TW201905183A - Liquid crystal display element, use of liquid crystal composition, use of compound, compound, and liquid crystal composition - Google Patents

Abstract

The purpose of the present invention is to control the alignment of liquid crystal molecules of a liquid crystal display element not having an alignment film, by using a non-colored alignment-control-layer-forming monomer, and to provide a liquid crystal composition in which the non-colored alignment-control-layer-forming monomer shows good compatibility. The present invention uses a liquid crystal display element and a liquid crystal composition, the liquid crystal display element using a liquid crystal composition that contains an alignment-control-layer-forming monomer having a vinylene group in a partial structure thereof and that has a positive dielectric anisotropy.

Description

Liquid crystal display element, use of liquid crystal composition, compound, use of compound, and liquid crystal composition

The present invention relates to a liquid crystal display element, a liquid crystal composition, and a compound containing a liquid crystal composition having a positive dielectric anisotropy. In particular, the present invention relates to a liquid crystal display element using a liquid crystal composition containing an alignment control layer forming monomer having a vinyl group in a part of the structure, and the liquid crystal molecules can be aligned by the action of the compound. .

In liquid crystal display elements, the operation modes based on liquid crystal molecules are classified into phase change (PC), twisted nematic (TN), super twisted nematic (STN), and electrically controlled birefringence ( electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and other modes. The component-based driving methods are classified into a passive matrix (PM) and an active matrix (AM). PM is classified as static, multiplex, etc. AM is classified as thin film transistor (TFT), metal-insulator-metal (MIM), and the like. 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 manufacturing steps. The light source is classified into a reflection type using natural light, a transmission type using backlight, and a semi-transmission type using both natural light and backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation between the characteristics of the two 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 element can be used. A preferred upper limit temperature of the nematic phase is about 70 ° C or higher, and a preferred lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of a composition is related to the response time of the element. In order to display a moving image as a component, it is preferable that the response time is short. Ideally a response time shorter than 1 millisecond. Therefore, the viscosity of the composition is preferably small. Furthermore, it is preferable that the viscosity at low temperature is small.

[Table 1]

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy is required, that is, an appropriate optical anisotropy. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The value of the appropriate product depends on the type of operation mode. In the VA mode device, the value ranges from about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode devices, the value ranges from about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is preferred for an element having a small cell gap. The large dielectric anisotropy of the composition contributes to the low threshold voltage of the device, small power consumption, and large contrast. Therefore, a large dielectric anisotropy is preferred. The large specific resistance of the composition contributes to the large voltage holding ratio and large contrast of the device. Therefore, a composition having a large specific resistance in the initial stage is preferred. A composition having a large specific resistance after long-term use is preferred. The stability of the composition to ultraviolet rays and heat is related to the life of the device. When the stability is high, the life of the device is long. Such characteristics are preferable for AM elements used in liquid crystal monitors and liquid crystal televisions.

A composition having a positive dielectric anisotropy is used for an AM device having a TN mode. A composition having a negative dielectric anisotropy is used for an AM device having a VA mode. A composition having a positive or negative dielectric anisotropy is used for an AM device having an IPS mode or an FFS mode. In a polymer sustained alignment (PSA) type liquid crystal display device, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into a device. Next, the composition is irradiated with ultraviolet rays while a voltage is applied between the substrates of the element. The polymerizable compound is polymerized to form a polymer network structure in the composition. In this composition, the polymer can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened, and the afterimage of the image is improved. Such an effect of a polymer can be expected in a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA. In the IPS mode, the FFS mode, and the ECB mode, when no voltage is applied to the liquid crystal molecules, alignment needs to be performed in a direction substantially horizontal to the main surface of the substrate. In order to achieve such alignment control of liquid crystal molecules, alignment films such as polyimide have been used. In recent years, the narrow frame of the liquid crystal panel has been continuously promoted, and the bonding width between the alignment film and the sealant has been narrowed, so that the bonding strength is weak, and peeling may occur from the interface between the alignment film and the sealant. In order to prevent such problems, a method is proposed in which an existing alignment film such as polyimide is not used (Patent Documents 1 to 3).

The following methods are reported: instead of an alignment film such as polyimide, a low-molecular compound having a cinnamate group or a polyvinyl cinnamate, a low-molecular compound having a chalcone structure, Molecular compounds or dendrimers to control the alignment of liquid crystals (Patent Document 1). In the method of Patent Document 1, first, the low-molecular compound or polymer is dissolved in a liquid crystal composition as an additive. Next, the additive is subjected to phase separation to produce a thin film containing 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 a low molecular compound or polymer undergoes dimerization or isomerization by the linearly polarized light, its molecules are aligned in a fixed direction. In this method, by selecting the type of the low-molecular compound or polymer, an element in a horizontal alignment mode such as IPS or FFS and an element in a vertical alignment mode such as VA can be manufactured. In this method, it is important that the low-molecular compound or polymer is easily dissolved at a temperature higher than the upper limit temperature of the liquid crystal composition, and when it is returned to room temperature, the compound easily undergoes phase separation from the liquid crystal composition. Among them, it is difficult to ensure compatibility of the low-molecular compound or polymer with the liquid crystal composition. In the methods of Patent Documents 2 and 3, a dendritic polymer having azobenzene as a partial structure is dissolved in a liquid crystal composition as an additive. Next, a thin film of the compound is formed on the substrate by phase-separating the compound. At this time, the liquid crystal composition is aligned vertically with respect to the substrate. Secondly, linearly polarized light is irradiated without heating the substrate. When the dendrimer is dimerized or isomerized by the linearly polarized light, its molecules are aligned in a horizontal direction with respect to the substrate. Components can be manufactured in horizontal alignment modes such as IPS or FFS. In this method, in order to facilitate the dissolution and phase separation of the dendrimer, it is necessary to appropriately combine the dendrimer and the liquid crystal composition. When a dendrimer having azobenzene as a partial structure is used, there is a problem in that the coloring is derived from azobenzene. Patent Document 4 discloses a polymer-dispersed liquid crystal optical element including a polymer resin obtained by photopolymerizing a chiral nematic liquid crystal with a (meth) acrylate compound having a stilbene skeleton. The liquid crystal optical element here is a device that reduces driving voltage and hysteresis. Since a chiral nematic liquid crystal is an essential component, it is a polymer-dispersed liquid crystal optical element that becomes transparent or selective when no voltage is applied, and becomes a scattering state when voltage is applied. Therefore, the structure is different from the invention of the present application . In addition, there is no suggestion or description that the (meth) acrylic acid ester compound having a stilbene skeleton causes horizontal alignment of the liquid crystal compound by polarized light irradiation. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2015/146369 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2015-64465 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 2015-125151 [Patent Literature 4] Japanese Patent Laid-Open No. 08 -92561

[Problems to be Solved by the Invention] An object of the present invention is to provide a liquid crystal composition that uses a liquid crystal composition containing an alignment control layer to form a monomer, and does not require a conventional alignment film formed of polyimide or the like or a liquid crystal forming step thereof. Display element. Furthermore, there is provided an alignment control layer-forming monomer which exhibits good compatibility with the liquid crystal composition and is free of color, so as to realize a liquid crystal display element having excellent transmittance characteristics and contrast. [Means for solving problems]

The present invention uses a liquid crystal display element, a liquid crystal composition, and a compound using a liquid crystal composition. The liquid crystal composition contains an alignment control layer forming monomer having a vinyl group in part of the structure, and has positive dielectric anisotropy. . The present invention is as follows. A liquid crystal display element that sandwiches a liquid crystal layer between a pair of substrates disposed opposite to each other and bonded together via a sealant, and has alignment control between the pair of substrates and the liquid crystal layer to control alignment of liquid crystal molecules. Layer, the liquid crystal layer has positive dielectric anisotropy, and in the liquid crystal display element, the alignment control layer includes forming an alignment control layer by sandwiching a liquid crystal composition between the pair of substrates. A polymer produced by polymerizing a monomer, the liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (A) to formula (D) as a first additive and as the alignment control layer Forms monomers and liquid crystal compounds. In the formulae (A) to (D), P ¹⁰ , P ²⁰ , P ³⁰ , and P ^{40 are each} independently a group selected from the groups represented by the formulae (Q-1) to (Q-5); In the formulae (Q-1) to (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. C 1 to 5 alkyl groups; Sp ¹⁰ , Sp ²⁰ , and Sp ^{40 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be fluorine, chlorine, or formula ( Q-6) Substitution, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH-; Sp ^{30 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted with fluorine, chlorine, or formula (Q-6), and at least one -CH ₂ -may be substituted through -O- , -CO-, -COO-, or -OCO- substitution; In formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted with fluorine or chlorine, and at least one -CH ₂ -may be -O-, -CO- , -COO-, or -OCO- substitution; Ring A ¹⁰ and Ring A ^{20 are} independently phenyl, 4-biphenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidine-5- Group, pyridin-2-yl, pyridin-5-yl, fluoren-2-yl, fluoren-3-yl, phenanthrene-2-yl, or anthracen-2-yl, in these rings, at least one hydrogen may be passed through fluorine , 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. Among these groups, at least One hydrogen may be substituted by fluorine or chlorine; ring A ¹¹ , ring A ²¹ , ring A ¹² , ring A ²² and ring A ^{30 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1 4,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl, decalin-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, perhydrocyclopenta [a] phenanthrene- 3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradechydrocyclopenta [a] phenanthrene-3,17 -Diyl, the adjacent bonds are -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO-, when R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, alkyl having 1 to 10 carbons, or at least one hydrogen substituted with fluorine having 1 to 10 alkyl, it is 1, 4-phenylene, 4,4'-biphenylyl, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-di Radical, phenanthrene-2,7-diyl, or anthracene-2,6-diyl. In these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, and 2 to 12 carbons. Alkenyl, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons, in which at least one hydrogen may be substituted with fluorine or chlorine; ring A ⁴⁰ is 1,4- Cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenyl, 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, pyrene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] Phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecylhydrocyclopenta [a] Phenanthrene-3,17-diyl, adjacent bonds are -CH = CH-, -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO -At 1,4-phenylene, 4,4'-biphenyl, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene -2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, in these rings, at least one hydrogen may pass through P ²⁰ -Sp ^20- , fluorine, chlorine, carbon number 1 to 12 alkyl groups, alkenyl groups having 2 to 12 carbon atoms, alkoxy groups having 1 to 11 carbon atoms, or alkenyloxy groups having 2 to 11 carbon atoms, at least one of these groups may be substituted with fluorine Or chlorine substitution; Z ^{10 is} independently -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO-; R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, an alkyl group having 1 to 10 carbons, or at least one hydrogen substituted with fluorine is an alkyl group having 1 to 10 carbons; Z ^{10 is} independently for ^{-CH = CH -, - CR 10} = CR 20 -, - CO-CH = CH -, - CH = CH-CO -, - OCO-CH = CH-, or -CH = CH-COO- R ¹⁰ and R ²⁰ are independently alkyl of hydrogen, fluoro, cyano, having 1 to 10 carbons, a hydrogen or at least one fluorine-substituted alkyl group having a carbon number 1 to 10; Z ¹¹ independently a single bond or a C 1 to 6 alkylene groups, at least one -CH ₂ -of which may be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; Z ²⁰ and Z ^{21 are} independently a single bond, and the carbon number is 1 to 6 At least one of the alkylene group or the alkylene group having 2 to 6 carbon atoms is an alkylene group having 2 to 6 carbon atoms. Among these alkylene and alkenyl groups, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO-, and the other at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in which at least one hydrogen may be substituted by fluorine or chlorine; k ¹⁰ and n ^{10 are} independently integers from 0 to 3, k ¹⁰ and n The sum of ¹⁰ is an integer from 1 to 6; n ²⁰ is 1 or 2; n ³⁰ is 1 or 2. A liquid crystal display element includes a liquid crystal composition and an electrode in the liquid crystal display element between a pair of substrates, and an alignment control layer in the liquid crystal composition is irradiated with linear polarized light due to an upper limit temperature of a nematic phase. A monomer is formed and reacted. A polymer stable alignment type liquid crystal display element includes a liquid crystal composition in the liquid crystal display element, and a polymerizable compound in the liquid crystal composition is polymerized. A use of a liquid crystal composition, which is a liquid crystal composition in the liquid crystal display element, and is used in a liquid crystal display element. A use of a liquid crystal composition, wherein the liquid crystal composition is a liquid crystal composition in the liquid crystal display element, and is used in a polymer stable alignment type liquid crystal display element. A compound represented by the formula (A-2). In formula (A-2), P ⁵⁰ and P ^{60 are} independently a group selected from the group represented by formula (Q-1); in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently Ground is hydrogen, fluorine, methyl, or at least one hydrogen substituted by fluorine with 1 to 5 carbons; Sp ⁵⁰ and Sp ^{60 are} independently alkylenes with 1 to 12 carbons. One hydrogen may be substituted with fluorine or formula (Q-6), and at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-; in formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen group having 1 to 5 carbon atoms substituted with fluorine or chlorine; Sp ^{41 is} independently a single bond or 1 to 12 carbon alkylene groups, at least one hydrogen of which may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO- Z ¹² is -CO-, or -OCO-; R ^{50 is} independently hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or at least one alkyl group having 1 to 10 carbon atoms substituted with fluorine; k ¹⁰ And n ^{10 are} independently integers of 0 to 3, and the sum of k ¹⁰ and n ¹⁰ is an integer of 1 to 4. Use of a compound, which is the compound, which is used as a monomer for forming an alignment control layer. A liquid crystal composition is the liquid crystal composition. [Effect of the invention]

