal display element of the present invention, will be described. This compound is the first additive. This compound absorbs ultraviolet rays and causes reactions such as dimerization and isomerization and a polymerization reaction. In the present invention, the compounds of formula (A-1), formula (A-2), formula (B-1) and formula (B-1) It is represented by (B-2).

式（Ａ−１）および式（Ａ−２）において、Ｐ^１０は独立して、式（Ｑ−１）から式（Ｑ−５）で表される基から選択された基であり；
式（Ｑ−１）から式（Ｑ−５）において、Ｍ^１０、Ｍ^２０、およびＭ^３０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；
式（Ａ−１）および式（Ａ−２）において、
Ｓｐ^１０およびＳｐ^１１は独立して、単結合または炭素数１から１２のアルキレンであり、このアルキレンの少なくとも１つの水素はフッ素、塩素または式（Ｑ−６）で置き換えられていてもよく、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−または−Ｃ≡Ｃ−で置き換えられてもよく；

In formulas (A-1) and (A-2), P ¹⁰ is independently a group selected from the groups represented by formulas (Q-1) to (Q-5);
In formulas (Q-1) to (Q-5), M ¹⁰ , M ²⁰ , and M ³⁰ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine. An alkyl having 1 to 5 carbons replaced by
In formula (A-1) and formula (A-2),
Sp ¹⁰ and Sp ¹¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or formula (Q-6), and at least one of _-CH 2 -, -O -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or - May be replaced by C≡C-;

式（Ｑ−６）において、Ｍ^１１、Ｍ^２１、およびＭ^３１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^４１は独立して、単結合または炭素数１から１２のアルキレンであり、このアルキレンの少なくとも１つの水素はフッ素または塩素で置き換えられていてもよく、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；
式（Ａ−１）、式（Ａ−２）、式（Ｂ−１）および式（Ｂ−２）において、
環Ａ^１０、環Ａ^２０、環Ａ^３０、環Ａ^４０および環Ａ^５０は独立して、１，４−シクロへキシレン、１，４−シクロヘキセニレン、１，４−フェニレン、４，４’−ビフェニレン、ナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイル、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル、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、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−ジイル、ペルヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイル、または２，３，４，７，８，９，１０，１１，１２，１３，１４，１５，１６，１７−テトラデカヒドロシクロペンタ［ａ］フェナントレン−３，１７−ジイルであるが、隣接する構造が−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−の場合は、１，４−フェニレン、４，４’−ビフェニレン、ナフタレン−２，６−ジイル、ピリミジン−２，５−ジイル、ピリジン−２，５−ジイル、フルオレン−２，７−ジイル、フェナントレン−２，７−ジイル、アントラセン−２，６−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、ヒドロキシ、塩素、炭素数１から１２のアルキル、炭素数２から１２のアルケニル、炭素数１から１１のアルコキシ、または炭素数２から１１のアルケニルオキシ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；
式（Ａ−１）および式（Ａ−２）において、Ｚ^１０は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
式（Ａ−２）において、Ｚ^１１は−ＣＨ＝ＣＨ−ＣＯ−または−ＣＯ−ＣＨ＝ＣＨ−であり；
式（Ａ−１）および式（Ａ−２）において、ｎ^１０は０から４の整数であり；
式（Ｂ−１）および式（Ｂ−２）において、
Ｒ^２０は水素、フッ素、塩素、ヒドロキシ、シアノ、ニトロ、トリフルオロメチル、炭素数１から１０のアルキルまたは炭素数１から１０のアルコキシであり；
Ｓｐ^２０およびＳｐ^２１は独立して単結合または炭素数１から１２のアルキレンであり、このアルキレンの少なくとも１つの水素はフッ素で置き換えられていてもよく、少なくとも１つの−ＣＨ_２−は、−Ｏ−、−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−または−Ｃ≡Ｃ−で置き換えられてもよく；
Ｚ^２０は独立して、単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ_２ＣＨ_２−、−ＣＨ_２ＣＨ_２−ＣＯＯ−、−Ｃ≡Ｃ−ＣＯＯ−、−ＯＣＯ−Ｃ≡Ｃ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＯＮＨ−、−ＮＨＣＯ−、−（ＣＨ_２）_４−、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−または−Ｃ≡Ｃ−であり；
ｎ^２０は０から３の整数である。

In formula (Q-6), M ¹¹ , M ²¹ , and M ³¹ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine. To 5 alkyls;
Sp ⁴¹ is independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine or chlorine, and at least one —CH ₂ — is —O. -, -CO-, -COO-, or -OCO- may be substituted;
In formula (A-1), formula (A-2), formula (B-1) and formula (B-2),
Ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , ring A ⁴⁰ and ring A ⁵⁰ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 4,4 ′. -Biphenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3 -Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, per Hydrocyclopenta [a] phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclo And the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO-C≡C-. , -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl. , Pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, in which at least one hydrogen is fluorine, hydroxy, It may be replaced by chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons. There are, at least one hydrogen may be replaced by fluorine or chlorine;
In formulas (A-1) and (A-2), Z ¹⁰ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —. _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O-, _{-OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡ C-;
In formula (A-2), Z ¹¹ is —CH═CH—CO— or —CO—CH═CH—;
In the formula (A-1) and the formula (A-2), n ¹⁰ is an integer of 0 to 4;
In formula (B-1) and formula (B-2),
R ²⁰ is hydrogen, fluorine, chlorine, hydroxy, cyano, nitro, trifluoromethyl, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons;
Sp ²⁰ and Sp ²¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, and at least one —CH ₂ — is —O. -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-;
Z ²⁰ is independently a single bond, -COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - ( _{CH 2) 4 -, - CH} 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or a -C≡C-;
n ²⁰ is an integer of 0 to 3.

The orientational monomer having a cinnamate group or chalcone group and a hydroxyl group, which is the first additive, undergoes photoisomerization from a trans form to a cis form and formation of a cyclobutane ring by dimerization when irradiated with ultraviolet rays. Further, it is considered that the first additive is easily adsorbed on the substrate interface side due to the interaction between the hydroxyl group and the substrate interface. Further, since it has a polymerizable group, it is immobilized by polymerization. Utilizing this property, a thin film capable of aligning liquid crystal molecules can be prepared. In order to prepare this thin film, linearly polarized light is suitable for the ultraviolet rays to be irradiated. First, the first additive is added to the liquid crystal composition in the range of 0.1 to 10 parts by weight, when the total amount of the liquid crystal compounds is 100 parts by weight, which is the first additive. The composition is warmed to dissolve. This composition is injected into a device having no alignment film. Next, while heating the device, the thin film made of the first additive adsorbed on the substrate interface side is irradiated with linearly polarized light to promote photoisomerization and dimerization. The photoisomerized compound and the dimerized compound are arranged in a certain direction. At the same time, photopolymerization also occurs and the thin film is immobilized on the substrate. The formed thin film has a function as a liquid crystal alignment film.

  The composition used in 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 compositions and devices will be explained. Thirdly, the combination of components in the composition, the preferable ratio of the components and the basis thereof will be described. Fourthly, the preferred forms of the component compounds will be described. Fifth, preferable component compounds are shown. Sixth, the additives that may be added to the composition will be described. Seventh, the method of synthesizing the component compounds will be explained. Eighth, the use of the composition will be explained. Ninth, the method of manufacturing the device 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 are optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into composition A and composition B from the viewpoint of the liquid crystal compound. The composition A may further contain other liquid crystal compound in addition to the liquid crystal compound selected from the compound (1) and the compound (2). The "other liquid crystal compound" is a liquid crystal compound different from the compound (1) and the compound (2). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

  The composition B consists essentially of a liquid crystal compound selected from the compound (1) and the compound (2). The term “substantially” means that the composition may contain an additive, but contains no other liquid crystal compound. Composition B has fewer components than composition A. From the viewpoint of cost reduction, 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 compositions and devices 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 medium, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison among the component compounds, and the symbol 0 (zero) means that the dielectric anisotropy is extremely small.

  The main effects of the component compounds on the properties of the composition when the component compounds are mixed with the composition are as follows. An orienting monomer having a cinnamate group or chalcone group and a hydroxyl group is the first additive. This compound is oriented in a certain direction at the molecular level when it undergoes dimerization, isomerization and polymerization by polarized light. Therefore, the thin film formed from the first additive aligns the liquid crystal molecules similarly to the alignment film such as polyimide. The compound (1) as the first component increases the dielectric anisotropy. The compound (2) as the second component lowers the viscosity or raises the maximum temperature. The third component, compound (3), increases the dielectric constant in the minor axis direction. The second additive, compound (4), gives a polymer by polymerization, which reduces the response time of the device and improves image sticking.

  Thirdly, the combination of components in the composition, the preferable ratio of the components and the basis thereof will be described. The preferred combination of the components in the composition is the first component + additive, the first component + second component + additive, the first component + third component + additive, or the first component + second component + third component. + Additive. A more preferable combination is the first component + second component + additive.

  The preferred ratio of the first additive is about 0.1 part by weight or more when the total amount of the liquid crystal compounds is 100 parts by weight for aligning the liquid crystal molecules, and about 1 part by weight for preventing display failure of the device. It is 10 parts by weight or less. A more desirable ratio is in the range of approximately 0.3 part by weight to approximately 6 parts by weight. A particularly desirable ratio is in the range of approximately 0.5 part by weight to approximately 4 parts by weight.

