TW201905184A - Liquid crystal display element, use of liquid crystal composition, use of compound, and liquid crystal composition - Google Patents

Abstract

The purpose of the present invention is to control the alignment of a liquid crystalline molecule in a liquid crystal display element having no alignment film by using a colorless oriented monomer having a specific structure, and to provide a liquid crystalline composition with which a colorless oriented monomer can exhibit good compatibility. In a liquid crystal display element having no alignment film according to the present invention, the alignment of a liquid crystalline molecule can be controlled by subjecting a liquid crystalline composition to polarization exposure while heating at a temperature higher than the upper limit of the temperature of the liquid crystalline composition, wherein the liquid crystalline composition contains an oriented monomer having a cinnamate or chalcone group and a hydroxyl group as a first additive and has a positive dielectric anisotropy.

Description

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

The present invention relates to a liquid crystal display element and a liquid crystal composition containing a liquid crystal composition having a positive dielectric anisotropy. In particular, it relates to a liquid crystal display element using a liquid crystal composition, the liquid crystal composition containing an aligning monomer, and by the action of the compound, it is possible to achieve liquid crystal molecules without using an alignment film such as polyimide Alignment.

In the liquid crystal display element, the classification based on the operation mode of the liquid crystal molecules is phase change (PC), twisted nematic (TN), super twisted nematic (STN), electronically 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 passive matrix (PM) and active matrix (AM). PM is classified as static, multiplex, etc., AM is classified as thin film transistor (TFT), metal-insulator-metal (MIM), etc. 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 classification based on the light source is 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 relationship 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 device can be used. The preferred upper limit temperature of the nematic phase is approximately 70 ° C or higher, and the preferred lower limit temperature of the nematic phase is approximately -10 ° C or lower. The viscosity of the composition is related to the response time of the device. In order to display a moving image with a component, the response time is preferably short. The ideal response time is less than 1 millisecond. Therefore, it is preferable that the viscosity of the composition is small. Furthermore, the viscosity at low temperature is preferably small.

The optical anisotropy of the composition is related to the contrast of the device. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast. The value of the appropriate product depends on the type of operation mode. In the VA mode element, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, the element having a small cell gap is preferably a composition having a large optical anisotropy. The large dielectric anisotropy of the composition contributes to the low threshold voltage of the device, small power consumption, and large contrast. Therefore, it is preferably a large dielectric anisotropy. The large specific resistance of the composition contributes to a large voltage retention rate and a large contrast ratio of the device. Therefore, in the initial stage, a composition having a large specific resistance is preferable. It is preferably a composition having a large specific resistance after long-term use. 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 devices used in liquid crystal monitors, liquid crystal televisions, and the like.

In an AM element having a TN mode, a composition having positive dielectric anisotropy is used. In an AM element having a VA mode, a composition having negative dielectric anisotropy is used. In an AM element having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, the composition to which a small amount of polymerizable compound is added is injected into the device. Next, while applying a voltage between the substrates of the element, the composition was irradiated with ultraviolet rays. 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 the liquid crystal molecules, so the response time of the element is shortened and the afterimage of the image is improved. Such an effect of a polymer can be expected in an element having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

The following methods are reported: instead of an alignment film such as polyimide, a low-molecular compound having a cinnamate group or polyvinyl cinnamate, a low-molecular compound having a chalcone structure, and a low-azobenzene structure Molecular compounds or dendrimers 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 the liquid crystal composition in the form of an additive. Next, a thin film containing the low-molecular compound or polymer is formed on the substrate by phase-separating the additive. Finally, the substrate is irradiated with linear 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 linear polarized light, the molecules are arranged in a fixed direction. In this method, a device with a horizontal alignment mode such as IPS or FFS and a device with a vertical alignment mode such as VA can be manufactured by selecting the type of low-molecular compound or polymer. In this method, it is important that the low-molecular compound or polymer easily dissolves at a temperature higher than the upper limit temperature of the liquid crystal composition, and when the temperature is returned to room temperature, the compound easily separates from the liquid crystal composition. Among them, it is difficult to ensure the compatibility of the low-molecular compound or polymer with the liquid crystal composition.