According to the present invention, by using a liquid crystal composition containing an alignment control layer-forming monomer, a liquid crystal display element that is difficult to peel even in a narrow frame can be manufactured. In addition, by using an alignment control layer-forming monomer having excellent solubility and no coloring in a liquid crystal composition, a liquid crystal display element having excellent transmittance characteristics and contrast can be realized. Furthermore, an alignment film formation step is not required in the manufacture of the liquid crystal display element, and the manufacturing cost of the liquid crystal display element can be reduced.

The terms used in this manual are as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. "Liquid crystal display device" is a generic term for a liquid crystal display panel and a liquid crystal display module. A "liquid crystal compound" is a compound that has a nematic phase and a smectic liquid crystal phase, and although it does not have a liquid crystal phase, it is used to adjust the temperature range, viscosity, and dielectric anisotropy of the nematic phase A general term for compounds mixed in the composition. The compound has a six-membered ring such as 1,4-cyclohexyl or 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. The liquid crystal compound which has an alkenyl group is not polymerizable in the meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. To this composition, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound are added as needed. That is, when it is convenient to add an additive, the ratio of the liquid crystal compound is also expressed by a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. The ratio of the additives is expressed by a weight percentage (parts by weight) based on the weight of the liquid crystal composition containing no additives. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Sometimes parts per million by weight (ppm) is used. The proportion of the polymerization initiator is exceptionally expressed based on the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as the "lower limit temperature". "High specific resistance" means that the composition has a large specific resistance in the initial stage, and also has a large specific resistance after long-term use. "Large voltage retention" means that the element has a large voltage retention not only at room temperature in the initial stage, but also at a temperature close to the upper limit temperature, and not only at room temperature but also after It also has a large voltage holding ratio at a temperature close to the upper limit temperature. In order to investigate the characteristics of a composition or an element, a change with time is sometimes used. The expression "improving dielectric anisotropy" refers to a composition with a positive dielectric anisotropy, which means that its value increases positively, and a composition with a negative dielectric anisotropy means a negative value. Increase to the ground.

The compound represented by formula (1) may be simply referred to as "compound (1)". At least one kind of compound selected from the group of compounds represented by formula (1) may be simply referred to as "compound (1)". "Compound (1)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1). The same applies to compounds represented by other formulas. The expression "at least one" A "" means that the number of "A" is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their positions are You can also choose unlimitedly. This rule also applies to the expression "at least one 'A' is replaced by 'B'".

The expression "at least one -CH ₂ -may be substituted with -O-" is used in this specification. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by non-adjacent -CH ₂ -substituted with -O-. However, adjacent -CH ₂ -will not be replaced by -O-. This is because -OO-CH _2- (peroxide) is formed during the substitution. That is, the expression refers to both "one -CH ₂ -may be substituted with -O-" and "at least two non-adjacent -CH ₂ -may be substituted with -O-". This rule applies not only when substituted with -O-, but also when substituted with a divalent group such as -CH = CH- or -COO-.

In the chemical formula of the component compound, the symbol of the terminal group R ¹ is used for various compounds. In these compounds, the two groups represented by any two R ¹ may be the same or different. For example, there may be a case where R ¹ of the compound (1-1) is an ethyl group and R ¹ of the compound (1-2) is an ethyl group. There are also cases where R ¹ of compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to other terminal group marks. In formula (1), when the subscript 'a' is 2, there are two rings A. In this compound, the two rings represented by the two rings A may be the same or different. When the subscript 'a' is greater than 2, this rule also applies to any two rings A. This rule also applies to symbols such as Z ¹ and ring D.

Symbols A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as a six-membered ring and a condensed ring. In the formula (4), a diagonal line crossing one side of the hexagon indicates that any hydrogen on the ring may be substituted with a group such as -Sp ¹ -P ¹ . Subscripts such as 'e' indicate the number of substituted groups. When the subscript 'e' is 0 (zero), there is no such substitution. When the subscript 'e' is 2 or more, there are multiple -Sp ¹ -P ¹ on the ring F ³ . The plural groups represented by -Sp ¹ -P ¹ may be the same or different.

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

The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. In order to raise the upper limit temperature, the stereo configuration associated with 1,4-cyclohexyl is a trans configuration that is better than a cis configuration.

The present invention includes the following items.

Item 1. A liquid crystal display element that sandwiches a liquid crystal layer between a pair of substrates disposed opposite to each other and bonded together via a sealant, and has alignment control of liquid crystal molecules between the pair of substrates and the liquid crystal layer. An alignment control layer of the liquid crystal layer having positive dielectric anisotropy, and in the liquid crystal display element, the alignment control layer includes a liquid crystal composition sandwiched between the pair of substrates and aligned The control layer forms a polymer produced by polymerizing a monomer, and the liquid crystal composition contains at least one compound selected from the group of compounds represented by formula (A) to formula (D) as a first additive and as the first additive. The alignment control layer forms a monomer and a liquid crystal compound. In the formulae (A) to (D), P ¹⁰ , P ²⁰ , P ³⁰ , and P ^{40 are each} independently a group selected from the groups represented by the formulae (Q-1) to (Q-5); In the formulae (Q-1) to (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. C 1 to 5 alkyl groups; Sp ¹⁰ , Sp ²⁰ , and Sp ^{40 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be fluorine, chlorine, or formula ( Q-6) Substitution, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH-; Sp ^{30 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted with fluorine, chlorine, or formula (Q-6), and at least one -CH ₂ -may be substituted through -O- , -CO-, -COO-, or -OCO- substitution; In formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted with fluorine or chlorine, and at least one -CH ₂ -may be -O-, -CO- , -COO-, or -OCO- substitution; Ring A ¹⁰ and Ring A ^{20 are} independently phenyl, 4-biphenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidine-5- Group, pyridin-2-yl, pyridin-5-yl, fluoren-2-yl, fluoren-3-yl, phenanthrene-2-yl, or anthracen-2-yl, in these rings, at least one hydrogen may be passed through fluorine , 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. Among these groups, at least One hydrogen may be substituted by fluorine or chlorine; ring A ¹¹ , ring A ²¹ , ring A ¹² , ring A ²² and ring A ^{30 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1 4,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl, decalin-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, perhydrocyclopenta [a] phenanthrene- 3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradechydrocyclopenta [a] phenanthrene-3,17 -Diyl, the adjacent bonds are -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO-, when R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, alkyl having 1 to 10 carbons, or at least one hydrogen substituted with fluorine having 1 to 10 alkyl, it is 1, 4-phenylene, 4,4'-biphenylyl, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene-2,7-di Radical, phenanthrene-2,7-diyl, or anthracene-2,6-diyl. In these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, and 2 to 12 carbons. Alkenyl, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons, in which at least one hydrogen may be substituted with fluorine or chlorine; ring A ⁴⁰ is 1,4- Cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenyl, 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, pyrene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] Phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecylhydrocyclopenta [a] Phenanthrene-3,17-diyl, adjacent bonds are -CH = CH-, -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO -At 1,4-phenylene, 4,4'-biphenyl, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, fluorene -2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, in these rings, at least one hydrogen may pass through P ²⁰ -Sp ^20- , fluorine, chlorine, carbon number 1 to 12 alkyl groups, alkenyl groups having 2 to 12 carbon atoms, alkoxy groups having 1 to 11 carbon atoms, or alkenyloxy groups having 2 to 11 carbon atoms, at least one of these groups may be substituted with fluorine Or chlorine substitution; Z ^{10 is} independently -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO-; R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, an alkyl group having 1 to 10 carbons, or at least one hydrogen substituted with fluorine is an alkyl group having 1 to 10 carbons; Z ^{10 is} independently for ^{-CH = CH -, - CR 10} = CR 20 -, - CO-CH = CH -, - CH = CH-CO -, - OCO-CH = CH-, or -CH = CH-COO- R ¹⁰ and R ²⁰ are independently alkyl of hydrogen, fluoro, cyano, having 1 to 10 carbons, a hydrogen or at least one fluorine-substituted alkyl group having a carbon number 1 to 10; Z ¹¹ independently a single bond or a C 1 to 6 alkylene groups, at least one -CH ₂ -of which may be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; Z ²⁰ and Z ^{21 are} independently a single bond, and the carbon number is 1 to 6 At least one of the alkylene group or the alkylene group having 2 to 6 carbon atoms is an alkylene group having 2 to 6 carbon atoms. Among these alkylene and alkenyl groups, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO-, and the other at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in which at least one hydrogen may be substituted by fluorine or chlorine; k ¹⁰ and n ^{10 are} independently integers from 0 to 3, k ¹⁰ and n The sum of ¹⁰ is an integer from 1 to 6; n ²⁰ is 1 or 2; n ³⁰ is 1 or 2.

Item 2. The liquid crystal display element according to Item 1, wherein the alignment control layer forming monomer in the liquid crystal composition is a formula (A-1), a formula (A-2), a formula (B), and a formula (C-1) ) And formula (D-1). In formula (A-1), formula (A-2), formula (B), formula (C-1) and formula (D-1), P ¹⁰ , P ²⁰ , P ³⁰ , P ⁴⁰ , P ⁵⁰ and P ^{60 is} independently a group selected from the group represented by formula (Q-1); in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, methyl, or at least one Hydrogen is substituted by fluorine with an alkyl group having 1 to 5 carbon atoms; Sp ¹⁰ , Sp ²⁰ , and Sp ^{40 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one hydrogen of the alkylene group may be substituted with fluorine Or substituted by formula (Q-6), at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- Substitution; Sp ^{30 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted with fluorine, chlorine, or formula (Q-6), and at least one -CH ₂ -may be substituted -O-, -CO-, -COO-, or -OCO- substitution; in formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, methyl, or at least one hydrogen atom Fluorine-substituted alkyl having 1 to 5 carbons; Sp ^{41 is} independently a single bond or an alkylene having 1 to 12 carbons, at least one hydrogen of which may be substituted with fluorine or chlorine, and at least one -CH ₂ - By -O -, - CO -, - COO-, -OCO- or substituted; Sp ⁵⁰ and Sp ⁶⁰ are independently an alkylene group having a carbon number of 2 to 12, which alkylene group may be at least one hydrogen, fluorine, chlorine Or formula (Q-6) substitution, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-; R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, Alkyl group having 1 to 10 carbons, or 1 to 10 alkyl group having at least one hydrogen substituted with fluorine; R ^{3 0} , R ^{4 0} , R ⁴¹ and R ^{5 0 are} independently hydrogen, fluorine, chlorine, carbon An alkyl group having 1 to 10 or an alkyl group having 1 to 10 carbons in which at least one hydrogen is substituted with fluorine; k ¹⁰ and n ^{10 are} independently 0, 1, or 2, and the sum of k ¹⁰ and n ¹⁰ is 2, 3 or 4; ring A ¹¹ and ring A ^{21 are} independently 1,4-phenylene, or naphthalene-2,6-diyl, and among these, at least one hydrogen may pass through fluorine, chlorine, and carbon number 1 to 12 Alkyl group, or at least one hydrogen substituted by fluorine, alkyl group having 1 to 12 carbon atoms; Z ¹¹ is a single bond, ethylene, methyleneoxy, -COO-, -OCO-, -OCOO-, Or -CH = CH-COO-; Z ¹² is -CO-, or -OCO-; k ¹⁰ and n ^{10 are} independently integers of 0 to 3, and the sum of k ¹⁰ and n ¹⁰ is an integer of 1 to 4; n ²⁰ is 1 or 2; n ³⁰ is 1 or 2; Z ²⁰ Z ²¹ is independently a single bond, -CO-CH = CH -, - CH = CH-CO -, - OCO-CH = CH -, - CH = CH-COO- or -CH = CH-, but not both be single bond.