  The preferable ratio of the first component is about 10% by weight or more based on the total amount of the liquid crystal compound in order to increase the dielectric anisotropy, and about 1% to decrease the minimum temperature or the viscosity. It is 85% by weight or less. A more desirable ratio is in the range of approximately 15% by weight to approximately 80% by weight. A particularly desirable ratio is in the range of approximately 20% by weight to approximately 75% by weight.

  The preferable ratio of the second component is about 10% by weight or more with respect to the total amount of the liquid crystal compounds in order to increase the maximum temperature or to decrease the viscosity, and to increase the dielectric anisotropy. It is 85% by weight or less. A more desirable ratio is in the range of approximately 15% by weight to approximately 80% by weight. A particularly desirable ratio is in the range of approximately 20% by weight to approximately 75% by weight.

  A desirable ratio of the third component is about 3% by weight or more based on the total amount of the liquid crystal compounds in order to increase the dielectric constant in the minor axis direction, and about 25% by weight or less to decrease the minimum temperature. . 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.

  The second additive may be added to the composition for the purpose of adapting to a polymer-supported orientation type device. The preferable ratio of this additive is about 0.03 parts by weight or more when the total amount of the liquid crystal compounds is 100 parts by weight for aligning the liquid crystal molecules, and about 10 parts by weight for preventing display failure of the device. It is less than or equal to parts by weight. A more desirable ratio is in the range of approximately 0.1 part by weight to approximately 2 parts by weight. A particularly desirable ratio is in the range of approximately 0.2 part by weight to approximately 1.0 part by weight.

Fourthly, the preferred forms of the component compounds will be described. In Formula (1), Formula (2), and Formula (3), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons. Desirable R ¹ is alkyl having 1 to 12 carbons for increasing the stability to ultraviolet rays or heat. R ² and R ³ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or 2 carbons in which at least one hydrogen is replaced by fluorine or chlorine. To 12 alkenyl. Preferred R ² or R ³ is alkenyl having 2 to 12 carbons for decreasing the viscosity and alkyl having 1 to 12 carbons for increasing the stability to ultraviolet rays or heat. 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, or alkenyloxy having 2 to 12 carbons. Desirable R ⁴ or R ⁵ is alkyl having 1 to 12 carbons for increasing stability to ultraviolet rays or heat, and alkoxy for having 1 to 12 carbons for increasing dielectric constant in the minor axis direction.

  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, It is 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 the alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for decreasing the viscosity. Cis is preferable in the alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl. Of these alkenyls, linear alkenyls are preferred to branched ones.

  Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More desirable 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 include fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl. , Or 8-fluorooctyl. A more preferable example is 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl for increasing the dielectric anisotropy.

  Preferred examples of alkenyl in which at least one hydrogen has been 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. A more preferred example is 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。
環Ｂおよび環Ｃ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−フェニレンである。好ましい環Ｂまたは環Ｃは、粘度を下げるために１，４−シクロヘキシレンであり、または光学異方性を上げるために１，４−フェニレンである。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、テトラヒドロピラン−２，５−ジイル、１，４−フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４−フェニレン、ナフタレン−２，６−ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン−２，６−ジイル、クロマン−２，６−ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン−２，６−ジイルである。
好ましい環Ｄまたは環Ｆは、粘度を下げるために１，４−シクロヘキシレンであり、短軸方向における誘電率を上げるためにテトラヒドロピラン−２，５−ジイルであり、光学異方性を上げるために１，４−フェニレンである。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−ジイルである。好ましい環Ｅは、短軸方向における誘電率を上げるために２，３−ジフルオロ−１，４−フェニレンである。Ring A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene. , Pyrimidine-2,5-diyl, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl. Preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene for increasing the optical anisotropy. Tetrahydropyran-2,5-diyl is

Or

And preferably

Is.
Ring B and ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring B or ring C is 1,4-cyclohexylene for decreasing the viscosity, or 1,4-phenylene for increasing the optical anisotropy. Ring D and ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen being replaced by fluorine or chlorine. 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is Chroman-2,6-diyl substituted with fluorine or chlorine.
Preferred ring D or ring F is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric constant in the minor axis direction, and for increasing the optical anisotropy. It is 1,4-phenylene. 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. It is 5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl. Preferred ring E is 2,3-difluoro-1,4-phenylene for increasing the dielectric constant in the minor axis direction.

Z ¹ is a single bond, ethylene, carbonyloxy, -CH = CF -, - CF = CF-, difluoromethyleneoxy, -CH = _CF-CF 2 O- or -CF = _CF-CF 2 is O-. Preferred Z ¹ is a single bond for decreasing the viscosity, and difluoromethyleneoxy for increasing the dielectric anisotropy. Z ² is a single bond, ethylene, or carbonyloxy. Preferred Z ² is a single bond for decreasing the viscosity. Z ³ and Z ⁴ are independently a single bond, ethylene, carbonyloxy, or methyleneoxy. Preferred Z ³ or Z ⁴ is a single bond for decreasing the viscosity, and methyleneoxy for increasing the dielectric constant in the minor axis direction.

X ¹ and X ² are independently hydrogen or fluorine. Preferred X ¹ or X ² is fluorine for increasing the dielectric anisotropy.

Y ¹ is fluorine, chlorine, alkyl having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, alkoxy having 1 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine, or at least Alkenyloxy having 2 to 12 carbons in which one hydrogen is replaced by fluorine or chlorine. Preferred Y ¹ is fluorine for decreasing the minimum temperature.

A preferred example of alkyl in which at least one hydrogen has been replaced by fluorine or chlorine is trifluoromethyl. A preferred example of alkoxy in which at least one hydrogen has been replaced by fluorine or chlorine is trifluoromethoxy. A preferred example of alkenyloxy in which at least one hydrogen has been replaced with fluorine or chlorine is trifluorovinyloxy.

  a is 1, 2, 3, or 4. Preferred a is 2 for lowering the minimum temperature and 3 for increasing the dielectric anisotropy. b is 1, 2, or 3. Preferred b is 1 for decreasing the viscosity and 2 or 3 for increasing the maximum temperature. 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.

In Formula (4), P ¹ , P ² , and P ³ are independently a polymerizable group. Preferred P ¹ , P ² , or P ³ is a polymerizable group selected from the group of groups represented by formula (P-1) to formula (P-5). More desirable 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 formula (P-1) or formula (P-2). Most preferred P ¹ , P ² , or P ³ is a group represented by formula (P-1). Preferred groups represented by the formula (P-1) is, -OCO-CH = CH ₂ or _{-OCO-C (CH} 3) a = CH _2. The wavy line in the formulas (P-1) to (P-5) indicates the binding site.

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. Is an alkyl having 1 to 5 carbon atoms replaced by. 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 independently a single bond or an 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 by fluorine or chlorine. Preferred ^Sp 1, Sp ² or Sp ^3, is a single _{bond, -CH 2 -CH 2 -, -} CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CO-CH = CH-, Alternatively, -CH = CH-CO-. More desirable Sp ¹ , Sp ² , or Sp ³ is a single bond.

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

Z ⁶ and Z ⁷ are independently a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, 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 by fluorine or chlorine. Preferred Z ⁶ or Z ⁷ is a single bond, —CH ₂ —CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, or —OCO—. More desirable Z ⁶ or Z ⁷ is a single bond.

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

  Fifth, preferable component compounds are shown. The orienting monomer which is a preferable first additive will be described. The oriented monomer preferably has at least one polymerizable group and at least one hydroxyl group. A thin film (polymer) obtained by polymerizing an orienting monomer having one polymerizable group and at least one hydroxyl group is flexible, but since it has an intermolecular force between the hydroxyl group and the substrate, It is considered that there is little deformation in the temperature environment in which the liquid crystal display element is driven. Therefore, the effect of maintaining the orientation control force is expected. In the case of an aligning monomer having two or more polymerizable groups and at least one hydroxyl group, it is considered that the cross-linking density of the thin film obtained after the polymerization increases and a strong film is formed, so that the orientation control power is obtained even in a high temperature environment. Expected to be maintained. The site that causes dimerization or isomerization due to polarized light is a part having a chalcone structure or a cinnamate structure. Similar effects can be expected even when a plurality of molecules are contained in the molecule. In order to control the solubility in the liquid crystal compound, a spacer may be introduced between the polymerizable group and the cyclic structure in order to increase the compatibility with the terminal chain of the liquid crystal compound. The spacer is preferably linear or branched. The length of the spacer is preferably 2 or more carbon atoms. The orienting monomers may be used alone or in combination of two or more. Specific examples of preferred orienting monomers are given below.

  Preferred first additives are compound (A-1-1) to compound (A-1-9) and compound (B-1-1) to compound (B-1-8). N and m in these compounds are independently 2 to 6.

  Preferred compound (1) includes compounds (1-1) to (1-39) according to item 6. In these compounds, at least one of the first components is compound (1-4), compound (1-12), compound (1-14), compound (1-15), compound (1-17), compound ( 1-18), compound (1-23), compound (1-24), compound (1-27), compound (1-29), or compound (1-30) is preferable. At least two of the first components are compound (1-12) and compound (1-15), compound (1-14) and compound (1-27), compound (1-18) and compound (1-24), The compound (1-18) and the compound (1-29), the compound (1-24) and the compound (1-29), or the combination of the compound (1-29) and the compound (1-30) is preferable.