In the methods of Patent Document 2 and Patent Document 3, a dendrimer having azobenzene as a partial structure is dissolved as an additive in the liquid crystal composition. 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 vertically aligned with respect to the substrate. Next, linearly polarized light is irradiated without heating the substrate. When the dendrimer is dimerized or isomerized by the linear polarized light, its molecules are arranged in a horizontal direction relative to the substrate. It can manufacture horizontal alignment mode components like IPS or FFS. In this method, in order to make the dendrimer easily soluble and phase-separate, it is necessary to appropriately combine the dendrimer and the liquid crystal composition. In the case of using a dendrimer having azobenzene as a partial structure, there is a problem of coloration derived from azobenzene. In addition, Patent Document 4 discloses a combination of a liquid crystal compound having a positive dielectric anisotropy and a polymerizable compound. Here, it is disclosed that by applying a voltage to a polymerizable compound contained in a liquid crystal medium and polymerizing it to give a pretilt angle, the response time and electro-optical characteristics of the liquid crystal cell are improved. In this method, even if the disclosed polymerizable compound is used, it is difficult to obtain the horizontal alignment of the liquid crystal compound by polarized light irradiation. In addition, there is no suggestion or description that the specific polymerizable compound can control the horizontal alignment of the liquid crystal compound by polarized light irradiation. Patent Literature 5 to Patent Literature 7 disclose a combination of a liquid crystal compound having positive dielectric anisotropy and a polymerizable compound having a polar group. Here, the polymerizable compound having a polar group contained in the liquid crystal medium is intended to control the alignment of the liquid crystal to be vertical. Even if the method described here is used, it is difficult to control the alignment of the liquid crystal compound to a level. In addition, there is no suggestion or description that the polymerizable compound having a polar group can control the horizontal alignment of the liquid crystal compound by polarized light irradiation. [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 Document 3] Japanese Patent Publication No. 2015-125151 [Patent Document 4] International Publication No. 2009 / 156118 [Patent Document 5] International Publication No. 2012/038026 [Patent Document 6] Japanese Patent Laid-Open No. 2015-168826 [Patent Document 7] International Publication No. 2016/015803

[Problem to be Solved by the Invention] The problem to be solved by the present invention is to provide a liquid crystal composition that uses a non-colored alignment monomer to control the alignment of liquid crystal molecules of a liquid crystal display element that does not have an alignment film, without color The aligned monomers show good compatibility. [Means to solve the problem]