Item 3. The liquid crystal display element according to Item 2, wherein the alignment control layer-forming monomer in the liquid crystal composition is a formula (A-1), a formula (A-2), or a formula (B), P ¹⁰ and P ²⁰ , P ³⁰ , P ⁴⁰ , P ⁵⁰ and P ^{60 are} independently a group selected from the group represented by formula (Q-1); in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently Is hydrogen, fluorine, methyl, or trifluoromethyl; Sp ¹⁰ and Sp ^{20 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one hydrogen of the alkylene group may be fluorine or formula (Q -6) substitution, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-; in formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently Is hydrogen, fluorine, methyl, or at least one hydrogen alkyl group having 1 to 5 carbon atoms substituted with fluorine; Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one of the alkylene groups Hydrogen may be substituted with fluorine or chlorine, and at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-; Sp ³⁰ is a single bond or an alkylene group having 1 to 12 carbon atoms, At least one hydrogen of the alkylene group may be substituted with fluorine, and at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-; Sp ⁴⁰ is a single bond; Sp ⁵⁰ and Sp ^{60 are} independently an alkylene group having 2 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted by fluorine, chlorine, or formula (Q-6), and at least one -CH ₂ -may be -O. -, -CO-, -COO-, or -OCO- substitution; R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, 1 to 10 carbons, or at least one carbon substituted with fluorine 1 to 10 alkyl groups; R ³⁰ , R ⁴⁰ and R ^{50 are} independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 10 carbons, or an alkyl group having 1 to 10 carbons in which at least one hydrogen is replaced with fluorine; Ring A ¹¹ and Ring A ^{21 are} independently 1,4-phenylene, or naphthalene-2,6-diyl, and among these, at least one hydrogen may be substituted with fluorine, methyl, ethyl, or trifluoromethyl Z ¹¹ is a single bond, -COO- or -OCO-; Z ¹² is -CO-, or -OCO-; k ¹⁰ and n ^{10 are} independently integers from 0 to 3, and the sum of k ¹⁰ and n ¹⁰ is 1 Integer to 4; n ²⁰ is 1 or 2; n ³⁰ is 1 or 2.

Item 4. The liquid crystal display element according to any one of Items 1 to 3, wherein a ratio of the alignment control layer-forming monomer in the liquid crystal composition is 0.1 to 10 parts by weight based on the total amount of the liquid crystal compound. Range.

Item 5. The liquid crystal display element according to any one of Items 1 to 4, which contains, as a first component, at least one compound selected from the group of compounds represented by Formula (1). In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; ring A is 1,4-cyclohexyl, 1 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-; X ¹ and X ^{2 are} independently hydrogen or Fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen alkyl group having 1 to 12 carbon atoms substituted with fluorine or chlorine, at least one hydrogen substituted with fluorine or chlorine alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen Alkenyloxy having 2 to 12 carbon atoms substituted with fluorine or chlorine; a is 1, 2, 3, or 4.

Item 6. The liquid crystal display element according to any one of Items 1 to 5, which contains at least one compound selected from the group of compounds represented by Formula (1-1) to Formula (1-39) as First ingredients. In the formulae (1-1) to (1-39), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons.

Item 7. The liquid crystal display element according to Item 5 or 6, wherein the ratio of the first component in the liquid crystal composition is in a range of 10% by weight to 85% by weight.

Item 8. The liquid crystal display element according to any one of Items 1 to 7, comprising at least one compound selected from the group of compounds represented by Formula (2) as a second component. In formula (2), R ² and R ^{3 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least one hydrogen atom through fluorine or chlorine Substituted alkenyl having 2 to 12 carbons; ring B and ring C are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2, 5-difluoro-1,4-phenylene; Z ² is a single bond, ethylene, or carbonyloxy; b is 1, 2, or 3.

Item 9. The liquid crystal display element according to any one of Items 1 to 8, which contains at least one compound selected from the group of compounds represented by Formula (2-1) to Formula (2-13) as第二 组合。 The second component. In the formulae (2-1) to (2-13), R ² and R ^{3 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine.

Item 10. The liquid crystal display element according to Item 8 or 9, wherein the ratio of the second component in the liquid crystal composition is in a range of 10% by weight to 85% by weight.

Item 11. The liquid crystal display element according to any one of Items 1 to 10, comprising at least one compound selected from the group of compounds represented by Formula (3) as a third component. In formula (3), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an olefin having 2 to 12 carbons Oxy; ring D and ring F are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene, naphthalene-2,6-diyl with at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, chromogen-2 with at least one hydrogen substituted with fluorine or chlorine, 6-diyl, or chromogen-2,6-diyl in which at least one 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-difluorochroman-2,6-diyl; Z ³ and Z ^{4 are} 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.

Item 12. The liquid crystal display element according to any one of Items 1 to 11, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-22) as Third ingredient. In the formulae (3-1) to (3-22), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyloxy group having 2 to 12 carbon atoms.

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

Item 14. The liquid crystal display element according to any one of Items 1 to 13, wherein the liquid crystal composition further contains at least one compound selected from the group of polymerizable compounds represented by Formula (4) as a second addition. Thing. In formula (4), ring F ³ and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-bis Oxane-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons Oxygen, or at least one hydrogen substituted with fluorine or chlorine and 1 to 12 carbons; ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-benzene Naphthalene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1 , 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5 -Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen of these rings may be via fluorine, Chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen substituted with an alkyl group having 1 to 12 carbon atoms substituted with fluorine or chlorine; Z ⁶ and Z ^{7 are} independently mono A bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -can be replaced by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )- Among these groups, at least one hydrogen may be substituted 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 a carbon number of 1 to 10 In which at least one -CH ₂ -can be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -can be substituted with -CH = CH- or -C≡C- substitution, in these groups, at least one hydrogen may be substituted 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.

Item 15. The liquid crystal display element according to Item 14, wherein in formula (4) in the liquid crystal composition, P ¹ , P ² , and P ^{3 are} independently selected from the formula (P-1) to the formula (P- 5) A group in the group of polymerizable groups represented by the group. In the formulae (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkyl having 1 to 5 carbons.

Item 16. The liquid crystal display element according to any one of Items 1 to 15, which contains at least one selected from the group of polymerizable compounds represented by formulas (4-1) to (4-27). The compound serves as a second additive in the liquid crystal composition. In Formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ^{6 are} independently selected from the group consisting of polymerizable groups represented by Formulas (P-1) to (P-3) Base in group, Here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. At least one -CH ₂ -in this alkylene group may be passed through -O-, -COO-, -OCO-, or- OCOO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Item 17. The liquid crystal display element according to any one of Items 14 to 16, wherein the ratio of the second additive in the liquid crystal composition is in the range of 0.03 parts by weight to 10 parts by weight based on the total amount of the liquid crystal compound. .

Item 18. The liquid crystal display element according to any one of Items 1 to 17, wherein the upper limit temperature of the nematic phase is 70 ° C or higher, and the optical anisotropy (measured at 25 ° C) at a wavelength of 589 nm is 0.07 Above, the dielectric anisotropy (measured at 25 ° C) at a frequency of 1 kHz is 2 or more.

Item 19. A liquid crystal display element having a liquid crystal composition and an electrode in the liquid crystal display element according to any one of items 1 to 18 between a pair of substrates, and having a temperature above an upper limit of a nematic phase. When linearly polarized light is irradiated, the alignment control layer in the liquid crystal composition forms a monomer to react.

Item 20. The liquid crystal display element according to any one of items 1 to 19, wherein the operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and the driving method of the liquid crystal display element is an active matrix the way.

Item 21. The liquid crystal display element according to any one of items 1 to 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. A polymer-stabilized alignment type liquid crystal display element comprising the liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17, and a polymerizable compound in the liquid crystal composition is polymerized. .

Item 23. Use of a liquid crystal composition, which is the liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17, and is used in a liquid crystal display element.

Item 24. Use of a liquid crystal composition, which is the liquid crystal composition in the liquid crystal display element according to any one of items 1 to 17, and is used for a polymer-stable alignment type liquid crystal display element in.

Item 25. A compound represented by Formula (A-2). In formula (A-2), P ⁵⁰ and P ^{60 are} independently a group selected from the group represented by formula (Q-1); in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently Ground is hydrogen, fluorine, methyl, or at least one hydrogen substituted by fluorine with 1 to 5 carbons; Sp ⁵⁰ and Sp ^{60 are} independently alkylenes with 1 to 12 carbons. One hydrogen may be substituted with fluorine or formula (Q-6), and at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-; in formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen group having 1 to 5 carbon atoms substituted with fluorine or chlorine; Sp ^{41 is} independently a single bond or 1 to 12 carbon alkylene groups, at least one hydrogen of which may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO- Z ¹² is -CO-, or -OCO-; R ^{50 is} independently hydrogen, fluorine, an alkyl group having 1 to 10 carbon atoms, or at least one alkyl group having 1 to 10 carbon atoms substituted with fluorine; k ¹⁰ And n ^{10 are} independently integers of 0 to 3, and the sum of k ¹⁰ and n ¹⁰ is an integer of 1 to 4.

Item 26. Use of a compound as described in Item 25, which is used as a monomer for forming an alignment control layer.

Item 27. A liquid crystal composition which is the liquid crystal composition in the liquid crystal display element according to any one of Items 1 to 17.

The present invention also includes the following items. (A) The composition further contains at least one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. (B) An AM device containing the composition. (C) A polymer stabilized alignment (PSA) type AM device comprising the composition, and the composition further includes a polymerizable compound. (D) A polymer stabilized alignment (PSA) type AM device comprising the composition and polymerizing a polymerizable compound in the composition. (E) An element containing the composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (F) A transmissive element containing the composition. (G) Use of the composition as a composition having a nematic phase. (H) Use as an optically active composition by adding an optically active compound to the composition.

The alignment control layer-forming monomer contained in the liquid crystal composition used in the liquid crystal display element of the present invention will be described. The alignment control layer-forming monomer refers to a compound that absorbs polarized light and causes a reaction such as dimerization or isomerization. In the present invention, Formula (A), Formula (A-1), Formula (A-2), Compounds represented by formula (B), formula (C), formula (C-1), formula (D), and formula (D-1).