Preferred compound (2) is the compound (2-1) to the compound (2-13) according to item 9. In these compounds, at least one of the second components is compound (2-1), compound (2-3), compound (2-5), compound (2-6), or compound (2-7). It is preferable. At least two of the second components are compound (2-1) and compound (2-5), compound (2-1) and compound (2-6), compound (2-1) and compound (2-7), compound. A combination of (2-3) and compound (2-5), compound (2-3) and compound (2-6), compound (2-3) and compound (2-7) is preferable.

Preferred compound (3) includes compounds (3-1) to (3-22) according to item 12. In these compounds, at least one of the third components is compound (3-1), compound (3-3), compound (3-4), compound (3-6), compound (3-8), or compound. It is preferably (3-10). At least two of the third components are compound (3-1) and compound (3-6), compound (3-3) and compound (3-6), compound (3-3) and compound (3-10), The compound (3-4) and the compound (3-6), the compound (3-4) and the compound (3-8), or the combination of the compound (3-6) and the compound (3-10) is preferable.

  Sixth, the additives that may be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, 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 (4-1) to compound (4-5). The preferable ratio of the optically active compound is about 5 parts by weight or less, when the total amount of the liquid crystal compounds is 100 parts by weight. A more desirable ratio is in the range of approximately 0.01 parts by weight to approximately 2 parts by weight.

In order to prevent a decrease in the specific resistance due to heating in the air, or to maintain a large voltage holding ratio not only at room temperature but also at a temperature near the upper limit temperature after using the device for a long time, an antioxidant composition is used. Is added to the product. Preferred examples of the antioxidant include compound (5) in which n is an integer of 1 to 9 and the like.

  In compound (5), preferred n is 1, 3, 5, 7, or 9. More desirable n is 7. Since the compound (5) in which n is 7 has low volatility, it is effective in 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 is used for a long time. A preferable ratio of the antioxidant is about 50 ppm or more in order to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or the lower limit temperature. A more desirable ratio is in the range of approximately 100 ppm to approximately 300 ppm.

  Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. A desirable ratio of these absorbents and stabilizers is about 50 ppm or more for obtaining the effect, and about 10,000 ppm or less for not lowering the upper limit temperature or for not raising the lower limit 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, anthraquinone dye or the like is added to the composition in order to adapt to a GH (guest host) mode device. The preferred proportion of dye is in the range of about 0.01 to about 10 parts by weight. An antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is added to the composition to prevent foaming. The preferable ratio of the defoaming agent is about 1 ppm or more to obtain the effect, and about 1000 ppm or less to prevent display defects. A more desirable ratio is in the range of approximately 1 ppm to approximately 500 ppm.

  Polymerizable compounds are used to adapt to polymer-supported orientation (PSA) type devices. Compound (4) is suitable for this purpose. A polymerizable compound different from compound (4) may be added to the composition together with compound (4). Instead of the compound (4), a polymerizable compound different from the compound (4) may be added to the composition. Preferred 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. The reactivity of the polymerizable compound and the pretilt angle of the liquid crystal molecule can be adjusted by changing the type of the compound (4) or by combining the polymerizable compound different from the compound (4) in an appropriate ratio. . By optimizing the pretilt angle, a short response time of the device can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast ratio and a long life can be achieved.

  A polymerizable compound such as the compound (4) is polymerized by irradiation with ultraviolet rays. The polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and are described in the literature. For example, the photopolymerization initiator Omnirad651 (registered trademark; IGM Resins), Omnirad184 (registered trademark; IGM Resins), or Omnirad1173 (registered trademark; IGM Resins) is suitable for radical polymerization. The preferred ratio of the photopolymerization initiator is in the range of about 0.1 part by weight to about 5 parts by weight based on the total amount of the polymerizable compound. A more desirable ratio is in the range of approximately 1 part by weight to approximately 3 parts by weight.

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

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

  Seventh, the method of synthesizing the component compounds will be explained. These compounds can be synthesized by known methods. A synthetic method is illustrated. The compound (1-1) is synthesized by the method described in Japanese Patent Publication No. 2-503441. The compound (2-5) is synthesized by the method described in JP-A-57-165328. The compound (3-18) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compounds of formula (5) where n is 1 are available from Sigma-Aldrich Corporation. The compound (5) in which n is 7 and the like are synthesized by the method described in US Pat. No. 3,660,505. The compound having a cinnamate group or a chalcone group, a hydroxyl group and a polymerizable group as the first additive is synthesized by the method described in JP2012-87286A and JP2012-107198A. The polymerizable compound having an α-fluoroacrylate group is synthesized with reference to the method described in JP-A-2005-112850.

  Compounds for which no synthetic method is described include Organic Synthesis (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Organic Reactions, John Wiley & Sons, Inc.) Comprehensive Organic Synthesis, Pergamon Press), New Experimental Chemistry Course (Maruzen), etc. The composition is prepared from the compounds thus obtained by known methods. For example, the component compounds are mixed and dissolved by heating.

  Eighth, the use of the composition will be explained. 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 component compounds or by mixing with other liquid crystal compounds. Furthermore, compositions having optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by this method. 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 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 a PM element. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA and FPA. The use for AM devices having 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 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 and a PD (polymer dispersed) type device in which a three-dimensional network polymer is formed in the composition.

Ninth, the method of manufacturing the device will be described. The first is a step of adding the first additive to the liquid crystal composition and heating the composition at a temperature higher than the upper limit temperature to dissolve the composition. The second is a step of injecting this composition into a liquid crystal display device. In this step, when the liquid crystal composition is heated and injected at a temperature higher than the upper limit temperature, the shear stress when the liquid crystal composition flows in the cell can be reduced, and the occurrence of alignment defects can be easily prevented. . The third is a step of irradiating polarized ultraviolet rays while the liquid crystal composition is heated to a temperature higher than the upper limit temperature. The first additive is dimerized or isomerized by linearly polarized light, and at the same time, the polymerization proceeds. Linearly polarized UV preferred integrated light quantity (J / cm ²⁾ is 0.1~20J / cm ² at the time of element surface reaches. A preferable range of the integrated light amount is 0.1 to 10 J / cm ² , and a more preferable range is 0.1 to 7 J / cm ² . The integrated light amount (J / cm ² ) can be calculated by the illuminance of ultraviolet rays (unit: mW / cm ² ) × irradiation time (unit: sec). It is preferable that the temperature condition at the time of irradiation of linearly polarized ultraviolet rays is set in the same manner as the heat treatment temperature. The irradiation time of the linearly polarized ultraviolet light is calculated from the illuminance of the lamp, and therefore it is preferable to perform the irradiation time as high as possible from the viewpoint of production efficiency. The polymer composed of the first additive is formed as a thin film on the substrate and immobilized. Since this polymer is arranged in a certain direction at the molecular level, the thin film has a function as a liquid crystal alignment film. By this method, a liquid crystal display element having no alignment film such as polyimide can be manufactured.

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

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

  Gas chromatographic analysis: A Shimadzu GC-14B gas chromatograph was used for the 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. A capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase dimethylpolysiloxane; nonpolar) manufactured by Agilent Technologies Inc. was used to separate the component compounds. The column was held at 200 ° C. for 2 minutes and then heated to 280 ° C. at a rate of 5 ° C./minute. 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 Shimadzu model C-R5A Chromatopac or its equivalent. The obtained gas chromatogram showed the retention time of peaks and the area of peaks corresponding to the component compounds.

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

  The ratio of the liquid crystal compound contained in the composition may be calculated by the following method. The mixture of liquid crystal compounds is detected by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystal compound. When the above-described capillary column 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 the characteristics of the composition and the device were measured, the composition was directly used as a sample. When measuring the characteristics of a compound, a sample for measurement was prepared by mixing this compound (15% by weight) with a mother liquid crystal (85% by weight). The characteristic value of the compound was calculated by extrapolation from the value obtained by the measurement. (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. in 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. Values of the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were obtained by this extrapolation method.

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 methods. Most of these are the methods described in the JEITA standard (JEITA / ED-2521B), which is deliberated and established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA), or modifications thereof. Was the way. No thin film transistor (TFT) was attached to the TN device used for the measurement.

(1) Maximum temperature of the nematic phase (NI; ° C): The sample was placed on a hot plate of a melting point measuring device equipped with a polarization 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 maximum temperature of the nematic phase may be abbreviated as “maximum 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 , T _C 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 rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for measurement.

(4) Viscosity (rotary viscosity; γ1; measured at 25 ° C .; mPa · s): The measurement is performed by the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). I obeyed. The sample was put in a TN device having a twist angle of 0 ° and a distance (cell gap) between two glass substrates of 5 μm. A voltage of 16V to 19.5V was applied to the device in steps of 0.5V. After 0.2 seconds of non-application, application was repeated under the conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and no application (2 seconds). The peak current and the peak time of the transient current generated by this application were measured. The value of rotational viscosity was obtained from these measured values and the calculation formula (8) described on page 40 in the paper by M. Imai et al. The value of the dielectric anisotropy necessary for this calculation was measured in the item (6) using the device whose rotational viscosity was measured.