In the liquid crystal display element without an alignment film of the present invention, if the liquid crystal composition is heated and subjected to polarized light exposure at a temperature higher than the upper limit temperature of the liquid crystal composition, the alignment of the liquid crystal molecules can be controlled. It contains an aligning monomer having a cinnamate group or a chalcone group, and a hydroxyl group as the first additive, and has positive dielectric anisotropy. The present invention provides a liquid crystal display element that sandwiches a liquid crystal layer between a pair of substrates that are opposed to each other and are bonded together via a sealant, and that includes alignment control of liquid crystal molecules between the pair of substrates and the liquid crystal layer The alignment control layer of the liquid crystal layer includes a liquid crystal composition having positive dielectric anisotropy, the liquid crystal composition containing a liquid crystal composition selected from formula (A-1), formula (A-2), formula (B-1 ) And at least one compound in the group of compounds represented by formula (B-2) as a first additive and as an alignment monomer and a liquid crystal compound, the alignment control layer includes The polymer formed by polymerization of the substance. In formula (A-1) and formula (A-2), P ^{10 is} independently a group selected from the groups represented by formula (Q-1) to formula (Q-5); formula (Q-1) to In formula (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine In the formula (A-1) and formula (A-2), Sp ¹⁰ and Sp ^{11 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 by -O-, -CO-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C- substitution; In formula (Q-6), M ¹¹ , M ²¹ , and M ^{31 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with 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 by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO- , -COO-, or -OCO- substitution; in formula (A-1), formula (A-2), formula (B-1) and formula (B-2), ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenylene, naphthalene- 2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1 , 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, stilbene-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-Tetrahydrocyclopenta [a] phenanthrene-3,17-diyl, the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO- , -OCO-C≡C-, -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene -2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, stilbene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6- Diyl, in these rings, at least one hydrogen can be substituted by fluorine, hydroxyl, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or carbon number Alkenyloxy substitution of 2 to 11, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; In formula (A-1) and formula (A-2), Z ^{10 is} independently a single bond, -COO -, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO -C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; In formula (A-2), Z ¹¹ is -CH = CH-CO- or -CO-CH = CH-; in formula (A-1) and formula (A-2), n ¹⁰ is an integer of 0 to 4; in formula (B-1) and formula (B-2), R ²⁰ is hydrogen, fluorine, chlorine , Hydroxyl, cyano, nitro, trifluoro Methyl, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons; Sp ²⁰ and Sp ^{21 are} independently a single bond or alkylene having 1 to 12 carbons, at least one of which Hydrogen can be substituted by fluorine, at least one -CH ₂ -can be substituted by -O-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -can be substituted by -CH = CH- or -C≡C- Substitution; Z ^{20 is} independently a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO -, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-( CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; n ²⁰ is an integer from 0 to 3. The present invention provides a liquid crystal display element having a liquid crystal composition and an electrode in the liquid crystal display element between a pair of substrates, and by irradiating linearly polarized light, the first additive in the liquid crystal composition reacts. The present invention provides a polymer-stabilized alignment type liquid crystal display element, which contains the liquid crystal composition in the liquid crystal display element, and the polymerizable compound in the liquid crystal composition is polymerized. The invention provides a use of a liquid crystal composition, which is a liquid crystal composition in the liquid crystal display element, which is used in a liquid crystal display element. The present invention provides the use of a liquid crystal composition, which is a liquid crystal composition in the liquid crystal display element, which is used in a polymer-stabilized alignment type liquid crystal display element. The present invention provides the use of a compound represented by formula (A-1), formula (A-2), formula (B-1) and formula (B-2) in the liquid crystal display device , Which is used as a monomer for alignment control layer formation. The present invention provides a liquid crystal composition, which is a liquid crystal composition in the liquid crystal display element. [Effect of invention]

By using the liquid crystal composition containing the alignment monomer of the present invention, since the alignment film formation step is unnecessary, a liquid crystal display element with reduced manufacturing cost can be obtained. In addition, a liquid crystal composition having good compatibility with the alignment monomer and having positive dielectric anisotropy can be obtained.

How to use the terms in this manual is as follows. Sometimes the terms "liquid crystal composition" and "liquid crystal display element" are simply referred to as "composition" and "element", respectively. "Liquid crystal display element" is a general term for liquid crystal display panel and liquid crystal display module. "Liquid crystal compound" is a compound having a nematic phase and a smectic phase equivalent liquid crystal phase, and although it does not have a liquid crystal phase, for the purpose of adjusting the characteristics of the temperature range, viscosity, dielectric anisotropy of the nematic phase The general term for compounds mixed in the composition. This 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 having an alkenyl group is not polymerizable in its meaning.

The liquid crystal composition is prepared by mixing multiple liquid crystal compounds. If necessary, additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the composition. Even when it is convenient to add an additive, the ratio of the liquid crystal compound is also expressed as a weight percentage (weight%) based on the weight of the liquid crystal composition containing no additive. The ratio of the additive is expressed by the weight percentage (weight%) based on the weight of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total weight of the liquid crystal compound. Sometimes parts per million by weight (ppm) are used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

Sometimes the "upper limit temperature of the nematic phase" is simply referred to as the "upper limit temperature". Sometimes the "lower limit temperature of the nematic phase" is 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. "High voltage retention rate" means that the device has a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and not only at room temperature but also after a long period of use It also has a large voltage retention rate at a temperature close to the upper limit temperature. In order to study the characteristics of a composition or an element, a time-dependent change test is sometimes used. The expression "improving dielectric anisotropy" refers to a composition whose dielectric anisotropy is positive, which means that its value increases positively, and to a composition whose dielectric anisotropy is negative, it means its value is negative Increase to the ground.