In formula (A), formula (A-1), formula (A-2), formula (B), formula (C), formula (C-1), formula (D) and formula (D-1), P ^{10, P 20, P 30,} P 40, P 50 and P ⁶⁰ are independently selected from the formula (Q-1) to the formula (Q-5) a group represented by the group of formula (Q-1) to the formula (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine . Formula (Q-1) is preferred, and M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, methyl, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine. More preferred M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, methyl, or trifluoromethyl. Sp ¹⁰ , Sp ²⁰ , and Sp ^{40 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted with fluorine, chlorine, or formula (Q-6), and at least one- CH ₂ -can be substituted by -O-, -CO-, -COO-, or -OCO-. It is preferably a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted by fluorine, and at least one -CH ₂ -may be -O-, -CO-, -COO-, or -OCO- substituted. The better Sp ⁴⁰ is a single key. Sp ^{30 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted with fluorine, chlorine, or formula (Q-6), and at least one -CH ₂ -may be -O. -, -CO-, -COO-, or -OCO- substitution. It is preferably a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted by fluorine, and at least one -CH ₂ -may be -O-, -CO-, -COO-, or -OCO- substituted. In formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. base. Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be replaced by fluorine or chlorine, and at least one -CH ₂ -may be -O-, -CO-,- COO-, or -OCO- substitution. Sp ⁵⁰ and Sp ^{60 are} independently an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted by fluorine, chlorine or formula (Q-6), and at least one -CH ₂ -may be -O. -, -CO-, -COO-, or -OCO- substitution. Preferred is an alkylene group having 2 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted by fluorine, chlorine or formula (Q-6), and at least one -CH ₂ -may be -O-, -CO- , -COO-, or -OCO-. Ring A ¹⁰ and Ring A ^{20 are} independently phenyl, 4-biphenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidin-5-yl, pyridin-2-yl, pyridin-5 -Yl, fluoren-2-yl, fluoren-3-yl, phenanthr-2-yl, or anthracen-2-yl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons , An alkenyl group having 2 to 12 carbon atoms, an alkoxy group having 1 to 11 carbon atoms, or an alkenyloxy group having 2 to 11 carbon atoms, in which at least one hydrogen may be substituted with fluorine or chlorine. Ring A ¹¹ , ring A ²¹ , ring A ¹² , ring A ²² and ring A ^{30 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4, 4'-biphenyl, naphthalene-2,6-diyl, decalin-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyridine Uran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrene-2,7-diyl , Phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10 , 11,12,13,14,15,16,17-tetradechydrocyclopenta [a] phenanthrene-3,17-diyl, the adjacent bonds are -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO-, and R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, carbon When an alkyl group having 1 to 10 or an alkyl group having 1 to 10 carbons in which at least one hydrogen is substituted with fluorine is 1,4-phenylene, 4,4'-biphenylyl, naphthalene-2,6 -Diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, the In these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or alkenyl having 2 to 11 carbons Oxygen extraction , The plurality of groups, at least one hydrogen may be substituted by fluorine or chlorine. Ring A ⁴⁰ is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenyl, naphthalene-2,6-diyl, ten Hydronaphthalene-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, pyrene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl , Perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecane Cyclopenta [a] phenanthrene-3,17-diyl with adjacent bonds -CH = CH-, -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or When -CH = CH-COO-, 1,4-phenylene, 4,4'-biphenyl, 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 these rings, at least one hydrogen may pass through P ²⁰ -Sp ^20- , fluorine , 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. Among these groups, at least One hydrogen can be replaced by fluorine or chlorine. Ring A ¹¹ and Ring A ^{21 are} independently 1,4-phenylene, naphthalene-2,6-diyl, and among these, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, or At least one hydrogen is substituted with a fluorine-substituted alkyl group having 1 to 12 carbon atoms. Z ^{10 is} independently -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH-COO -, R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, an alkyl group having 1 to 10 carbons, or an alkyl group having 1 to 10 carbons in which at least one hydrogen is replaced with fluorine. Z ^{11 is} independently a single bond or an alkylene group having 1 to 6 carbon atoms. In this alkylene group, at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO-, or- OCOO- substituted, at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted with fluorine or chlorine. A single bond, ethylene, methyleneoxy, -COO-, -OCO-, or -OCOO- is preferred, and a single bond, -COO- or -OCO- is more preferred. Z ¹² is -CO- or -OCO-. Z ²⁰ and Z ^{21 are} independently a single bond, an alkylene group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and at least one of them is an alkenyl group having 2 to 6 carbon atoms. Among these alkylene and alkenyl groups, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, -OCO-, or -OCOO-, and at least one other-(CH ₂ ) ₂ -It may be substituted by -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted by fluorine or chlorine. Single bond, -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, -CH = CH-COO-, or -CH = CH- are preferred, but not single bonds . R ³⁰ , R ⁴⁰ , R ⁴¹ and R ^{50 are} independently hydrogen, fluorine, chlorine, an alkyl group having 1 to 10 carbons, or an alkyl group having 1 to 10 carbons in which at least one hydrogen is replaced with fluorine. k ¹⁰ and n ^{10 are} independently integers of 0 to 3, and the sum of k ¹⁰ and n ¹⁰ is an integer of 1 to 6, preferably the sum of k ¹⁰ and n ¹⁰ is an integer of 1 to 4. n ²⁰ is 1 or 2. n ³⁰ is 1 or 2.

It is considered that the alignment control layer-forming monomer having a vinylidene group is irradiated with ultraviolet light to generate formation of a cyclobutane ring by photoisomerization or dimerization of a trans isomer to a cis isomer. This property can be used to prepare a thin film capable of aligning liquid crystal molecules. In order to prepare the film, the ultraviolet rays to be irradiated are suitably linearly polarized light. First, the alignment control layer-forming monomer is added to the liquid crystal composition in a range of 0.1% to 10% by weight, and the composition is heated in order to dissolve the alignment control layer-forming monomer. This composition was injected into a device without an alignment film. Second, while linearly polarizing light is irradiated to the element above the upper limit temperature of the nematic phase, photoisomerization or dimerization of the monomers forming the alignment control layer is promoted. The photoisomerized compounds or the dimerized compounds are aligned in a fixed direction. At the same time, photopolymerization occurs and a thin film is formed 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 composition or device will be described. Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, preferred embodiments of the component compounds will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Eighth, the use of the composition will be described. Ninth, a method of manufacturing an element will be described.

First, the composition of the composition will be described. This composition contains a plurality of liquid crystal compounds. This composition may contain additives. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. From the viewpoint of a liquid crystal compound, the composition is classified into a composition A and a composition B. The composition A may contain other liquid crystal compounds 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 a compound is mixed in the composition for the purpose of further adjusting the characteristics.

The composition B contains substantially only a liquid crystal compound selected from the compound (1) and the compound (2). The term "substantially" means that the composition may contain additives, but does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. From the viewpoint of cost reduction, the composition B is superior to the composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is superior to the composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or device will be described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L is large or high, M is medium, and S is small or low. The symbols L, M, and S are classifications based on a qualitative comparison between the component compounds, and the symbol 0 (zero) means that the dielectric anisotropy is extremely small.

[Table 2]

When the component compounds are mixed in the composition, the main effects of the component compounds on the characteristics of the composition are as follows. The alignment control layer-forming monomer is the first additive. When the alignment control layer-forming monomer is dimerized or isomerized by polarized light, it is arranged at a molecular level in a fixed direction. Therefore, a thin film prepared from an alignment control layer-forming monomer aligns liquid crystal molecules in the same manner as an alignment film such as polyimide. The compound (1) as the first component improves the dielectric anisotropy. The compound (2) as the second component decreases the viscosity or raises the upper limit temperature. The compound (3) as the third component increases the dielectric constant in the minor axis direction. The compound (4) as a second additive provides a polymer by polymerization, which shortens the response time of the device and improves the afterimage of the image.

Third, the combination of components in the composition, the preferred ratio of the components, and the basis thereof will be described. A preferred combination of ingredients in the composition is a first ingredient + a first additive, a first ingredient + a second ingredient + a first additive, a first ingredient + a third ingredient + a first additive, or a first ingredient + The second component + the third component + the first additive. A further preferred combination is a first component + a second component + a first additive. A second additive may be further added to these combinations.

In order to align the liquid crystal molecules, based on the total amount of liquid crystal compounds, the preferred ratio of the alignment control layer-forming monomer as the first additive is about 0.1 parts by weight or more. A preferred ratio of the alignment control layer-forming monomer is about 10 parts by weight or less. A further preferred ratio is in the range of about 0.3 parts by weight to about 6 parts by weight. A particularly preferred ratio is in the range of about 0.5 parts by weight to about 4 parts by weight.

In order to improve the dielectric anisotropy, the preferred ratio of the first component is about 10% by weight or more. In order to lower the lower limit temperature or reduce the viscosity, the preferred ratio of the first component is about 85% by weight or less. A further preferred ratio is in the range of about 15% by weight to about 80% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 75% by weight.

In order to increase the upper limit temperature or to reduce the viscosity, the preferred ratio of the second component is about 10% by weight or more. In order to improve the dielectric anisotropy, the preferred ratio of the second component is about 85% by weight or less. A further preferred ratio is in the range of about 15% by weight to about 80% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 75% by weight.

In order to increase the dielectric constant in the minor axis direction, the preferred ratio of the third component is about 3% by weight or more. In order to lower the lower limit temperature, the preferred ratio of the third component is about 25% by weight or less. A further preferred ratio is in the range of about 5 wt% to about 20 wt%. A particularly preferred ratio is in the range of about 5 wt% to about 15 wt%.

The second additive may be added to the composition for the purpose of being suitable for a polymer-stabilized alignment device. In order to align the liquid crystal molecules, a preferable ratio of the additive is about 0.03 parts by weight or more based on the total amount of the liquid crystal compound. In order to prevent display failure of the device, a preferable ratio of the additive is about 10 parts by weight or less. A further preferred ratio is in the range of about 0.1 parts by weight to about 2 parts by weight. A particularly preferred ratio is in the range of about 0.2 parts by weight to about 1.0 part by weight.

Fourth, preferred embodiments of the component compounds will be described. In Formula (1), Formula (2), and Formula (3), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. In order to improve the stability to ultraviolet rays or heat, preferred R ¹ is an alkyl group having 1 to 12 carbon atoms. R ² and R ^{3 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine 12 alkenyl. In order to reduce the viscosity, preferred R ² or R ³ is an alkenyl group having 2 to 12 carbon atoms, and in order to improve the stability to ultraviolet rays or heat, preferred R ² or R ³ is an alkyl group having 1 to 12 carbon atoms. R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkenyloxy group having 2 to 12 carbons. In order to improve the stability to ultraviolet rays or heat, a preferred R ⁴ or R ⁵ is an alkyl group having 1 to 12 carbons. In order to increase the dielectric constant in the minor axis direction, a preferred R ⁴ or R ⁵ is a carbon number 1 to 12 alkoxy.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. In order to reduce the viscosity, further preferred alkyl groups are methyl, ethyl, propyl, butyl, or pentyl.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, or heptyloxy. In order to reduce the viscosity, further preferred alkoxy groups are methoxy or ethoxy.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3 -Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. In order to reduce the viscosity, further preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred stereo configuration of -CH = CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity and the like, among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl, etc. Trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred. Among these alkenyl groups, linear alkenyl groups are preferred to branched alkenyl groups.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to reduce viscosity, further preferred alkenyloxy is allyloxy or 3-butenyloxy.

Preferred examples of the alkyl group in which at least one hydrogen is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7 -Fluoroheptyl, or 8-fluorooctyl. In order to increase the dielectric anisotropy, further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.

Preferred examples of the alkenyl group in which at least one hydrogen is substituted 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. In order to reduce the viscosity, further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring A is 1,4-cyclohexyl, 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. In order to improve optical anisotropy, the preferred ring A is 1,4-phenylene or 2-fluoro-1,4-phenylene. Tetrahydropyran-2,5-diyl is or , Preferably .

Ring B and Ring C are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene base. To reduce viscosity, the preferred ring B or ring C is 1,4-cyclohexyl, or to improve the optical anisotropy, the preferred ring B or ring C is 1,4-phenylene. Ring D and Ring F are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen atom Fluorine or chlorine substituted 1,4-phenylene, naphthalene-2,6-diyl, at least one hydrogen substituted with fluorine or chlorine naphthalene-2,6-diyl, chromogen-2,6-diyl , Or at least one chromogen-2,6-diyl substituted with fluorine or chlorine. To reduce viscosity, the preferred ring D or ring F is 1,4-cyclohexyl. In order to increase the dielectric constant in the minor axis direction, the preferred ring D or ring F is tetrahydropyran-2,5-. In order to improve the optical anisotropy of the diradical, the preferred ring D or ring F 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, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromogen-2,6-diyl. In order to increase the dielectric constant in the minor axis direction, the preferred ring E is 2,3-difluoro-1,4-phenylene.