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

(6) Dielectric anisotropy (Δε; measured at 25 ° C.): A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 μm and a twist angle was 80 degrees. A sine wave (10 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε∥) of the liquid crystal molecule in the major axis direction was measured. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds, the dielectric constant (ε⊥) in the short axis direction of the liquid crystal molecule was measured. The value of the dielectric anisotropy was calculated from the formula Δε = ε∥−ε⊥.

(7) Threshold voltage (Vth; measured at 25 ° C .; V): LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The sample was put in a normally white mode TN device in which the distance (cell gap) between the two glass substrates was 0.45 / Δn (μm) and the twist angle was 80 degrees. The voltage (32 Hz, rectangular wave) applied to this element was increased stepwise from 0 V to 10 V by 0.02 V. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve in which the transmittance is 100% when the light amount is maximum and the transmittance is 0% when the light amount is minimum was created. The threshold voltage is represented by the voltage when the transmittance reaches 90%.

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

(9) Voltage holding ratio (VHR-2; measured at 80 ° C .;%): The voltage holding ratio was measured by 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 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 device and irradiated with light for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Inc.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, the voltage that decays for 16.7 milliseconds was measured. A composition having a large VHR-3 has great stability to ultraviolet rays. 90% or more is preferable and 95% or more of VHR-3 is more preferable.

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

(12) Response time (τ; measured at 25 ° C .; ms): Measurement was carried out with LCD Evaluation System Model LCD-5100 made by Otsuka Electronics Co., Ltd. The light source was a halogen lamp. The low-pass filter (Low-pass filter) was set to 5 kHz. The sample was put in a normally white mode TN device in which the distance (cell gap) between the two glass substrates was 5.0 μm and the twist angle was 80 degrees. A rectangular wave (60 Hz, 5 V, 0.5 seconds) was applied to this device. At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the light amount was maximum, and the transmittance was 0% when the light amount was minimum. The rise time (τr: rise time; millisecond) is the time required for the transmittance to change from 90% to 10%. The fall time (τf: fall time; millisecond) is the time required to change the transmittance from 10% to 90%. The response time was represented by the sum of the rise time and the fall time thus obtained.

(13) Elastic constant (K; measured at 25 ° C .; pN): An HP4284A LCR meter manufactured by Yokogawa-Hewlett Packard Co. was used for measurement. The sample was placed in a horizontal alignment device in which the distance (cell gap) between two glass substrates was 20 μm. An electric charge of 0 V to 20 V was applied to this device, and the electrostatic capacity and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) values using the formula (2.98) and formula (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). Then, the values of K11 and K33 were obtained from the formula (2.99). Next, K22 was calculated by using the values of K11 and K33 obtained earlier in the equation (3.18) on page 171. The elastic constant was represented by the average value of K11, K22, and K33 thus obtained.

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

(15) Helical pitch (P; measured at room temperature; μm): The helical pitch was measured by the wedge method. See "Liquid Crystal Handbook", page 196 (issued in 2000, Maruzen). The sample was poured into a wedge-shaped cell, allowed to stand at room temperature for 2 hours, and then the distance (d2-d1) between the disclination lines was observed with a polarizing microscope (Nikon Corporation, trade name MM40 / 60 series). The spiral pitch (P) was calculated from the following equation in which the angle of the wedge cell was represented by θ. P = 2 × (d2-d1) × tan θ.

  The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration of 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) means another liquid crystal compound. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the characteristic values of the composition are summarized.

Table 3 compounds using symbols notation _{R- (A 1) -Z 1 -} ····· Z n - (A n) -R '

Example of device 1. Raw Material A composition containing an alignment monomer was injected into an element having no alignment film. After irradiation with linearly polarized light, the alignment of liquid crystal molecules in this device was confirmed. First, the raw materials will be explained. The raw material is a composition such as the orientation monomer and the composition (M1) to the composition (M20). The orientation monomer was appropriately selected from the compounds described below. The composition is as follows.

[Composition (M1)]
3-HHXB (F, F) -F (1-4) 6%
3-BB (F, F) XB (F, F) -F (1-18) 13%
3-HHBB (F, F) -F (1-19) 4%
4-HHBB (F, F) -F (1-19) 5%
3-HBBXB (F, F) -F (1-23) 3%
3-BB (F) B (F, F) XB (F) -F (1-28) 2%
4-BB (F) B (F, F) XB (F, F) -F (1-29) 8%
5-BB (F) B (F, F) XB (F, F) -F (1-29) 7%
3-HH-V (2-1) 44%
V-HHB-1 (2-5) 6%
2-BB (F) B-3 (2-8) 2%
NI = 79.8 ° C .; Tc <−30 ° C .; Δn = 0.106; Δε = 8.5; Vth = 1.45 V; η = 11.6 mPa · s; γ1 = 60.0 mPa · s.

[Composition (M2)]
5-HXB (F, F) -F (1-1) 3%
3-HHXB (F, F) -F (1-4) 3%
3-HHXB (F, F) -CF3 (1-5) 3%
3-HGB (F, F) -F (1-6) 3%
3-HB (F) B (F, F) -F (1-9) 5%
3-BB (F, F) XB (F, F) -F (1-18) 6%
3-HHBB (F, F) -F (1-19) 6%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(1-31) 2%
3-BB (2F, 3F) XB (F, F) -F (1-32) 4%
3-B (2F, 3F) BXB (F, F) -F (1-33) 5%
3-HHB (F, F) XB (F, F) -F (1) 4%
3-HB-CL (1) 3%
3-HHB-OCF3 (1) 3%
3-HH-V (2-1) 22%
3-HH-V1 (2-1) 10%
5-HB-O2 (2-2) 5%
3-HHEH-3 (2-4) 3%
3-HBB-2 (2-6) 7%
5-B (F) BB-3 (2-7) 3%
NI = 71.2 ° C .; Tc <−20 ° C .; Δn = 0.099; Δε = 6.1; Vth = 1.74V; η = 13.2 mPa · s; γ1 = 59.3 mPa · s.

[Composition (M3)]
5-HXB (F, F) -F (1-1) 6%
3-HHXB (F, F) -F (1-4) 6%
V-HB (F) B (F, F) -F (1-9) 5%
3-HHB (F) B (F, F) -F (1-20) 7%
2-BB (F) B (F, F) XB (F) -F (1-28) 3%
3-BB (F) B (F, F) XB (F) -F (1-28) 3%
4-BB (F) B (F, F) XB (F) -F (1-28) 4%
5-HB-CL (1) 5%
2-HH-5 (2-1) 8%
3-HH-V (2-1) 10%
3-HH-V1 (2-1) 7%
4-HH-V (2-1) 10%
4-HH-V1 (2-1) 8%
5-HB-O2 (2-2) 7%
4-HHEH-3 (2-4) 3%
1-BB (F) B-2V (2-8) 3%
1O1-HBBH-3 (-) 5%
NI = 78.5 ° C .; Tc <−20 ° C .; Δn = 0.095; Δε = 3.4; Vth = 1.50 V; η = 8.4 mPa · s; γ1 = 54.2 mPa · s.

[Composition (M4)]
3-HHEB (F, F) -F (1-3) 5%
3-HHXB (F, F) -F (1-4) 7%
5-HBEB (F, F) -F (1-10) 5%
3-BB (F, F) XB (F, F) -F (1-18) 10%
2-HHB (F) B (F, F) -F (1-20) 3%
3-HB (2F, 3F) BXB (F, F) -F (1-34) 3%
3-BB (2F, 3F) BXB (F, F) -F (1-35) 2%
5-HHB (F, F) XB (F, F) -F (1) 6%
2-HH-3 (2-1) 8%
3-HH-V (2-1) 20%
3-HH-V1 (2-1) 7%
4-HH-V (2-1) 6%
5-HB-O2 (2-2) 5%
V2-B2BB-1 (2-9) 3%
3-HHEBH-3 (2-11) 5%
3-HHEBH-5 (2-11) 5%
NI = 90.3 ° C .; Tc <−20 ° C .; Δn = 0.089; Δε = 5.5; Vth = 1.65 V; η = 13.6 mPa · s; γ1 = 60.1 mPa · s.

[Composition (M5)]
3-BB (F, F) XB (F, F) -F (1-18) 12%
3-HHBB (F, F) -F (1-19) 5%
4-HHBB (F, F) -F (1-19) 4%
3-HBBXB (F, F) -F (1-23) 3%
3-BB (F) B (F, F) XB (F) -F (1-28) 3%
3-BB (F) B (F, F) XB (F, F) -F (1-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-29) 5%
5-BB (F) B (F, F) XB (F, F) -F (1-29) 4%
2-HH-3 (2-1) 6%
3-HH-5 (2-1) 6%
3-HH-V (2-1) 25%
3-HH-VFF (2-1) 6%
5-HB-O2 (2-2) 7%
V-HHB-1 (2-5) 6%
V-HBB-2 (2-6) 5%
NI = 78.3 ° C .; Tc <−20 ° C .; Δn = 0.107; Δε = 7.0; Vth = 1.55 V; η = 11.6 mPa · s; γ1 = 55.6 mPa · s.