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

In this specification, expressions such as "at least one -CH ₂ -may be substituted by -O-" are used. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by substituting -O ₂ -with non-adjacent -CH _2- . However, adjacent -CH ₂ -will not be substituted with -O-. This is because -OO-CH _2- (peroxide) is generated by this 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 to the substitution of -O-, but also to the substitution of -CH = CH- or -COO- and other divalent groups.

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, the R of the compound (1-1) ^is ethyl and R Compound (1-2) ¹ is ethyl. In some cases, R ¹ of compound (1-1) is ethyl and R ¹ of compound (1-2) is propyl. This rule also applies to other end group symbols. 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, the rule also applies to any two rings A. This rule also applies to symbols such as Z ¹ and ring D.

Symbols such as A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings. In formula (4), the diagonal line that cuts the 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. The multiple groups represented by -Sp ¹ -P ¹ may be the same or may be different.

2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl that 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. Straight chain alkyl is better than branched alkyl. These cases are also the same for terminal groups such as alkoxy groups and alkenyl groups. In order to increase the upper limit temperature, the stereo configuration associated with 1,4-cyclohexyl is that the trans configuration is superior to the cis configuration.

The present invention is as follows.

Item 1. A liquid crystal display element that sandwiches a liquid crystal layer between a pair of substrates that are opposed to each other and bonded together via a sealant, and that includes alignment control of liquid crystal molecules between the pair of substrates and the liquid crystal layer The alignment control layer of the liquid crystal layer includes a liquid crystal composition having positive dielectric anisotropy, the liquid crystal composition containing a liquid crystal composition selected from formula (A-1), formula (A-2), formula (B-1 ) And at least one compound in the group of compounds represented by formula (B-2) as a first additive and as an alignment monomer and a liquid crystal compound, the alignment control layer includes The polymer formed by polymerization of the substance. In formula (A-1) and formula (A-2), P ^{10 is} independently a group selected from the groups represented by formula (Q-1) to formula (Q-5); formula (Q-1) to In formula (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine In the formula (A-1) and formula (A-2), Sp ¹⁰ and Sp ^{11 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 by -O-, -CO-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C- substitution; In formula (Q-6), M ¹¹ , M ²¹ , and M ^{31 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with 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 by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO- , -COO-, or -OCO- substitution; in formula (A-1), formula (A-2), formula (B-1) and formula (B-2), ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenylene, naphthalene- 2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1 , 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, stilbene-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-Tetrahydrocyclopenta [a] phenanthrene-3,17-diyl, the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO- , -OCO-C≡C-, -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene -2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, stilbene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6- Diyl, in these rings, at least one hydrogen can be substituted by fluorine, hydroxyl, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or carbon number Alkenyloxy substitution of 2 to 11, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; In formula (A-1) and formula (A-2), Z ^{10 is} independently a single bond, -COO -, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO -C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; In formula (A-2), Z ¹¹ is -CH = CH-CO- or -CO-CH = CH-; in formula (A-1) and formula (A-2), n ¹⁰ is an integer of 0 to 4; in formula (B-1) and formula (B-2), R ²⁰ is hydrogen, fluorine, chlorine , Hydroxyl, cyano, nitro, trifluoro Methyl, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons; Sp ²⁰ and Sp ^{21 are} independently a single bond or alkylene having 1 to 12 carbons, at least one of which Hydrogen can be substituted by fluorine, at least one -CH ₂ -can be substituted by -O-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -can be substituted by -CH = CH- or -C≡C- Substitution; Z ^{20 is} independently a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO -, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-( CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; n ²⁰ is an integer from 0 to 3.