Z ¹ is a single bond, ethylene, carbonyloxy, or difluoromethyleneoxy. In order to reduce the viscosity, the preferred Z ¹ is a single bond, and to improve the dielectric anisotropy, the preferred Z ¹ is a difluoromethyleneoxy group. Z ² is a single bond, ethylene, or carbonyloxy. To reduce viscosity, the preferred Z ² is a single bond. Z ³ and Z ^{4 are} independently a single bond, ethylene, carbonyloxy, or methyleneoxy. In order to reduce the viscosity, the preferred Z ³ or Z ⁴ is a single bond. In order to increase the dielectric constant in the minor axis direction, the preferred Z ³ or Z ⁴ is a methyleneoxy group.

X ¹ and X ^{2 are} independently hydrogen or fluorine. To increase the dielectric anisotropy, preferred X ¹ or X ² is fluorine.

Y ¹ is fluorine, chlorine, at least one alkyl group having 1 to 12 carbon atoms substituted with fluorine or chlorine, at least one hydrogen group having 1 to 12 carbon atoms substituted with fluorine or chlorine, or at least one hydrogen group with fluorine Or a chlorine-substituted alkenyloxy group having 2 to 12 carbon atoms. In order to lower the lower limit temperature, Y ¹ is preferably fluorine.

A preferred example of the alkyl group in which at least one hydrogen is substituted with fluorine or chlorine is trifluoromethyl. A preferred example of the alkoxy group in which at least one hydrogen is substituted with fluorine or chlorine is trifluoromethoxy. A preferred example of the alkenyloxy group in which at least one hydrogen is substituted with fluorine or chlorine is trifluorovinyloxy.

a is 1, 2, 3, or 4. In order to lower the lower limit temperature, a is preferably 2 and in order to increase the dielectric anisotropy, a is preferably 3. b is 1, 2, or 3. In order to reduce the viscosity, the preferred b is 1, and in order to increase the upper limit temperature, the preferred b is 2 or 3. c is 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less. In order to reduce the viscosity, the preferred c is 1, and in order to increase the upper limit temperature, the preferred c is 2 or 3. In order to reduce the viscosity, the preferred d is 0, and to lower the lower limit temperature, the preferred d is 1.

In formula (4), P ¹ , P ² , and P ^{3 are} independently a polymerizable group. Preferably, 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). Further preferably, P ¹ , P ² , or P ³ is a group represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P ¹ , P ² , or P ³ is a group represented by formula (P-1) or formula (P-2). The most preferable P ¹ , P ² , or P ³ is a group represented by the formula (P-1). A preferred group represented by the formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The waveform lines of the formulas (P-1) to (P-5) indicate the bonded portions.

In the formulae (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkyl having 1 to 5 carbons. In order to improve reactivity, preferred M ¹ , M ² , or M ³ is hydrogen or methyl. Further preferred M ¹ is hydrogen or methyl, and further preferred M ² or M ³ is hydrogen.

Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. At least one of the alkylene groups may be -CH ₂ -via -O-, -COO-, -OCO- Or -OCOO- substitution, at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferably, Sp ¹ , Sp ² , or Sp ³ is a single bond, -CH ₂ -CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH- , Or -CH = CH-CO-. Further preferred Sp ¹ , Sp ² , or Sp ³ are single bonds.

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 these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one Hydrogen is substituted by a C1-C12 alkyl group substituted by fluorine or chlorine. Preferred ring F ³ or ring I is phenyl. Ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 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 may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen is substituted by a C1-C12 alkyl group substituted by fluorine or chlorine. Preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁶ and Z ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, at least one of -CH ₂ -may pass through -O-, -CO-, -COO-, or -OCO -Substitution, at least one -CH ₂ -CH ₂ -may be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C ( CH ₃ )-substituted, in which at least one hydrogen may be substituted with fluorine or chlorine. Preferably, Z ⁶ or Z ⁷ is a single bond, -CH ₂ -CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Further preferred Z ⁶ or Z ⁷ are single bonds.

h is 0, 1, or 2. The preferred h 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, preferred component compounds are shown. A preferred alignment control layer forming monomer will be described. The alignment control layer-forming monomer preferably has at least two polymerizable groups. When there is only one polymerizable group, it is considered that the alignment control layer obtained after polymerization becomes a soft film. Therefore, in a temperature environment where the liquid crystal display element is driven, the alignment control layer is easily deformed and the alignment control force is also easily reduced. It is considered that when there are at least two polymerizable groups, the cross-link density of the alignment control layer obtained after polymerization is increased to become a strong film. Therefore, it is considered that deformation of the alignment control layer is difficult to occur even in a high-temperature environment. . The site where dimerization or isomerization occurs due to polarized light is vinylidene. In the case of having a chalcone structure or a cinnamate structure containing vinylidene group, the same effect is obtained, so it is preferable. When controlling the solubility in a liquid crystal compound, in order to improve compatibility with the terminal chain of the liquid crystal compound, a spacer may be introduced between the polymerizable group and the central structure. The spacer is preferably linear or branched. The length of the spacer is preferably 2 or more. It is also possible to use a combination of two or more kinds of alignment control layers. A specific example of a preferred alignment control layer-forming monomer is exemplified. Compound (A-1-1) to Compound (A-1-8), Compound (AA-1) to Compound (AA-15), Compound (A-2-1) to Compound (A-2-12) , Compound (B-1-1) to compound (B-1-17), compound (C-1-1) to compound (C-1-10), and compound (D-1-1) to compound (D- 1-9). Compound (A-1-4) to compound (A-1-7), compound (AA-5), compound (AA-7), compound (A-2-1) to compound (A-2-2), N in the compound (A-2-7) to the compound (A-2-12) is independently 2 to 12. Among the compounds (A-2-1) to (A-2-2) and the compounds (A-2-7) to (A-2-12), from the viewpoint of improving compatibility with liquid crystal compounds, In other words, more preferable n is 2 to 10. Examples of preferred alignment control layer-forming monomers having a cinnamate structure other than the compounds described above include compounds (I-1) to compounds (I-1) described in paragraphs 0029 to 0033 of Japanese Patent Laid-Open No. 2011-202168. I-34), compounds (I-36) to compounds (I-39), compounds (I-1) to compounds (I-52) described in paragraphs 0031 to 0042 of Japanese Patent Laid-Open No. 2010-285499 Compound (I-56) to Compound (I-59), Compound (I-60) to Compound (I-62).

Preferred compound (1) is the compound (1-1) to compound (1-39) according to item 6. Among these compounds, it is preferred that 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). It is preferred that 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), compound (1-18) and compound (1-29), compound (1-24) and compound (1-29), or a combination of compound (1-29) and compound (1-30).

Preferred compound (2) is the compound (2-1) to compound (2-13) according to item 9. Among these compounds, it is preferred that 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 that at least two of the second component are compound (2-1) and compound (2-5), compound (2-1) and compound (2-6), compound (2-1) and compound (2- 7) The combination of compound (2-3) and compound (2-5), compound (2-3) and compound (2-6), compound (2-3) and compound (2-7).

Preferred compound (3) is the compound (3-1) to compound (3-22) according to item 12. Among these compounds, it is preferred that 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 (3-10). It is preferable that at least two of the third component are compound (3-1) and compound (3-6), compound (3-3) and compound (3-6), compound (3-3) and compound (3- 10), compound (3-4) and compound (3-6), compound (3-4) and compound (3-8), or a combination of compound (3-6) and compound (3-10).

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, 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 giving a torsion angle to the helical structure of the liquid crystal molecules. Examples of such compounds are compounds (Op-1) to (Op-5). A preferable ratio of the optically active compound is about 5 parts by weight or less based on the total amount of the liquid crystal compound. A further preferred ratio is in the range of about 0.01 part by weight to about 2 parts by weight.

In order to prevent the decrease in specific resistance caused by heating in the atmosphere, or to maintain a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, the antioxidant Added to the composition. Preferable examples of the antioxidant include a compound (G) in which n is an integer of 1 to 9, and the like.

In the compound (G), preferred n is 1, 3, 5, 7, or 9. Further preferably n is 7. The compound (G) in which n is 7 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, due to its low volatility. In order to obtain the effect, a preferred ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature, or to not raise the lower limit temperature, the preferred ratio of the antioxidant is about 600 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. In addition, a light stabilizer such as an amine having a steric hindrance is also preferable. In order to obtain the effect, the preferred ratio of these absorbers or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature, or to not raise the lower limit temperature, the preferred ratio of these absorbers or stabilizers is about 10,000. ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

In order to be suitable for a device in a guest host (GH) mode, a dichroic dye such as an azo pigment, an anthraquinone pigment, or the like is added to the composition. A preferable ratio of the coloring matter is in the range of about 0.01 to about 10 parts by weight based on the total amount of the liquid crystal compound. To prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition. In order to obtain the effect, the preferred ratio of the defoaming agent is about 1 ppm or more, and in order to prevent poor display, the preferred ratio of the defoaming agent is about 1000 ppm or less. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for a polymer stabilized alignment (PSA) type device, a polymerizable compound is used. Compound (4) is suitable for this purpose. The compound (4) and a polymerizable compound different from the compound (4) may be added to the composition together. 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 acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxetane, oxetane), and vinyl group. Ketones and other compounds. Further preferred examples are derivatives of acrylates or methacrylates. By changing the kind of the compound (4), or by combining a polymerizable compound different from the compound (4) in an appropriate ratio, the reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules can be adjusted. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast or a long life can be achieved.

A polymerizable compound such as the compound (4) or the alignment control layer-forming monomer is polymerized by irradiation with ultraviolet rays. The polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization, appropriate types of initiators, and appropriate amounts are known to those having ordinary skill in the art and are described in the literature. For example, Omnirad 651 (registered trademark; IGM Resins) as a photopolymerization initiator, Omnirad 184 (registered trademark; IGM Resins), or Austrian Omnirad 1173 (registered trademark; IGM Resins) is suitable for free radical polymerization. A preferred ratio of the photopolymerization initiator is in the range of about 0.1 parts by weight to about 5 parts by weight based on the total amount of the polymerizable compound. A further preferred ratio is in the range of about 1 part by weight to about 3 parts by weight.

When a polymerizable compound such as the storage compound (4) or the alignment control layer-forming monomer is used, 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, a hydroquinone derivative such as methyl hydroquinone, 4-tert-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 electrically negative and tend to have a partial negative charge. Carbon and hydrogen are neutral or tend to have a partially positive charge. Polarity is caused by the uneven distribution of partial charges among different kinds of atoms in a compound. For example, the polar compound has at least one of a partial structure such as -OH, -COOH, -SH, -NH ₂ ,>NH,> N-.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Illustrative synthesis methods. Compound (1-1) was synthesized by a method described in Japanese Patent Application Publication No. Hei 2-503441. Compound (2-5) was synthesized by a method described in Japanese Patent Laid-Open No. 57-165328. Compound (3-18) is synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. Antioxidants are commercially available. The compound of formula (5) in which n is 1 is available from Sigma-Aldrich Corporation. Compound (5) and the like where n is 7 are synthesized by a method described in US Pat. No. 3,660,505. The alignment control layer forming monomer having a vinyl group is formed by using International Publication No. 2013/077343, International Publication No. 2002/048281, International Publication No. 2015/004947, US Publication No. 2013-0277609, and Japanese Patent Laid-Open Publication 63-8361. The alignment control layer-forming monomer having an α-fluoroacrylate group is synthesized by a method described in Japanese Patent Laid-Open No. 2005-112850.