[Composition (M6)]
3-HHXB (F, F) -F (1-4) 3%
3-BBXB (F, F) -F (1-17) 3%
3-BB (F, F) XB (F, F) -F (1-18) 8%
3-HHBB (F, F) -F (1-19) 5%
4-HHBB (F, F) -F (1-19) 4%
3-BB (F) B (F, F) XB (F, F) -F (1-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-29) 6%
5-BB (F) B (F, F) XB (F, F) -F (1-29) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 5%
3-HHB-O1 (2-5) 2%
V-HHB-1 (2-5) 5%
2-BB (F) B-3 (2-8) 6%
F3-HH-V (-) 15%
NI = 80.4 ° C .; Tc <−20 ° C .; Δn = 0.106; Δε = 5.8; Vth = 1.40 V; η = 11.6 mPa · s; γ1 = 61.0 mPa · s.

[Composition (M7)]
3-HGB (F, F) -F (1-6) 3%
5-GHB (F, F) -F (1-7) 4%
3-GB (F, F) XB (F, F) -F (1-14) 5%
3-BB (F) B (F, F) -CF3 (1-16) 2%
3-HHBB (F, F) -F (1-19) 4%
3-GBB (F) B (F, F) -F (1-22) 2%
2-dhBB (F, F) XB (F, F) -F (1-25) 4%
3-GB (F) B (F, F) XB (F, F) -F (1-27) 3%
3-HGB (F, F) XB (F, F) -F (1) 5%
7-HB (F, F) -F (1) 3%
2-HH-3 (2-1) 14%
2-HH-5 (2-1) 4%
3-HH-V (2-1) 26%
1V2-HH-3 (2-1) 5%
1V2-BB-1 (2-3) 3%
2-BB (F) B-3 (2-8) 3%
3-HB (F) HH-2 (2-10) 4%
5-HBB (F) B-2 (2-13) 6%
NI = 78.4 ° C .; Tc <−20 ° C .; Δn = 0.094; Δε = 5.6; Vth = 1.45 V; η = 11.5 mPa · s; γ1 = 61.7 mPa · s.

[Composition (M8)]
3-HBB (F, F) -F (1-8) 5%
5-HBB (F, F) -F (1-8) 4%
3-BB (F) B (F, F) -F (1-15) 3%
3-BB (F) B (F, F) XB (F, F) -F (1-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-29) 5%
3-BB (F, F) XB (F) B (F, F) -F (1-30) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(1-31) 4%
3-HH2BB (F, F) -F (1) 3%
4-HH2BB (F, F) -F (1) 3%
2-HH-5 (2-1) 8%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 7%
4-HH-V1 (2-1) 6%
5-HB-O2 (2-2) 5%
7-HB-1 (2-2) 5%
VFF-HHB-O1 (2-5) 8%
VFF-HHB-1 (2-5) 3%
NI = 80.0 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 4.6; Vth = 1.71 V; η = 11.0 mPa · s; γ1 = 47.2 mPa · s.

[Composition (M9)]
3-HHB (F, F) -F (1-2) 8%
3-GB (F) B (F) -F (1-11) 2%
3-GB (F) B (F, F) -F (1-12) 3%
3-BB (F, F) XB (F, F) -F (1-18) 8%
3-GB (F) B (F, F) XB (F, F) -F (1-27) 6%
5-GB (F) B (F, F) XB (F, F) -F (1-27) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 10%
1V2-HH-3 (2-1) 8%
3-HH-VFF (2-1) 8%
V2-BB-1 (2-3) 2%
5-HB (F) BH-3 (2-12) 5%
5-HBBH-3 (2) 5%
NI = 78.6 ° C .; Tc <−20 ° C .; Δn = 0.088; Δε = 5.6; Vth = 1.85 V; η = 13.9 mPa · s; γ1 = 66.9 mPa · s.

[Composition (M10)]
3-HHEB (F, F) -F (1-3) 4%
5-HHEB (F, F) -F (1-3) 3%
3-HBEB (F, F) -F (1-10) 3%
5-HBEB (F, F) -F (1-10) 3%
3-BB (F) B (F, F) -F (1-15) 3%
3-GB (F) B (F, F) XB (F, F) -F (1-27) 5%
4-GB (F) B (F, F) XB (F, F) -F (1-27) 5%
5-HB-CL (1) 5%
3-HHB-OCF3 (1) 4%
3-HHB (F, F) XB (F, F) -F (1) 5%
5-HHB (F, F) XB (F, F) -F (1) 3%
3-HGB (F, F) XB (F, F) -F (1) 5%
2-HH-5 (2-1) 3%
3-HH-5 (2-1) 5%
3-HH-V (2-1) 24%
4-HH-V (2-1) 5%
1V2-HH-3 (2-1) 5%
3-HHEH-3 (2-4) 5%
5-B (F) BB-2 (2-7) 3%
5-B (F) BB-3 (2-7) 2%
NI = 82.9 ° C; Tc <-20 ° C; Δn = 0.093; Δε = 6.9; Vth = 1.50V; η = 16.3 mPa · s; γ1 = 65.2 mPa · s.

[Composition (M11)]
3-HHXB (F, F) -F (1-4) 9%
3-HBB (F, F) -F (1-8) 3%
3-BB (F) B (F, F) -F (1-15) 4%
3-BB (F) B (F, F) -CF3 (1-16) 4%
3-BB (F, F) XB (F, F) -F (1-18) 5%
3-GBB (F) B (F, F) -F (1-22) 3%
4-GBB (F) B (F, F) -F (1-22) 4%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 10%
5-HB-O2 (2-2) 10%
7-HB-1 (2-2) 5%
V2-BB-1 (2-3) 3%
3-HHB-1 (2-5) 4%
1V-HBB-2 (2-6) 5%
5-HBB (F) B-2 (2-13) 6%
NI = 79.6 ° C .; Tc <−20 ° C .; Δn = 0.111; Δε = 4.7; Vth = 1.86V; η = 9.7 mPa · s; γ1 = 49.9 mPa · s.

[Composition (M12)]
3-BB (F, F) XB (F, F) -F (1-18) 14%
5-BB (F) B (F, F) XB (F, F) -F (1-29) 7%
7-HB (F, F) -F (1) 6%
2-HH-5 (2-1) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 3%
3-HH-VFF (2-1) 10%
3-HHB-1 (2-5) 4%
3-HHB-3 (2-5) 5%
3-HHB-O1 (2-5) 3%
1-BB (F) B-2V (2-8) 3%
3-HHEBH-3 (2-11) 3%
3-HHEBH-4 (2-11) 4%
3-HHEBH-5 (2-11) 3%
NI = 83.0 ° C .; Tc <−20 ° C .; Δn = 0.086; Δε = 3.8; Vth = 1.94V; η = 7.5 mPa · s; γ1 = 51.5 mPa · s.

[Composition (M13)]
3-HBB (F, F) -F (1-8) 5%
5-HBB (F, F) -F (1-8) 4%
3-BB (F) B (F, F) -F (1-15) 3%
3-BB (F) B (F, F) XB (F, F) -F (1-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-29) 5%
3-BB (F, F) XB (F) B (F, F) -F (1-30) 3%
5-BB (F) B (F, F) XB (F) B (F, F) -F
(1-31) 4%
3-HH2BB (F, F) -F (1) 3%
4-HH2BB (F, F) -F (1) 3%
2-HH-5 (2-1) 8%
3-HH-V (2-1) 28%
4-HH-V1 (2-1) 7%
5-HB-O2 (2-2) 2%
7-HB-1 (2-2) 5%
VFF-HHB-O1 (2-5) 8%
VFF-HHB-1 (2-5) 3%
2-BB (2F, 3F) B-3 (3-9) 4%
3-HBB (2F, 3F) -O2 (3-10) 2%
NI = 81.9 ° C .; Tc <−20 ° C .; Δn = 0.109; Δε = 4.8; Vth = 1.75V; η = 13.3 mPa · s; γ1 = 57.4 mPa · s.

[Composition (M14)]
3-HHEB (F, F) -F (1-3) 4%
3-HBEB (F, F) -F (1-10) 3%
5-HBEB (F, F) -F (1-10) 3%
3-BB (F) B (F, F) -F (1-15) 3%
3-HBBBX (F, F) -F (1-23) 6%
4-GBB (F, F) XB (F, F) -F (1-26) 2%
5-GBB (F, F) XB (F, F) -F (1-26) 2%
3-GB (F) B (F, F) XB (F, F) -F (1-27) 5%
4-GB (F) B (F, F) XB (F, F) -F (1-27) 5%
5-HHB (F, F) XB (F, F) -F (1) 3%
5-HEB (F, F) -F (1) 3%
5-HB-CL (1) 2%
3-HHB-OCF3 (1) 4%
3-HH-5 (2-1) 4%
3-HH-V (2-1) 21%
3-HH-V1 (2-1) 3%
4-HH-V (2-1) 4%
1V2-HH-3 (2-1) 6%
5-B (F) BB-2 (2-7) 3%
5-B (F) BB-3 (2-7) 2%
3-HB (2F, 3F) -O2 (3-1) 3%
3-BB (2F, 3F) -O2 (3-4) 2%
3-HHB (2F, 3F) -O2 (3-6) 4%
F3-HH-V (-) 3%
NI = 78.2 ° C .; Tc <−20 ° C .; Δn = 0.101; Δε = 6.7; Vth = 1.45 V; η = 17.8 mPa · s; γ1 = 67.8 mPa · s.