Item 2. The liquid crystal display element according to Item 1, wherein in Formula (A-1) and Formula (A-2) according to Item 1, P ^{10 is} independently Formula (Q-1); Formula (Q -1), M ^{10 is} independently hydrogen, fluorine, methyl, or trifluoromethyl; M ²⁰ and M ³⁰ are hydrogen; Sp ¹⁰ and Sp ^{11 are} independently single bonds or alkylene having 2 to 12 carbon atoms Group, at least one hydrogen of the alkylene group may be substituted by fluorine, chlorine or formula (Q-6), at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-, At least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-; in formula (Q-6), M ^{11 is} independently hydrogen, fluorine, methyl, or trifluoromethyl; M ²¹ and M ³¹ are hydrogen; Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of which may be substituted by fluorine, and at least one -CH ₂ -may be substituted by -O- , -CO-, -COO-, or -OCO- substitution; in formula (A-1), formula (A-2), formula (B-1) and formula (B-2), ring A ¹⁰ and ring A ²⁰ , Ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-cyclohexyl, 1,4-phenylene, 4,4'-biphenylene, naphthalene-2,6-diyl 1,2,3,4-tetrahydronaphthalene-2,6-diyl, the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO -C≡C-, -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene-2, 6-diyl, in these rings, at least one hydrogen may be substituted by fluorine, hydroxyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkoxy; Formula (A-1 ) And formula (A-2), Z ^{10 is} independently a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH -, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; formula (A- 2), Z ¹¹ is -CH = CH-CO- or -CO-CH = CH-; In formula (A-1) and formula (A-2), n ¹⁰ is an integer from 0 to 4; formula (B -1) and in formula (B-2), R ²⁰ is hydrogen, fluorine, hydroxyl, C 1-5 alkyl or C 1-5 alkoxy; Sp ²⁰ and Sp ^{21 are} independently single bonds Or an alkylene group having 1 to 12 carbon atoms, at least one -CH _{2 of the} alkylene group -May be substituted by -O-; n ^{2 0} is an integer from 0 to 3.

Item 3. The liquid crystal display element according to Item 1 or Item 2, wherein in Formula (A-1) and Formula (A-2) described in Item 1, P ^{10 is} independently formula (Q-1); In formula (Q-1), M ^{10 is} independently hydrogen or methyl; M ²⁰ and M ³⁰ are hydrogen; Sp ¹⁰ and Sp ^{11 are} independently a single bond or an alkylene group having 2 to 12 carbon atoms, the alkylene group At least one hydrogen of the group may be substituted by formula (Q-6), 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- or -C≡C-; in formula (A-1) and formula (A-2), Z ^{10 is} independently a single bond, -COO-, -OCO-, -CH = CH -COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O -, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; in formula (A-2), Z ¹¹ is -CH = CH-CO- or -CO-CH = CH-; ring A ¹⁰ , ring A ²⁰ , Ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-phenylene, 1,4-cyclohexyl, naphthalene-2,6-diyl, or tetrahydronaphthalene-2,6-bis Group, the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO-C≡C-, -CH = CH-, -CF = CF- or In the case of -C≡C-, it is 1,4-phenylene or naphthalene-2,6-diyl. In this 1,4-phenylene, any hydrogen can be substituted by fluorine, hydroxyl, trifluoromethyl , An alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; in formula (A-1) and formula (A-2), n ¹⁰ is an integer of 0 to 2; formula (B- 1) and in formula (B-2), R ²⁰ is hydrogen, fluorine, hydroxyl, C 1-5 alkyl or C 1-5 alkoxy; Sp ²⁰ and Sp ^{21 are} independently a single bond or An alkylene group having 1 to 12 carbon atoms, at least one -CH ₂ -of which may be substituted with -O-; n ²⁰ is an integer of 0 to 3.

Item 4. The liquid crystal display element according to any one of Item 1 to Item 3, wherein when the total amount of the liquid crystal compound is 100 parts by weight, the ratio of the alignment monomer as the first additive It is in the range of 0.1 parts by weight to 10 parts by weight.