Compounds without a synthetic method can be synthesized by methods described in the following books: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" Reactions "(John Wiley & Sons, Inc.)," Comprehensive Organic Synthesis "(Pergamon Press)," New Experimental Chemistry Lecture "( Maruzen) and so on. The composition is prepared from a compound obtained in the above-mentioned manner by a known method. For example, the component compounds are mixed and then dissolved in each other by heating.

Eighth, the use of the composition will be described. Most of the compositions have a lower limit temperature of about -10 ° C or lower, an upper limit temperature of about 70 ° C or higher, and optical anisotropy in a 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 can be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in a range of about 0.10 to about 0.30 can also be prepared by this method. The 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, and can be used as an optically active composition by adding an optically active compound.

This composition can be used for an AM device. Furthermore, it can be used for a PM device. This composition can be used for AM devices and PM devices with PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. Particularly preferred is for AM devices having VA mode, OCB mode, IPS mode, or FFS mode. In an AM device having an IPS mode or an FFS mode, when no voltage is applied, the arrangement of the liquid crystal molecules may be parallel to the glass substrate, or may be vertical. These elements can be reflective, transmissive, or transflective. It is preferably used for a transmissive element. It can also be used for amorphous silicon-TFT elements or polycrystalline silicon-TFT elements. It can also be used for nematic curvilinear aligned phase (NCAP) devices made by microencapsulating the composition, or polymer dispersed by forming a three-dimensional network polymer in the composition. , PD) type components.

Ninth, a method of manufacturing an element will be described. The first step is to add the alignment control layer-forming monomer to the liquid crystal composition and heat the composition at a temperature higher than the upper limit temperature to dissolve the composition. The second step is to inject the composition into a liquid crystal display element. In this step, if 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 step is to irradiate the linearly polarized ultraviolet rays while heating the liquid crystal composition to a temperature higher than the upper limit temperature. The alignment control layer-forming monomer undergoes dimerization or isomerization by linearly polarized ultraviolet light, and also undergoes polymerization. The preferable cumulative light amount (J / cm ² ) of the linearly polarized ultraviolet rays is 0.1 J / cm ² to 20 J / cm ² when it reaches the surface of the device. A preferable range of the accumulated light amount is 0.1 J / cm ² to 10 J / cm ² , and a more preferable range is 0.1 J / cm ² to 7 J / cm ² . The cumulative light amount (J / cm ² ) can be obtained by the ultraviolet irradiance (unit: mW / cm ² ) × irradiation time (unit: sec). The temperature conditions at the time of linearly polarized ultraviolet irradiation are preferably set in the same manner as the heat treatment temperature. The linearly polarized ultraviolet irradiation time is calculated based on the illuminance of the lamp. Therefore, from the viewpoint of production efficiency, it is preferable to perform the illuminance as high as possible. The polymer containing the alignment control layer-forming monomers is aligned at a molecular level in a fixed direction and fixed on the substrate, so the thin film has a function as a liquid crystal alignment film. A liquid crystal display element without an alignment film such as polyimide can be manufactured by this method. [Example]

The present invention will be further described in detail through examples. The invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The characteristics of the compound, composition, and device were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed at room temperature, 500 MHz, and 16 times of accumulation. Tetramethylsilane was used as the internal standard. ^{In the 19} F-NMR measurement, CFCl _{3 was} used as an internal standard, and the total number of measurements was performed 24 times. In the description of the nuclear magnetic resonance spectrum, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet. (Quintet), sex means sixt (sextet), m means multiplet, and br means broad.

Gas chromatographic analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas was helium (2 mL / min). The sample gasification chamber was set to 280 ° C, and the detector (flame ionization detector (FID)) was set to 300 ° C. For the separation of constituent compounds, a capillary column DB-1 (30 m in length, 0.32 mm in inner diameter, and 0.25 μm in thickness) manufactured by Agilent Technologies Inc. was used; the fixed liquid phase was dimethylpolysilicon Oxane; non-polar). After the column was held at 200 ° C for 2 minutes, the temperature was raised to 280 ° C at a rate of 5 ° C / min. After the sample was prepared as an acetone solution (0.1% by weight), 1 μL of the sample was injected into the sample gasification chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed a retention time of a peak and an area of the peak corresponding to the component compounds.

As a solvent for diluting the sample, chloroform, hexane, or the like can be used. In order to separate the component compounds, the following capillary columns can be used. HP-1 manufactured by Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Rtx-1 manufactured by Restek Corporation (length 30 m, internal Diameter 0.32 mm, film thickness 0.25 μm), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd of Australia. To prevent compound peaks from overlapping, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, and film thickness 0.25 μm) manufactured by Shimadzu Corporation can be used.

The ratio of the liquid crystal compound contained in the composition can be calculated by the following method. A gas chromatograph (FID) was used to detect a mixture of liquid crystal compounds. The area ratio of the peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of various liquid crystal compounds can be regarded as one. Therefore, the ratio (% by weight) of the liquid crystalline compound can be calculated from the peak area ratio.

Measurement sample: When measuring the characteristics of the composition and the device, the composition is directly used as a sample. When measuring the characteristics of a compound, a sample for measurement was prepared by mixing the compound (15% by weight) with a mother liquid crystal (85% by weight). From the values obtained by the measurement, the characteristic values of the compounds were calculated by extrapolation. (Extrapolated value) = ｛(measured value of the sample)-0.85 × (measured value of the mother liquid crystal)｝ /0.15. When the smectic phase (or crystal) is precipitated at 25 ° C in this ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, and 1% by weight: 99% % Order change. This extrapolation method was used to find the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound.

The following mother liquid crystals were used. The proportion of the component compounds is expressed in% by weight.

Measurement method: The characteristics were measured by the following method. Most of these methods are methods described in the JEITA standard (JEITA · ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA) or modified and modified.成 的 方法。 into the method. In the TN device used for the measurement, a thin film transistor (TFT) was not mounted.

(1) Upper limit temperature of the nematic phase (NI; ° C): A sample is placed on a hot plate of a melting point measuring device equipped with a polarizing microscope, and heated at a rate of 1 ° C / min. The temperature at which a part of the sample changed from a nematic phase to an isotropic liquid was measured. The upper limit temperature of the nematic phase may be simply referred to as the "upper limit temperature".

(2) Lower limit temperature (T _C ; ℃) of nematic phase: Put the sample with nematic phase into the glass bottle at 0 ℃, -10 ℃, -20 ℃, -30 ℃, and -40 ℃ After storing in a freezer for 10 days, the liquid crystal phase was observed. For example, when the sample is in the state of a nematic phase at -20 ° C and changes to a crystal or a smectic phase at -30 ° C, T _{C is} described as <-20 ° C. The lower limit temperature of the nematic phase may be simply referred to as "lower limit temperature".

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

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

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

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

(7) Threshold voltage (Vth; measured at 25 ° C; V): The LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample was placed in a normally white mode TN device with a gap (cell gap) of two glass substrates of 0.45 / Δn (μm) and a twist angle of 80 degrees. The voltage (32 Hz, rectangular wave) applied to this device is 0.02 V as a unit and gradually increases from 0 V to 10 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 having a transmittance of 100% when the amount of light reaches the maximum and a transmittance of 0% when the amount of light reaches the minimum is made. The threshold voltage is expressed by the voltage when the transmittance reaches 90%.

(8) Voltage holding ratio (VHR-1; measured at 25 ° C;%): The TN device used in the measurement has a polyimide alignment film, and the distance (cell gap) between the two glass substrates is 5 μm. This device was sealed with an adhesive hardened with ultraviolet rays after the sample was put in the sample. A pulse voltage (5 V, 60 microseconds) was applied to the TN device to charge it. Using a high-speed voltmeter, the attenuated voltage was measured during 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. The area B is the area without attenuation. The voltage holding ratio is expressed as a percentage of the area A to the area B.

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

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

(11) Voltage holding ratio (VHR-4; measured at 25 ° C;%): After heating the TN element filled with the sample in a constant temperature bath at 80 ° C for 500 hours, measure the voltage holding ratio and evaluate the thermal resistance. stability. In the measurement of VHR-4, the attenuated voltage was measured during 16.7 milliseconds. A composition having a large VHR-4 has a large stability to heat.

(12) Response time (τ; measured at 25 ° C; ms): The LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a normally white mode TN device with a distance (cell gap) of two glass substrates of 5.0 μm and a twist angle of 80 degrees. A rectangular wave was applied to the device (60 Hz, 5 V, 0.5 seconds). At this time, the device was irradiated with light from the vertical direction, and the amount of light transmitted through the device was measured. The transmittance is considered to be 100% when the amount of light reaches the maximum, and the transmittance is considered to be 0% when the amount of light is the smallest. Rise time (τr: rise time; milliseconds) is the time required for the transmittance to change from 90% to 10%. Fall time (τf: fall time; milliseconds) is the time required to change from 10% to 90% of the transmittance. The response time is represented by the sum of the rise time and the fall time obtained in the manner described above.

(13) Elastic constant (K; measured at 25 ° C; pN): An HP4284A type LCR tester manufactured by Hewlett-Packard Co., Ltd. was used for the measurement. A sample was placed in a horizontal alignment element with a gap (cell gap) of two glass substrates of 20 μm. A charge of 0 volts to 20 volts was applied to the device, and the capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), the measured capacitance (C) and the applied voltage (V) are fitted, and according to the equation ( 2.99) to obtain the values of K11 and K33. Next, K22 is calculated by using the values of K11 and K33 previously obtained in the formula (3.18) on page 171 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun). The elastic constant is represented by the average value of K11, K22, and K33 calculated | required as mentioned above.

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

(15) Helical pitch (P; measured at room temperature; μm): Helical pitch is measured by the wedge method. Refer to "LCD Fact Sheet" on page 196 (issued in 2000, Maruzen). The sample was injected into the wedge-shaped unit and left at room temperature for 2 hours, and then the interval to the misalignment line was observed with a polarizing microscope (Nikon (stock), trade name MM40 / 60 series) (d2-d1) . The helical pitch (P) is calculated from the following formula which expresses the angle of the wedge-shaped unit as θ. P = 2 × (d2-d1) × tanθ.

The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is a trans configuration. The number in parentheses after the mark corresponds to the number of the compound. The symbol (-) refers to 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.

Expression of compounds using symbols R- (A ₁ ) -Z ₁ -¼¼Z _n- (A _n ) -R '[Table 3]

Example of element 1. Raw material A composition to which an alignment control layer-forming monomer is added is injected into an element having no alignment film. After the linearly polarized ultraviolet rays were irradiated, the alignment of the liquid crystal molecules in the device was confirmed. First, the raw materials will be described. The raw material is appropriately selected from the composition (M1) to the composition (M20). The monomer for forming the alignment control layer is the compound (A-1-1) or the compound (A-2-1-1). And compound (A-2-2-1), compound (A-2-3), compound (A-2-4), compound (B-1), compound (C-1-1), compound (D- 1-5), compound (D-1-7) and compound (D-1-8) are appropriately selected. 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 ℃; Tc <-30 ℃; 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 ℃; Tc <-20 ℃; Δn = 0.099; Δε = 6.1; Vth = 1.74 V; 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 (1-2) 3% 3-BB (F) B (F, F) XB (F) -F (1-2) 3% 4-BB (F) B (F, F) XB (F)- F (1-2) 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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; 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 ℃; 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 ℃; Tc <-20 ℃ 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 ℃; Tc <-20 ℃; Δn = 0.093; Δε = 6.9; Vth = 1.50 V; 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 ℃; Tc <-20 ℃; Δn = 0.111; Δε = 4.7; Vth = 1.86 V; 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-HHEB H-5 (2-11) 3% NI = 83.0 ℃; Tc <-20 ℃; Δn = 0.086; Δε = 3.8; Vth = 1.94 V; η = 7.5 mPa · s; γ1 = 51.5 mPa · s.