[Composition (M15)]
3-HHB (F, F) -F (1-2) 10%
3-HHXB (F, F) -F (1-4) 2%
3-GHB (F, F) -F (1-7) 5%
3-BB (F) B (F, F) -F (1-15) 6%
3-BB (F, F) XB (F, F) -F (1-18) 14%
4-BB (F) B (F, F) XB (F, F) -F (1-29) 10%
5-BB (F) B (F, F) XB (F, F) -F (1-29) 6%
2-HH-3 (2-1) 5%
3-HH-4 (2-1) 11%
3-HH-O1 (2-1) 5%
5-HB-O2 (2-2) 8%
3-HHB-1 (2-5) 6%
3-HHB-3 (2-5) 6%
3-HHB-O1 (2-5) 6%
NI = 77.6 ° C .; Tc <−20 ° C .; Δn = 0.109; Δε = 10.6; Vth = 1.34V; η = 22.6 mPa · s; γ1 = 92.4 mPa · s.

[Composition (M16)]
3-HBB-F (1) 3%
3-BB (F, F) XB (F) -OCF3 (1) 3%
3-HHB (F) -F (1) 3%
3-HGB (F, F) -F (1-6) 3%
5-GHB (F, F) -F (1-7) 3%
3-HBB (F, F) -F (1-8) 4%
3-BB (F, F) XB (F, F) -F (1-17) 5%
3-HHBB (F, F) -F (1-19) 5%
3-HBBX (F, F) -F (1-23) 5%
3-BBVFFXB (F, F) -F (1-37) 8%
3-HH-V (2-1) 39%
1-HH-V1 (2-1) 3%
1-HH-2V1 (2-1) 4%
3-HHEH-5 (2-4) 3%
1-BB (F) B-2V (2-8) 3%
3-HHEBH-3 (2-11) 3%
5-HBB (F) B-2 (2-13) 3%
NI = 85.2 ° C .; Tc <−20 ° C .; Δn = 0.102; Δε = 4.1; γ1 = 43.0 mPa · s.

[Composition (M17)]
3-HHBB (F) -F (1) 3%
2-HHEB (F, F) -F (1-3) 3%
5-BB (F) B (F, F) -F (1-15) 7%
3-HHB (F) B (F, F) -F (1-20) 3%
3-GB (F) B (F, F) XB (F, F) -F (1-27) 3%
3-BB (F, F) XB (F) B (F, F) -F (1-30) 3%
3-HHVFFXB (F, F) -F (1-38) 5%
3-BBVFFXB (F, F) -F (1-37) 5%
3-HBBVFFXB (F, F) -F (1-39) 3%
2-HH-5 (2-1) 5%
3-HH-V (2-1) 20%
5-HH-V (2-1) 12%
3-HH-V1 (2-1) 4%
4-HH-V1 (2-1) 5%
2-HH-2V1 (2-1) 3%
1-BB-3 (2-3) 3%
V2-BB (F) B-1 (2-8) 5%
V2-B (F) BB-1 (2-7) 5%
3-HB (F) HH-5 (2-10) 3%
NI = 85.8 ° C .; Tc <−20 ° C .; Δn = 0.115; Δε = 4.2; γ1 = 41.4 mPa · s.

[Composition (M18)]
3-BB (F) XB (F) B (F, F) -F (1) 5%
3-HGB (F, F) -F (1-6) 3%
5-GHB (F, F) -F (1-7) 4%
3-GB (F, F) XB (F, F) -F (1-14) 5%
3-HHBB (F, F) -F (1-19) 4%
2-dhBB (F, F) XB (F, F) -F (1-25) 4%
3-GB (F) B (F, F) XB (F, F) -F (1-27) 3%
3-HGB (F, F) XB (F, F) -F (1) 5%
7-HB (F, F) -F (1) 3%
2-HH-3 (2-1) 14%
2-HH-5 (2-1) 4%
3-HH-V (2-1) 26%
1V2-HH-3 (2-1) 5%
1V2-BB-1 (2-3) 3%
2-BB (F) B-3 (2-8) 3%
3-HB (F) HH-2 (2-10) 4%
5-HBB (F) B-2 (2-13) 5%
NI = 78.4 ° C .; Tc <−20 ° C .; Δn = 0.094; Δε = 5.6; Vth = 1.45 V; η = 11.5 mPa · s; γ1 = 61.7 mPa · s.

[Composition (M19)]
3-HBB (F, F) -F (1-8) 5%
5-HBB (F, F) -F (1-8) 4%
3-BB (F) B (F, F) XB (F, F) -F (1-29) 3%
4-BB (F) B (F, F) XB (F, F) -F (1-29) 5%
3-BB (F, F) XB (F) B (F, F) -F (1-30) 10%
3-HH2BB (F, F) -F (1) 3%
4-HH2BB (F, F) -F (1) 3%
2-HH-5 (2-1) 4%
3-HH-V (2-1) 25%
3-HH-V1 (2-1) 10%
4-HH-V1 (2-1) 7%
5-HB-O2 (2-2) 5%
7-HB-1 (2-2) 5%
VFF-HHB-O1 (2-5) 8%
VFF-HHB-1 (2-5) 3%
NI = 79.3 ° C .; Tc <−20 ° C .; Δn = 0.099; Δε = 5.0; Vth = 1.64V; η = 10.4 mPa · s; γ1 = 44.7 mPa · s.

[Composition (M20)]
3-GBXB (F) B (F, F) -F (1) 5%
3-HHB (F, F) -F (1-2) 7%
3-GB (F) B (F) -F (1-11) 2%
3-GB (F) B (F, F) -F (1-12) 3%
3-BB (F, F) XB (F, F) -F (1-18) 7%
3-GB (F) B (F, F) XB (F, F) -F (1-27) 4%
5-GB (F) B (F, F) XB (F, F) -F (1-27) 5%
3-HH-V (2-1) 30%
3-HH-V1 (2-1) 10%
1V2-HH-3 (2-1) 8%
3-HH-VFF (2-1) 8%
V2-BB-1 (2-3) 2%
5-HB (F) BH-3 (2-12) 4%
5-HBBH-3 (2) 5%
NI = 79.7 ° C .; Tc <−20 ° C .; Δn = 0.091; Δε = 5.7; Vth = 1.83 V; η = 14.9 mPa · s; γ1 = 69.3 mPa · s.

  The first additive, the orienting monomer, is the following compound.

2. Alignment of liquid crystal molecules <Polarized light exposure conditions>
Using a 250 W ultra-high pressure mercury lamp (multi-light manufactured by USHIO INC.) And a wire grid polarizer (ProFlux (UVT-260A manufactured by MOXTEK)), 3 mW / cm ² (irradiance of wavelength 313 nm is UV irradiance manufactured by USHIO INC.). (Measured using UIT-150 and UVD-S313 in total).
Example 1
The compound (A-1-1-1), which is the first additive, was added to the composition (M15) at a ratio of 0.3 parts by weight. This mixture was injected into an IPS device having no alignment film at 90 ° C. (above the maximum temperature of the nematic phase). While heating the IPS element at 90 ° C., the element was irradiated with ultraviolet rays (313 nm, 5.0 J / cm ² ) linearly polarized from the normal direction to obtain an element in which an orientation control layer was formed. The irradiated ultraviolet light becomes linearly polarized light by passing through the polarizer. Next, the device in which the alignment control layer was formed was set in a polarization microscope and the alignment state of the liquid crystal was observed. The polarizer and the analyzer of the polarization microscope were arranged so that their transmission axes were orthogonal to each other. First, so that the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope are parallel, that is, the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarization microscope is 0 degree, The device was placed on the horizontal rotating stage of a polarizing microscope. Light was irradiated from the lower side of the device, that is, from the polarizer side, and the presence or absence of light passing through the analyzer was observed. Orientation was determined to be "good", since no light was observed to pass through the analyzer. In addition, in the same observation, when the light transmitted through the analyzer was observed, the orientation was determined to be “poor”. Next, the device was rotated on a horizontal rotation stage of the polarization microscope, and the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules was changed from 0 degree. The intensity of the light transmitted through the analyzer increases as the angle formed by the transmission axis of the polarizer of the polarization microscope and the alignment direction of the liquid crystal molecules increases, and reaches the maximum when the angle is 45 degrees. confirmed. In the device obtained as described above, the liquid crystal molecules were oriented in a direction substantially horizontal to the main surface of the substrate of the device, and it was determined to be “horizontal orientation”.
In Example 1, no light leakage was observed, so the orientation was good. The liquid crystal molecules were horizontally aligned.

Example 2
The compound (B-1-2-1), which is the first additive, was added to the composition (M1). A device was produced in the same manner as in Example 1 using this mixture. When the presence or absence of light leakage was observed in the same manner as in Example 1, no light leakage was observed, and the alignment was good.

Example 3
The compound (B-1-3-1), which is the first additive, was added to the composition (M11) at a ratio of 0.5 part by weight. This mixture was injected into an IPS device having no alignment film at 95 ° C. (above the maximum temperature of the nematic phase). The device was irradiated with linearly polarized light (313 nm, 2.0 J / cm ² ) from the normal direction at 100 ° C. (above the upper limit temperature). When the presence or absence of light leakage was observed in the same manner as in Example 1, no light leakage was observed, and the alignment was good.