Item 5. The liquid crystal display element according to any one of Item 1 to Item 4, which contains at least one compound selected from the group of compounds represented by formula (1) as the first component. In formula (1), R ¹ is C 1-12 alkyl, C 1-12 alkoxy, or C 2-12 alkenyl; 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; Z ¹ is a single bond, ethylidene, 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 substituted with fluorine or chlorine, a C 1-12 alkyl group, at least one hydrogen substituted with fluorine or chlorine, a C 1-12 alkoxy group, or at least one hydrogen Alkenyloxy having 2 to 12 carbons substituted with fluorine or chlorine; a is 1, 2, 3, or 4.

Item 6. The liquid crystal display element according to any one of Item 1 to Item 5, which contains at least one compound selected from the group of compounds represented by Formula (1-1) to Formula (1-39) as The first ingredient. In formula (1-1) to formula (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 Item 6, wherein the ratio of the first component to the total amount of the liquid crystal compound is in the range of 10% by weight to 85% by weight.

Item 8. The liquid crystal display element according to any one of Item 1 to Item 7, which contains at least one compound selected from the group of compounds represented by formula (2) as the second component. In formula (2), R ² and R ^{3 are} independently a C 1-12 alkyl group, a C 1-12 alkoxy group, a C 2-12 alkenyl group, or at least one hydrogen group 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, ethyl ester, or carbonyloxy; b is 1, 2, or 3.

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

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

Item 11. The liquid crystal display element according to any one of Item 1 to Item 10, 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 a C 1-12 alkyl group, a C 1-12 alkoxy group, a C 2-12 alkenyl group, or a C 2-12 alkenyl group Yloxy; 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 substituted with at least one hydrogen by fluorine or chlorine, naphthalene-2,6-diyl substituted by at least one hydrogen by fluorine or chlorine, chroman-2, 6-diyl, or chroman-2,6-diyl with at least one hydrogen substituted with 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, ethylidene, 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 Item 1 to Item 11, which contains at least one compound selected from the group of compounds represented by Formula (3-1) to Formula (3-22) as The third component. In formula (3-1) to formula (3-22), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons , Or an alkenyloxy group having 2 to 12 carbon atoms.

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

Item 14. The liquid crystal display element according to any one of Item 1 to Item 13, which further contains at least one compound selected from the group of polymerizable compounds represented by formula (4) as the second additive. In formula (4), ring F ³ and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-di Oxane-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in these rings, at least one hydrogen can be substituted by fluorine, chlorine, C 1-12 alkyl, C 1-12 alkyl Oxygen, or at least one hydrogen substituted with fluorine or chlorine, C 1-12 alkyl; ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene Group, 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 can be Chlorine, C 1-12 alkyl, C 1-12 alkoxy, or C 1-12 alkyl substituted with at least one hydrogen by 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 -may be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )- In which, 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 an alkylene group having 1 to 10 carbon atoms In the alkylene group, at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may 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), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of Formula (P-1) to Formula (P-5) A group in a group of polymerizable groups. In formula (P-1) to formula (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 is substituted with fluorine or chlorine C1-C5 alkyl.

Item 16. The liquid crystal display element according to any one of Item 1 to Item 15, which contains at least one selected from the group of polymerizable compounds represented by Formula (4-1) to Formula (4-27) The compound serves as the second additive. In formula (4-1) to formula (4-27), P ⁴ , P ⁵ , and P ^{6 are} independently selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3) The base in the 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 substituted 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. In this alkylene group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or- OCOO-substituted, at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by 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 is 0.03 parts by weight to 10 parts by weight when the total amount of the liquid crystal compound is 100 parts by weight Scope.

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, and 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 Item 1 to Item 18 between a pair of substrates, and by irradiating linearly polarized light, the liquid crystal The first additive in the composition reacts.

Item 20. The liquid crystal display element of item 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 method.