[Composition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℃; Tc <-20 ℃; Δn = 0.109; Δε = 4.8; Vth = 1.75 V; 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-HBBXB (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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; Δn = 0.109; Δε = 10.6; Vth = 1.34 V; 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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; 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 ℃; Tc <-20 ℃; Δn = 0.099; Δε = 5.0; Vth = 1.64 V; 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 ℃; Tc <-20 ℃; Δn = 0.091; Δε = 5.7; Vth = 1.83 V; η = 14.9 mPa · s; γ1 = 69.3 mPa · s.

The first additive is the following compound.

2. Orientation of liquid crystal molecules <Polarized light exposure conditions> A 250 W ultra-high pressure mercury lamp (Multi-Light manufactured by Ushio Electric Co., Ltd.) and a wire grid polarizer (Mott ProFlux (UVT-260A) manufactured by MOXTEK Co., Ltd., and irradiated with 3 mW / cm ² (Ultraviolet illuminance meter UIT-150 and UVD-S313 manufactured by Ushio Electric Corporation were used to measure Intensity of light). Example 1 Based on the total amount of the composition (M1), an alignment control layer-forming monomer (A-1-1) was added to the composition (M1) in a proportion of 0.3 parts by weight. This mixture was injected into an IPS device without an alignment film at 90 ° C (above the upper limit temperature). While heating the IPS element at 90 ° C (above the upper limit temperature), the element was irradiated with linearly polarized ultraviolet rays (313 nm, 5.0 J / cm ² ) from the normal direction, thereby obtaining an element having an alignment control layer formed thereon. The irradiated ultraviolet rays pass through a polarizer, thereby becoming linearly polarized light. Next, the element on which the alignment control layer was formed was set on a polarizing microscope to observe the alignment state of the liquid crystal. The polarizer and the analyzer of a polarizing microscope are arranged so that their respective transmission axes are orthogonal to each other. First, the alignment direction of the liquid crystal molecules is parallel to the transmission axis of the polarizer of the polarizing microscope, that is, the angle formed by the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope is 0 degrees. The element is set on a horizontal rotating platform of a polarizing microscope. Light was irradiated from the lower side of the element, that is, the polarizer side, and the presence or absence of light passing through the analyzer was observed. Since no light transmitted through the analyzer was observed, the alignment was judged to be "good". In addition, in the same observation, when the light transmitted through the analyzer is observed, the alignment is determined to be "bad". Secondly, the element is rotated on the horizontal rotation platform of the polarizing microscope, and the angle formed by the transmission axis of the polarizer of the polarizing microscope and the alignment direction of the liquid crystal molecules is changed from 0 degrees. It was confirmed that the intensity of the light transmitted through the analyzer increases as the angle formed by the transmission axis of the polarizer of the polarizing microscope and the alignment direction of the liquid crystal molecules increases, and becomes approximately maximum when the angle is 45 degrees. In the device obtained from the above, the liquid crystal molecules are aligned in a direction substantially horizontal to the main surface of the substrate of the device, and it is determined as "horizontal alignment".

Examples 2 to 24 The alignment control layer-forming monomer was added to the composition (M1) to the composition (M20) in a combination of Table 4. This mixture was used to set the injection temperature of the liquid crystal and the temperature at the time of polarized light exposure to the temperatures described in Table 4. Except that, an element was produced by the same method as in Example 1, and light leakage was observed by the same method as in Example 1. Is there.

Comparative Example 1 Except that an alignment control layer-forming monomer was not added to the composition (M1), it was injected into an IPS element without an alignment film by the same method as in Example 1 and subjected to heating and polarization exposure treatment. The same method as in Example 1 was used to observe the presence or absence of light leakage. The results of Examples 1 to 24 and Comparative Example 1 are summarized in Table 4.

[Table 4] Alignment of liquid crystal molecules

Comparative Example 2 The following alignment control layer-forming compound (R-1), which does not have a polymerizable group but has a cinnamate structure, was added to the composition (M1), and injected into a composition having no alignment by the same method as in Example 1. The film is subjected to a heated polarized light exposure process in an IPS element. The alignment state of the liquid crystal was observed by the same method as in Example 1. An area where light does not pass through the analyzer is confirmed in the element, and an area where light passes through the analyzer is also confirmed. The alignment was judged to be comprehensive.

3. Compatibility of the alignment control layer-forming monomer and the liquid crystal composition For the mixture of the liquid crystal composition obtained in the example and the alignment control layer-forming monomer and the liquid crystal composition obtained in the comparative example, The stability of the mixture of polymerizable compounds at room temperature was evaluated. After mixing, the solution was changed to an isotropic liquid at 100 ° C and left to cool to 25 ° C. After half a day at room temperature, the presence or absence of precipitation was confirmed. As a result, no precipitation was confirmed in the mixtures of Examples 1 to 24 and Comparative Example 1, and the compatibility of any of the alignment control layer-forming monomers was good.

As can be seen from Table 4, in Examples 1 to 24, although the composition or the type of the alignment control layer-forming monomer was changed, no light leakage was observed. In the case where a plurality of alignment control layers are used to form a monomer, the same tendency is observed. This result indicates that even if an alignment film such as polyimide is not included in the device, the alignment is good, and all the liquid crystal molecules are aligned in a fixed direction. On the other hand, in Comparative Example 1 containing no alignment control layer-forming monomer, light leakage was observed. In addition, sufficient alignment cannot be obtained in an alignment control layer-forming compound having no polymerizable group. From the above results, it is understood that a thin film formed from an alignment control layer-forming monomer having two or more polymerizable groups plays an important role in uniformizing the alignment of liquid crystal molecules. Moreover, it turns out that compatibility with a liquid crystal composition is also favorable. Monomers are formed on other alignment control layers (for example, compound (A-2-1-1), compound (A-2-2-1), compound (A-2-3), compound (A-2-4) , Compound (D-1-7), compound (D-1-8), compound (AA-4), compound (AA-13), compound (AA-14), compound (AA-15)) , Can also expect the same effect. Therefore, if the liquid crystal composition of the present invention is used, a liquid crystal display element having characteristics such as a wide temperature range of usable elements, short response time, high voltage retention, low threshold voltage, large contrast, and long life can be obtained. . Furthermore, a liquid crystal display element having a liquid crystal composition having a high upper temperature in the nematic phase, a low lower temperature in the nematic phase, a low viscosity, a suitable optical anisotropy, and a positive dielectric material can be obtained. Among the characteristics such as large anisotropy, large specific resistance, high stability to ultraviolet rays, and high stability to heat, at least one characteristic is satisfied. [Industrial availability]

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

no

Claims (27)