Example 4
The compound (A-1-1-1), which is the first additive, was added to the composition (M18) at a ratio of 0.5 part by weight. This mixture was injected into an IPS device having no alignment film at 90 ° C. (above the maximum temperature of the nematic phase). The device was irradiated with linearly polarized light (313 nm, 2.0 J / cm ² ) from the normal direction at 90 ° C. (above the upper limit temperature). When the presence or absence of light leakage was observed in the same manner as in Example 1, no light leakage was observed, and the alignment was good.

Example 5
The compound (B-1-2-1), which is the first additive, was added to the composition (M19) at a ratio of 0.5 part by weight. This mixture was injected into an IPS device having no alignment film at 90 ° C. (above the maximum temperature of the nematic phase). The device was irradiated with linearly polarized light (313 nm, 2.0 J / cm ² ) from the normal direction at 90 ° C. (above the upper limit temperature). When the presence or absence of light leakage was observed in the same manner as in Example 1, no light leakage was observed, and the alignment was good.

Example 6
The compound (A-1-1-1), which is the first additive, was added to the composition (M20) at a ratio of 0.5 part by weight. This mixture was injected into an IPS device having no alignment film at 90 ° C. (above the maximum temperature of the nematic phase). The device was irradiated with linearly polarized light (313 nm, 2.0 J / cm ² ) from the normal direction at 90 ° C. (above the upper limit temperature). When the presence or absence of light leakage was observed in the same manner as in Example 1, no light leakage was observed, and the alignment was good.

Example 7
The compound (A-1-1-1) and the compound (A-1-7-1), which are the first additives, were added to the composition (M20) at a ratio of 0.5 parts by weight, respectively. This mixture was injected into an IPS device having no alignment film at 90 ° C. (above the maximum temperature of the nematic phase). The device was irradiated with linearly polarized light (313 nm, 2.0 J / cm ² ) from the normal direction at 90 ° C. (above the upper limit temperature). When the presence or absence of light leakage was observed in the same manner as in Example 1, no light leakage was observed, and the alignment was good.

3. Compatibility of Alignment Monomer and Liquid Crystal Composition The stability of the mixture of the liquid crystal composition and the alignment monomer obtained in the above Examples at room temperature was evaluated. After mixing, the mixture was changed to an isotropic liquid at 100 ° C and allowed to cool to 25 ° C. When the presence or absence of precipitation was confirmed after half a day at room temperature, no precipitation was confirmed in the mixtures of Examples 1 to 7, and the compatibility of any of the oriented monomers was good.

Comparative Example 1
Only the composition (M15) was injected into the IPS device having no alignment film. When the presence or absence of light leakage was observed in the same manner as in Example 1, light leakage was observed, and the orientation was poor.

Comparative Examples 2-6
The composition (M1) alone, the composition (M11) alone, the composition (M18) alone, the composition (M19) alone, or the composition (M20) alone was injected into an IPS device having no alignment film. When the presence or absence of light leakage was observed in the same manner as in No. 1, light leakage was observed, and the orientation was poor.

In Examples 1 to 6, the type and amount of the composition and the first additive, and the heating temperature during polarized light exposure were changed, but no light leakage was observed. This result shows that the alignment is good even if the device does not have an alignment film such as polyimide, and all the liquid crystal molecules are aligned in a fixed direction. The same tendency was observed when a plurality of orienting monomers were used. On the other hand, light leakage was observed in Comparative Examples 1 to 6 which did not contain the first additive. From the above results, it can be seen that the thin film formed from the first additive plays an important role in the alignment of liquid crystal molecules. It is also found that the compatibility with the liquid crystal composition is good. The effect of such an orienting monomer can be obtained in the same manner other than the combination of other liquid crystal compositions disclosed in the above-mentioned examples. Similar effects can be obtained by using other aligning monomers (for example, compound (A-1-1) to compound (A-1-9), compound (B-1-1) to compound (B-1-8)). You can expect even when.
Therefore, using the liquid crystal composition of the present invention, a liquid crystal display device having characteristics such as a wide temperature range in which the device can be used, a short response time, a high voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime. Is obtained.
Furthermore, a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a large positive dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, a high stability against heat. A liquid crystal display device having a liquid crystal composition satisfying at least one of the above characteristics can be obtained.

  The liquid crystal composition of the present invention can be used for liquid crystal monitors, liquid crystal televisions and the like.

Claims (26)

The liquid crystal layer is sandwiched between a pair of substrates which are arranged facing each other and are bonded to each other via a sealant.
Between the pair of substrates and the liquid crystal layer, an alignment control layer that controls the alignment of liquid crystal molecules,
The liquid crystal layer is composed of a liquid crystal composition having a positive dielectric anisotropy,
The liquid crystal composition is a group of compounds represented by the formula (A-1), the formula (A-2), the formula (B-1) and the formula (B-2) as an aligning monomer which is a first additive. Containing at least one compound selected from and a liquid crystal compound,
The said orientation control layer is a liquid crystal display element which consists of the polymer produced by superposing | polymerizing the said 1st additive.

In formulas (A-1) and (A-2), P ¹⁰ is independently a group selected from the groups represented by formulas (Q-1) to (Q-5);
In formulas (Q-1) to (Q-5), M ¹⁰ , M ²⁰ , and M ³⁰ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen is fluorine or chlorine. An alkyl having 1 to 5 carbons replaced by
In formula (A-1) and formula (A-2),
Sp ¹⁰ and Sp ¹¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or formula (Q-6), and at least one of _-CH 2 -, -O -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or - May be replaced by C≡C-;

In formula (Q-6), M ¹¹ , M ²¹ , and M ³¹ are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or 1 carbon having at least one hydrogen replaced with fluorine or chlorine. To 5 alkyls;
Sp ⁴¹ is independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine or chlorine, and at least one —CH ₂ — is —O. -, -CO-, -COO-, or -OCO- may be substituted;
In formula (A-1), formula (A-2), formula (B-1) and formula (B-2),
Ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , ring A ⁴⁰ and ring A ⁵⁰ are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 4,4 ′. -Biphenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3 -Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, per Hydrocyclopenta [a] phenanthrene-3,17-diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclo And the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO-C≡C-. , -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl, pyrimidine-2,5-diyl. , Pyridine-2,5-diyl, fluorene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, in which at least one hydrogen is fluorine, hydroxy, It may be replaced by chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons. There are, at least one hydrogen may be replaced by fluorine or chlorine;
In formulas (A-1) and (A-2), Z ¹⁰ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —. _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O-, _{-OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡ C-;
In formula (A-2), Z ¹¹ is —CH═CH—CO— or —CO—CH═CH—;
In the formula (A-1) and the formula (A-2), n ¹⁰ is an integer of 0 to 4;
In formula (B-1) and formula (B-2),
R ²⁰ is hydrogen, fluorine, chlorine, hydroxy, cyano, nitro, trifluoromethyl, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons;
Sp ²⁰ and Sp ²¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, and at least one —CH ₂ — is —O. -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - may be replaced by -CH = CH- or -C≡C-;
Z ²⁰ is independently a single bond, -COO -, - OCO -, - CH = CH-COO -, - OCO-CH = CH -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF 2 -, - CONH -, - NHCO -, - ( _{CH 2) 4 -, - CH} 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or a -C≡C-;
n ²⁰ is an integer of 0 to 3. In formula (A-1) and formula (A-2) according to claim 1,
P ¹⁰ is independently formula (Q-1);
In formula (Q-1),
M ¹⁰ is independently hydrogen, fluorine, methyl, or trifluoromethyl;
M ²⁰ and M ³⁰ are hydrogen;
Sp ¹⁰ and Sp ¹¹ are independently a single bond or alkylene having 2 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by fluorine, chlorine or formula (Q-6), and one of _-CH 2 -, -O -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or - May be replaced by C≡C-;
In formula (Q-6), M ¹¹ is independently hydrogen, fluorine, methyl, or trifluoromethyl; M ²¹ and M ³¹ are hydrogen;
Sp ⁴¹ is independently a single bond or alkylene having 1 to 12 carbons, at least one hydrogen of this alkylene may be replaced by fluorine, and at least one —CH ₂ — is —O—, May be replaced with -CO-, -COO-, or -OCO-;
In formula (A-1), formula (A-2), formula (B-1) and formula (B-2),
Ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , ring A ⁴⁰ and ring A ⁵⁰ are independently 1,4-cyclohexylene, 1,4-phenylene, 4,4′-biphenylene, naphthalene-2,6. -Diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, but adjacent structures are -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO. In the case of-, -OCO-C≡C-, -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, or naphthalene-2,6. -Diyl, in which at least one hydrogen may be replaced by fluorine, hydroxy, trifluoromethyl, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons;
In formulas (A-1) and (A-2), Z ¹⁰ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —. _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O-, _{-OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡ C-;
In formula (A-2), Z ¹¹ is —CH═CH—CO— or —CO—CH═CH—;
In the formula (A-1) and the formula (A-2), n ¹⁰ is an integer of 0 to 4;
In formula (B-1) and formula (B-2),
R ²⁰ is hydrogen, fluorine, hydroxy, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Sp ²⁰ and Sp ²¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH ₂ — of this alkylene may be replaced by —O—;
The liquid crystal display element according to claim 1, wherein n ²⁰ is an integer of 0 to 3. In formula (A-1) and formula (A-2) according to claim 1,
P ¹⁰ is independently formula (Q-1);
In formula (Q-1),
M ¹⁰ is independently hydrogen or methyl;
M ²⁰ and M ³⁰ are hydrogen;
Sp ¹⁰ and Sp ¹¹ are independently a single bond or alkylene having 2 to 12 carbons, and at least one hydrogen of this alkylene may be replaced by the formula (Q-6), and at least one —CH. ₂ -, -O -, - CO -, - COO-, or may be replaced by -OCO-, at least one _-CH 2 -CH ₂ - is, -CH = CH- or -C≡C- May be replaced with;
In formulas (A-1) and (A-2), Z ¹⁰ is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OCO—CH═CH—, —. _{OCO-CH 2 CH 2 -,} - CH 2 CH 2 -COO -, - C≡C-COO -, - OCO-C≡C -, - CH 2 O -, - OCH 2 -, - CF 2 O-, _{-OCF 2 -, - CONH -,} - NHCO -, - (CH 2) 4 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH -, - CF = CF- or -C≡ C-;
In formula (A-2), Z ¹¹ is —CH═CH—CO— or —CO—CH═CH—;
Ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , ring A ⁴⁰ and ring A ⁵⁰ are independently 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl, or tetrahydronaphthalene-2. , 6-diyl, but the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO-C≡C-, -CH = CH-, In the case of -CF = CF- or -C≡C-, it is 1,4-phenylene or naphthalene-2,6-diyl, and in this 1,4-phenylene, any hydrogen is fluorine, hydroxy or trifluoromethyl. , Alkyl having 1 to 3 carbons, or alkoxy having 1 to 3 carbons;
In formula (A-1) and formula (A-2), n ¹⁰ is an integer of 0 to 2;
In formula (B-1) and formula (B-2),
R ²⁰ is hydrogen, fluorine, hydroxy, alkyl having 1 to 5 carbons or alkoxy having 1 to 5 carbons;
Sp ²⁰ and Sp ²¹ are independently a single bond or alkylene having 1 to 12 carbons, and at least one —CH ₂ — of this alkylene may be replaced by —O—;
n ²⁰ is an integer from 0 to 3,
The liquid crystal display element according to claim 1.   4. The ratio of the alignment monomer as the first additive is in the range of 0.1 parts by weight to 10 parts by weight when the total amount of the liquid crystal compounds is 100 parts by weight. 2. A liquid crystal display device according to item 1. The liquid crystal display device according to claim 1, which contains at least one compound selected from the group of compounds represented by formula (1) as a first component.