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

Item 22. A polymer-stabilized alignment type liquid crystal display element containing the liquid crystal composition in the liquid crystal display element according to any one of Item 14 to Item 17, and the 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 Item 1 to Item 17, which 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 Item 1 to Item 17, which is used in a polymer-stabilized alignment type liquid crystal display element in.

Item 25. Use of a compound of formula (A-1), formula (A-2), or formula (B-1) in the liquid crystal display element according to any one of items 1 to 3 And a compound represented by formula (B-2), which is used as a monomer for forming an alignment control layer.

Item 26. A liquid crystal composition, which is the liquid crystal composition in the liquid crystal display element according to any one of Item 1 to Item 17.

The present invention also includes the following items. (A) The composition further contains at least one additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoam agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound. (B) An AM device containing the above composition. (C) A polymer stabilized alignment (PSA) type AM device, which contains the composition, and the composition further contains a polymerizable compound. (D) A polymer stabilized alignment (PSA) type AM device containing the above-mentioned composition, and the polymerizable compound in the composition is polymerized. (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.

An alignment monomer having a cinnamate group, a chalcone group, and a hydroxyl group contained in the liquid crystal composition used in the liquid crystal display element of the present invention will be described. This compound is the first additive. This compound absorbs ultraviolet rays and causes reactions such as dimerization or isomerization and polymerization reactions. In the present invention, it is represented by formula (A-1), formula (A-2), formula (B-1) and formula ( B-2) said.

In formula (A-1) and formula (A-2), P ^{10 is} independently a group selected from the groups represented by formula (Q-1) to formula (Q-5); formula (Q-1) to In formula (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine In the formula (A-1) and formula (A-2), Sp ¹⁰ and Sp ^{11 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 by -O-, -CO-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C- substitution;

In formula (Q-6), M ¹¹ , M ²¹ , and M ^{31 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with 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 which may be substituted by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO- , -COO-, or -OCO- substitution; in formula (A-1), formula (A-2), formula (B-1) and formula (B-2), ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 4,4'-biphenylene, naphthalene- 2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1 , 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, stilbene-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-Tetrahydrocyclopenta [a] phenanthrene-3,17-diyl, the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO- , -OCO-C≡C-, -CH = CH-, -CF = CF- or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, naphthalene -2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, stilbene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6- Diyl, in these rings, at least one hydrogen can be substituted by fluorine, hydroxyl, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or carbon number Alkenyloxy substitution of 2 to 11, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; In formula (A-1) and formula (A-2), Z ^{10 is} independently a single bond, -COO -, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO -C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; In formula (A-2), Z ¹¹ is -CH = CH-CO- or -CO-CH = CH-; in formula (A-1) and formula (A-2), n ¹⁰ is an integer of 0 to 4; in formula (B-1) and formula (B-2), R ²⁰ is hydrogen, fluorine, chlorine , Hydroxyl, cyano, nitro, trifluoro Methyl, alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons; Sp ²⁰ and Sp ^{21 are} independently a single bond or alkylene having 1 to 12 carbons, at least one of which Hydrogen can be substituted by fluorine, at least one -CH ₂ -can be substituted by -O-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -can be substituted by -CH = CH- or -C≡C- Substitution; Z ^{20 is} independently a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO -, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-( CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; n ²⁰ is an integer from 0 to 3.