A liquid crystal display element that sandwiches a liquid crystal layer between a pair of substrates disposed opposite to each other and bonded together via a sealant, and has alignment control between the pair of substrates and the liquid crystal layer to control alignment of liquid crystal molecules. Layer, the liquid crystal layer has positive dielectric anisotropy, and in the liquid crystal display element, the alignment control layer includes forming an alignment control layer by sandwiching a liquid crystal composition between the pair of substrates. A polymer produced by polymerizing a monomer, the liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (A) to formula (D) as a first additive and as the alignment control layer Forming monomers and liquid crystalline compounds, In the formulae (A) to (D), P ¹⁰ , P ²⁰ , P ³⁰ , and P ^{40 are each} independently a group selected from the groups represented by the formulae (Q-1) to (Q-5); In the formulae (Q-1) to (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. C 1 to 5 alkyl groups; Sp ¹⁰ , Sp ²⁰ , and Sp ^{40 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one hydrogen of the alkylene group may be via fluorine, chlorine, or formula (Q-6) substitution, at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH-; Sp ^{30 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms. At least one hydrogen of the alkylene group may be substituted with fluorine, chlorine, or formula (Q-6), and at least one -CH ₂ -may be- O-, -CO-, -COO-, or -OCO- substitution; In formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine. Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkylene group may be substituted with fluorine or chlorine, and at least one -CH ₂ -may be -O-, -CO -, -COO-, or -OCO- substitution; Ring A ¹⁰ and Ring A ^{20 are} independently phenyl, 4-biphenyl, 1-naphthyl, 2-naphthyl, pyrimidin-2-yl, pyrimidine-5 -Yl, pyridin-2-yl, pyridin-5-yl, fluoren-2-yl, fluoren-3-yl, phenanthrene-2-yl, or anthracen-2-yl, in these rings, at least one hydrogen may pass through Fluorine, 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, among these groups, At least one hydrogen may be substituted with fluorine or chlorine; ring A ¹¹ , ring A ²¹ , ring A ¹² , ring A ²² and ring A ^{30 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl, decalin-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, pyrene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a ] Phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradechydrocyclopenta [a] phenanthrene- 3,17-diyl, the adjacent bonds are -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or When -CH = CH-COO-, and R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, an alkyl group having 1 to 10 carbons, or at least one hydrogen is substituted with an alkyl group having 1 to 10 carbons in fluorine, 1,4-phenylene, 4,4'-biphenyl, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrene-2, 7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl. In these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, and carbon 2 Alkenyl to 12, alkoxy having 1 to 11 carbons, or alkenyloxy having 2 to 11 carbons, in which at least one hydrogen may be substituted with fluorine or chlorine; ring A ⁴⁰ is 1, 4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenyl, 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-di , Pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyrene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopentane Benzo [a] phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradechydrocyclopenta [a] ] Phenanthrene-3,17-diyl, adjacent bonds are -CH = CH-, -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or -CH = CH- At COO-, it is 1,4-phenylene, 4,4'-biphenyl, naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, Fluorene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, at least one of these rings may pass through P ²⁰ -Sp ^20- , fluorine, chlorine, carbon Alkyl groups of 1 to 12, alkenyl groups of 2 to 12 carbons, alkoxy groups of 1 to 11 carbons, or alkenyloxy groups of 2 to 11 carbons, at least one hydrogen of these groups may be substituted by Fluorine or chlorine substitution; Z ^{10 is} independently -CH = CH-, -CR ¹⁰ = CR ^20- , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH-, or- CH = CH-COO-; R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, an alkyl group having 1 to 10 carbon atoms, or at least one hydrogen group substituted with fluorine is an alkyl group having 1 to 10 carbon atoms; Z ¹¹ independently a single bond or a C 1-6 alkylene group, said alkylene, at least one -CH ₂ - may be -O -, - CO -, - COO -, - OCO-, -OCOO- or substituted, at least one - (CH _{2) 2} - may be substituted with -CH = CH- or -C≡C-, the group of these At least one hydrogen may be substituted by fluorine or chlorine; Z ²⁰ and Z ^{21 are} independently a single bond, an alkylene group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, at least one of which is 2 to 6 carbon atoms 6 alkenylene group; and the plurality of alkylene and alkenylene groups, at least one -CH ₂ - may be -O -, - CO -, - COO -, - OCO-, -OCOO- or substituted, at least other One-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in which at least one hydrogen may be substituted by fluorine or chlorine; k ¹⁰ and n ^{10 are} independently 0 to 3 Integer, the sum of k ¹⁰ and n ¹⁰ is an integer from 1 to 6; n ²⁰ is 1 or 2; n ³⁰ is 1 or 2. The liquid crystal display element according to item 1 of the scope of patent application, wherein the alignment control layer forming monomer in the liquid crystal composition is a formula (A-1), a formula (A-2), a formula (B), a formula (C- 1) and formula (D-1), In formula (A-1), formula (A-2), formula (B), formula (C-1) and formula (D-1), P ¹⁰ , P ²⁰ , P ³⁰ , P ⁴⁰ , P ⁵⁰ and P ^{60 is} independently a group selected from the group represented by formula (Q-1); in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, methyl, or at least one Hydrogen is fluorine-substituted alkyl having 1 to 5 carbons; Sp ¹⁰ , Sp ²⁰ , and Sp ^{40 are} independently a single bond or an alkylene having 1 to 12 carbons, and at least one hydrogen of the alkylene may be passed through Fluorine or formula (Q-6) substitution, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-, at least one -CH ₂ CH ₂ -may be substituted by -CH = CH -Substitution; Sp ^{30 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted with fluorine, chlorine, or formula (Q-6), at least one -CH _2- May be substituted by -O-, -CO-, -COO-, or -OCO-; in formula (Q-6), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, methyl, or at least one hydrogen replaced by fluorine, alkyl having 1 to 5; Sp ⁴¹ independently a single bond or a C 1-12 alkylene group, said alkylene group may be at least one hydrogen replaced by fluorine or chlorine, at least one of -CH ₂ - may be -O -, - CO -, - substituted -COO-, or -OCO-; Sp ⁵⁰ and Sp ⁶⁰ are independently an alkylene group having a carbon number of 2 to 12, said at least one alkylene Hydrogen may be substituted with fluorine, chlorine or formula (Q-6), at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-; R ¹⁰ and R ^{20 are} independently hydrogen , Fluorine, cyano, 1 to 10 carbon alkyl groups, or at least one hydrogen substituted 1 to 10 carbon alkyl groups of fluorine; R ^{3 0} , R ^{4 0} , R ⁴¹ and R ^{5 0 are} independently hydrogen , Fluorine, chlorine, an alkyl group having 1 to 10 carbons, or an alkyl group having 1 to 10 carbons in which at least one hydrogen is replaced by fluorine; ring A ¹¹ and ring A ^{21 are} independently 1,4-phenylene, or Naphthalene-2,6-diyl, in which at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbons, or at least one hydrogen substituted with an alkyl group having 1 to 12 carbons; ¹¹ is a single bond, ethylene, methyleneoxy, -COO-, -OCO-, -OCOO-, or -CH = CH-COO-; Z ¹² is -CO-, or -OCO-; k ¹⁰ And n ^{10 are} independently integers from 0 to 3, and the sum of k ¹⁰ and n ¹⁰ is an integer from 1 to 4; n ²⁰ is 1 or 2; n ³⁰ is 1 or 2; Z ²⁰ and Z ^{21 are} independently single bonds , -CO-CH = CH-, -CH = CH-CO-, -OCO-CH = CH -, -CH = CH-COO- or -CH = CH-, but not single bonds at the same time. The liquid crystal display element according to item 2 of the scope of patent application, wherein the alignment control layer forming monomer in the liquid crystal composition is a formula (A-1), a formula (A-2) or a formula (B), P ¹⁰ , P ^{20, P 30, P 40,} P 50 and P ⁶⁰ are independently (Q-1) groups represented by the formula is selected from the group; in the formula ^{(Q-1), M 10} , M 20, and M ³⁰ independently Ground is hydrogen, fluorine, methyl, or trifluoromethyl; Sp ¹⁰ and Sp ^{20 are} independently a single bond or an alkylene group having 1 to 12 carbon atoms, and at least one hydrogen of the alkylene group may be fluorine or formula (Q-6) substitution, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-; in formula (Q-6), M ¹⁰ , M ²⁰ , and M ³⁰ Is independently hydrogen, fluorine, methyl, or at least one hydrogen substituted by fluorine with an alkyl group of 1 to 5 carbon atoms; Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, said alkylene group At least one hydrogen may be substituted with fluorine or chlorine, and at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-; Sp ³⁰ is a single bond or an extension of 1 to 12 carbons Alkyl, at least one hydrogen of the alkylene may be substituted by fluorine, and at least one -CH ₂ -may be taken by -O-, -CO-, -COO-, or -OCO- Sp ⁴⁰ is a single bond; Sp ⁵⁰ and Sp ^{60 are} independently an alkylene group having 2 to 12 carbon atoms, and at least one hydrogen of the alkylene group may be substituted with fluorine, chlorine, or formula (Q-6), at least One -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-; R ¹⁰ and R ^{20 are} independently hydrogen, fluorine, cyano, 1 to 10 carbon alkyl, or At least one hydrogen is substituted by fluorine with 1 to 10 carbon alkyl groups; R ³⁰ , R ⁴⁰ and R ^{50 are} independently hydrogen, fluorine, chlorine, 1 to 10 carbons with alkyl, or at least one hydrogen substituted with fluorine 1 to 10 carbon alkyl groups; ring A ¹¹ and ring A ^{21 are} independently 1,4-phenylene, or naphthalene-2,6-diyl, and among these, at least one hydrogen may be fluorine, methyl , Ethyl or trifluoromethyl substitution; Z ¹¹ is a single bond, -COO- or -OCO-; Z ¹² is -CO-, or -OCO-; k ¹⁰ and n ^{10 are} independently integers from 0 to 3, The sum of k ¹⁰ and n ¹⁰ is an integer from 1 to 4; n ²⁰ is 1 or 2; n ³⁰ is 1 or 2. The liquid crystal display element according to any one of claims 1 to 3, wherein the ratio of the alignment control layer-forming monomer in the liquid crystal composition is 0.1 parts by weight to 10 based on the total amount of the liquid crystal compound. Range of parts by weight. The liquid crystal display element according to item 1 of the scope of patent application, which contains, as a first component, at least one compound selected from the group of compounds represented by formula (1), In formula (1), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons; ring A is 1,4-cyclohexyl, 1 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-; X ¹ and X ^{2 are} independently hydrogen or Fluorine; Y ¹ is fluorine, chlorine, at least one hydrogen alkyl group having 1 to 12 carbon atoms substituted with fluorine or chlorine, at least one hydrogen substituted with fluorine or chlorine alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen Alkenyloxy having 2 to 12 carbon atoms substituted with fluorine or chlorine; a is 1, 2, 3, or 4. The liquid crystal display element according to item 5 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-39) as a first component, In the formulae (1-1) to (1-39), R ¹ is an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons. The liquid crystal display element according to item 5 or item 6 of the patent application range, wherein the ratio of the first component in the liquid crystal composition is in a range of 10% by weight to 85% by weight. The liquid crystal display element according to item 1 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (2) as a second component, In formula (2), R ² and R ^{3 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least one hydrogen atom through fluorine or chlorine Substituted alkenyl having 2 to 12 carbons; ring B and ring C are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2, 5-difluoro-1,4-phenylene; Z ² is a single bond, ethylene, or carbonyloxy; b is 1, 2, or 3. The liquid crystal display element according to item 8 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-13) as a second component, In the formulae (2-1) to (2-13), R ² and R ^{3 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal display element according to item 8 or item 9 of the scope of patent application, wherein the ratio of the second component in the liquid crystal composition is in the range of 10% by weight to 85% by weight. The liquid crystal display element according to item 1 of the scope of patent application, 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 an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an olefin having 2 to 12 carbons Oxy; ring D and ring F are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene, naphthalene-2,6-diyl with at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, chromogen-2 with at least one hydrogen substituted with fluorine or chlorine, 6-diyl, or chromogen-2,6-diyl in which at least one 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-difluorochroman-2,6-diyl; Z ³ and Z ^{4 are} 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 display element according to item 11 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-22) as a third component, In the formulae (3-1) to (3-22), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyloxy group having 2 to 12 carbon atoms. The liquid crystal display device according to claim 11 or claim 12, wherein the ratio of the third component is in a range of 3% to 25% by weight. The liquid crystal display element according to item 1 of the patent application scope, wherein the liquid crystal composition further contains 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-bis Oxane-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, alkyl having 1 to 12 carbons Oxygen, or at least one hydrogen substituted with fluorine or chlorine and 1 to 12 carbons; ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-benzene Naphthalene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1 , 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5 -Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen of these rings may be via fluorine, Chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen substituted with an alkyl group having 1 to 12 carbon atoms substituted with fluorine or chlorine; Z ⁶ and Z ^{7 are} independently mono Bond or alkylene having 1 to 10 carbons, at least one -CH ₂ -of which may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least One -CH ₂ CH ₂ -can be replaced by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )- Among these groups, at least one hydrogen may be substituted 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 a carbon number of 1 to 10 Alkylene, at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be- CH = CH- or -C≡C- substitution, in these groups, at least one hydrogen may be substituted 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. The liquid crystal display element according to item 14 of the scope of patent application, wherein in formula (4) in the liquid crystal composition, P ¹ , P ² , and P ^{3 are} independently selected from the formula (P-1) to the formula (P -5) a group in the group of polymerizable groups represented by, In the formulae (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. Alkyl having 1 to 5 carbons. The liquid crystal display element according to item 14 of the scope of patent application, which contains, as a liquid crystal composition, at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27). The second addition, In Formulas (4-1) to (4-27), P ⁴ , P ⁵ , and P ^{6 are} independently selected from the group consisting of polymerizable groups represented by Formulas (P-1) to (P-3) Base in group, Here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine; Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the alkylene groups, at least one of -CH ₂ -may pass through -O-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-, and among these groups, at least one hydrogen may be substituted with fluorine or chlorine. The liquid crystal display element according to any one of claims 14 to 16, in which the ratio of the second additive in the liquid crystal composition is 0.03 parts by weight to 10 parts by weight based on the total amount of the liquid crystal compound. Range. The liquid crystal display device according to item 1 of the scope of patent application, wherein the upper limit temperature of the nematic phase is 70 ° C or more, the optical anisotropy (measured at 25 ° C) at a wavelength of 589 nm is 0.07 or more, and the frequency is 1 kHz The dielectric anisotropy (measured at 25 ° C) is 2 or more. A liquid crystal display element having a liquid crystal composition and an electrode in a liquid crystal display element according to any one of claims 1 to 18 of a patent application range between a pair of substrates, and has an upper limit due to a nematic phase. The linearly polarized ultraviolet rays are irradiated above the temperature, and the alignment control layer in the liquid crystal composition forms a monomer to react. The liquid crystal display element according to item 1 of the scope of the patent application, wherein the operation mode of the liquid crystal display element is a coplanar switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced light reaction alignment mode, and a driving mode of the liquid crystal display element. Active matrix method. According to the liquid crystal display element described in the first item of the patent application scope, wherein the operation mode of the liquid crystal display element is a coplanar switching mode or a fringe field switching mode, and the driving method of the liquid crystal display element is an active matrix method. A polymer-stabilized alignment type liquid crystal display element comprising the liquid crystal composition in the liquid crystal display element according to any one of claims 1 to 17 of the scope of patent application, and the polymerizability in the liquid crystal composition. The compounds are polymerized. A use of a liquid crystal composition, wherein the liquid crystal composition is the liquid crystal composition in the liquid crystal display element according to any one of claims 1 to 17 of the scope of patent application, and is used in the liquid crystal display element. A use of a liquid crystal composition, which is the liquid crystal composition in the liquid crystal display element according to any one of claims 1 to 17 of the scope of application for a patent, which is used for a polymer stabilized alignment type liquid crystal Display element. A compound represented by formula (A-2), In formula (A-2), P ⁵⁰ and P ^{60 are} independently a group selected from the group represented by formula (Q-1); in formula (Q-1), M ¹⁰ , M ²⁰ , and M ^{30 are} independently Ground is hydrogen, fluorine, methyl, or at least one hydrogen substituted by fluorine with an alkyl group of 1 to 5 carbon atoms; Sp ⁵⁰ and Sp ^{60 are} independently alkylene groups having 1 to 12 carbon atoms. At least one hydrogen may be substituted with fluorine or formula (Q-6), and at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-; in formula (Q-6), M ^10, M ^20, and M ³⁰ are independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, at least one hydrogen or fluorine or chlorine-substituted alkyl group of 1 to 5 carbon atoms; Sp ⁴¹ is a single bond Or an alkylene group having 1 to 12 carbons, at least one hydrogen of which may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be -O-, -CO-, -COO-, or -OCO -Substituted; Z ¹² is -CO-, or -OCO-; R ^{50 is} independently hydrogen, fluorine, an alkyl group having 1 to 10 carbons, or at least one alkyl group having 1 to 10 carbon atoms substituted with fluorine; k ¹⁰ and n ^{10 are} independently integers of 0 to 3, and the sum of k ¹⁰ and n ¹⁰ is an integer of 1 to 4. Use of a compound as described in claim 25 of the scope of patent application, which is used as a monomer for forming an alignment control layer. A liquid crystal composition is the liquid crystal composition in a liquid crystal display element according to any one of claims 1 to 17 of the scope of patent application.