In the formula (1), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyl having 2 to 12 carbons; ring A is 1,4-cyclohexylene, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, pyrimidine-2,5-diyl, 1,3-dioxane 2,5-diyl or tetrahydropyran-2,5-diyl,; ^{Z 1} is a single bond, ethylene, carbonyloxy, -CH = CF -, - CF = CF-, difluoromethyleneoxy, -CH = _CF-CF 2 O- or -CF = _CF-CF 2 O- and is; ^{X 1} and ^{X 2} are each independently hydrogen or fluorine; ^{Y 1} is fluorine, chlorine, at least one hydrogen Alkyl having 1 to 12 carbons replaced with fluorine or chlorine, alkoxy having 1 to 12 carbons having at least one hydrogen replaced with fluorine or chlorine, or carbon having at least one hydrogen replaced with fluorine or chlorine. Is an alkenyloxy of the number 2 to 12; a is 1, 2, 3, or 4. The liquid crystal according to claim 1, which contains at least one compound selected from the group of compounds represented by formulas (1-1) to (1-39) as a first component. Display element.

In the formulas (1-1) to (1-39), R ¹ is alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyl having 2 to 12 carbons.   The liquid crystal display device according to claim 5, wherein the ratio of the first component is in the range of 10% by weight to 85% by weight with respect to the total amount of the liquid crystal compounds. The liquid crystal display element according to claim 1, which contains at least one compound selected from the group of compounds represented by formula (2) as the second component.

In the formula (2), R ² and R ³ 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. A substituted alkenyl having 2 to 12 carbons; ring B and ring C are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5 - be-difluoro-1,4-phenylene; ^{Z 2} is a single bond, ethylene or carbonyloxy,; b is 1, 2 or 3. 9. The liquid crystal according to claim 1, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-13) as the second component. Display element.

In formulas (2-1) to (2-13), R ² and R ³ are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or Alkenyl having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.   The liquid crystal display element according to claim 8 or 9, wherein the ratio of the second component is in the range of 10% by weight to 85% by weight with respect to the total amount of the liquid crystal compounds. The liquid crystal display element according to claim 1, which contains 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, or alkenyloxy having 2 to 12 carbons. Yes; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen being fluorine or chlorine. 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one Chroman-2,6-diyl in which hydrogen is replaced by fluorine or chlorine; 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 3} and ^{Z 4} are each independently a single bond, ethylene, carbonyloxy or methyleneoxy,; c is 1, 2, or 3,, d is , 0 or 1; the sum of c and d is 3 or less. The liquid crystal according to any one of claims 1 to 11, which contains, as a third component, at least one compound selected from the group of compounds represented by formulas (3-1) to (3-22). Display element.

In formulas (3-1) to (3-22), 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, or It is an alkenyloxy having 2 to 12 carbon atoms.   The liquid crystal display device according to claim 11 or 12, wherein the ratio of the third component is in the range of 3% by weight to 25% by weight with respect to the total amount of the liquid crystal compounds. The liquid crystal display device according to claim 1, further comprising at least one compound selected from the group of polymerizable compounds represented by formula (4) as the second additive.

In formula (4), ring F ³ and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-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. May be replaced by an alkyl having 1 to 12 carbons which is replaced by fluorine or chlorine; Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1. , 2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1 , 6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2, 5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen is fluorine, chlorine, It may be replaced by alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen has been replaced by fluorine or chlorine; Z ⁶ and Z ⁷ are independent. A single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, -COO-, or may be replaced by -OCO-, and at least one _-CH 2 CH ₂ - _{is, -CH = CH -, - C} (CH 3) = CH -, - CH = C (CH 3 ) -, or _{-C (CH 3) = C (} CH 3) - may be replaced by, in these groups, at least one hydrogen may be replaced by fluorine or ^chlorine; P 1, ^{P 2} , And P ³ are polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are independently a single bond or an alkylene having 1 to 10 carbons, and in this alkylene, at least one —CH ₂ — is, -O -, - COO -, - OCO-, or it may be replaced by -OCOO-, and at least one _-CH 2 CH ₂ - is replaced by -CH = CH- or -C≡C- Being Also, in these groups, at least one hydrogen may be replaced by fluorine or chlorine; h is 0, 1, or 2; e, f, and g are independently 0, 1, 2, 3, or 4, and the sum of e, f, and g is 1 or more. In the formula (4), P ¹ , P ² , and P ³ are independently a group selected from the group of polymerizable groups represented by the formula (P-1) to the formula (P-5). Item 15. The liquid crystal display device according to item 14.

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. Is an alkyl having 1 to 5 carbon atoms replaced by. The second additive contains at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27), in any one of claims 1 to 15. The liquid crystal display element described.

In formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ⁶ are independently a polymerizable group represented by formulas (P-1) to (P-3). Is a group selected from the group,

Where 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 independently a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —COO—, -OCO-, or -OCOO- in may be replaced, at least one _-CH 2 CH ₂ - may be replaced by -CH = CH- or -C≡C-, and in the groups, at least One hydrogen may be replaced by fluorine or chlorine.   The ratio of the second additive is in the range of 0.03 parts by weight to 10 parts by weight when the total amount of the liquid crystal compounds is 100 parts by weight, and the ratio of the second additive is in any one of claims 14 to 16. Liquid crystal display device.   The maximum temperature of the nematic phase is 70 ° C. or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C.) is 0.07 or higher, and the dielectric anisotropy at a frequency of 1 kHz (measured at 25 ° C.) is 2 The liquid crystal display element according to any one of claims 1 to 17, which is the above.   The liquid crystal composition in the liquid crystal display device according to any one of claims 1 to 18 and an electrode are provided between a pair of substrates, and by irradiating linearly polarized light, the liquid crystal composition in the liquid crystal composition A liquid crystal display device in which the first additive has reacted.   The liquid crystal display element according to claim 19, 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 a driving method of the liquid crystal display element is an active matrix method. 20. The liquid crystal display element according to claim 19, wherein an operation mode of the liquid crystal display element is an IPS mode or an FFS mode, and a driving method of the liquid crystal display element is an active matrix method.   A polymer-supported alignment type liquid crystal display device comprising the liquid crystal composition in the liquid crystal display device according to claim 1, wherein the polymerizable compound in the liquid crystal composition is polymerized.   Use of the liquid crystal composition in a liquid crystal display device according to any one of claims 1 to 17 in a liquid crystal display device.   Use of the liquid crystal composition in the liquid crystal display device according to any one of claims 1 to 17 in a polymer-supported alignment type liquid crystal display device. Alignment of compounds represented by formula (A-1), formula (A-2), formula (B-1) and formula (B-2) in the liquid crystal display element according to claim 1. Use as a monomer for forming a control layer. The liquid crystal composition in the liquid crystal display element according to claim 1.