As the first additive, an aligning monomer having a cinnamate group, a chalcone group, and a hydroxyl group is irradiated with ultraviolet rays to produce light isomerization or dimerization from the trans form to the cis form. Formation of cyclobutane ring. In addition, it is considered that the first additive is easily adsorbed on the substrate interface side due to the interaction between the hydroxyl group and the substrate interface. In addition, since it has a polymerizable group, it is fixed by polymerization. This property can be used to prepare thin films capable of aligning liquid crystal molecules. In order to prepare the film, the ultraviolet rays irradiated are suitably linearly polarized light. First, when the total amount of the liquid crystal compound is 100 parts by weight, the aligning monomer as the first additive is added to the liquid crystal composition in the range of 0.1 part by weight to 10 parts by weight. The substance dissolves, and the composition is heated. This composition was injected into an element having no alignment film. Next, while heating the element, the film containing the first additive adsorbed on the substrate interface side is irradiated with linear polarized light, thereby promoting photo-isomerization or dimerization. The photo-isomerized compounds or the dimerized compounds are arranged in a fixed direction. At the same time, photopolymerization also occurs, and the film is fixed 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 structure 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 element will be described. Third, the combination of components in the composition, the preferred ratio of the components, and their basis will be described. Fourth, the preferred forms of the component compounds will be described. Fifth, the preferred component compounds are shown. Sixth, the additives that can be added to the composition will be described. Seventh, the method of synthesizing the component compounds will be described. Eighth, the use of the composition will be described. Ninth, the method of manufacturing the element will be described.

First, the structure of the composition will be described. This composition contains various liquid crystal compounds. The 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 the liquid crystal compound, the composition is classified into composition A and composition B. In addition to the liquid crystal compound selected from the compound (1) and the compound (2), the composition A may further contain other liquid crystal compounds. "Other liquid crystal compounds" are liquid crystal compounds different from compound (1) and compound (2). Such compounds are mixed in the composition for the purpose of further adjusting the characteristics.

The composition B contains substantially only the liquid crystal compound selected from the compound (1) and the compound (2). The term "substantially" means that although the composition may contain additives, it 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, composition B is superior to composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, composition A is superior to composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the composition or element 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 means large or high, M means medium, and S means small or low. Symbols L, M, and S are classifications based on qualitative comparison between component compounds, and symbol 0 (zero) means that the dielectric anisotropy is extremely small.

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. An aligning monomer having a cinnamate group, a chalcone group, and a hydroxyl group is the first additive. When the compound is dimerized or isomerized and polymerized by polarized light, it is arranged in a fixed direction at the molecular level. Therefore, the thin film formed of the first additive aligns the liquid crystal molecules in the same manner as the alignment film such as polyimide. The compound (1) as the first component increases the dielectric anisotropy. The compound (2) as the second component lowers the viscosity or raises the upper limit temperature. The compound (3) as the third component increases the dielectric constant in the short axis direction. The compound (4) as the 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 their basis will be described. The preferred combination of the components in the composition is the first component + additive, the first component + second component + additive, the first component + third component + additive, or the first component + second component + third Ingredients + additives. A further preferred combination is the first component + the second component + the additive.

In order to align the liquid crystal molecules, when the total amount of the liquid crystal compound is set to 100 parts by weight, the preferred ratio of the first additive is about 0.1 parts by weight or more. The ratio 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 proportion of the first component is about 10% by weight or more relative to the total amount of the liquid crystal compound. 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 good 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 proportion of the second component relative to the total amount of the liquid crystal compound is about 10% by weight or more. To improve the dielectric anisotropy, the preferred proportion 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 good ratio is in the range of about 20% by weight to about 75% by weight.

In order to increase the dielectric constant in the short-axis direction, the preferred proportion of the third component relative to the total amount of the liquid crystal compound is about 3% by weight or more. To reduce the lower limit temperature, the preferred proportion of the third component is about 25% by weight %the following. A further preferred ratio is in the range of about 5% by weight to about 20% by weight. A particularly good ratio is in the range of about 5 wt% to about 15 wt%.

The second additive may also be added to the composition for the purpose of being suitable for a polymer-stabilized alignment type element. In order to align the liquid crystal molecules, when the total amount of the liquid crystal compound is set to 100 parts by weight, the preferred ratio of the additive is about 0.03 parts by weight or more. 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, the preferred forms 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, the preferable R ¹ is an alkyl group having 1 to 12 carbons. 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 a carbon number 2 to 2 having at least one hydrogen substituted with fluorine or chlorine 12 alkenyl. In order to reduce the viscosity, the preferred R ² or R ³ is an alkenyl group having 2 to 12 carbon atoms. In order to improve the stability to ultraviolet rays or heat, the preferred R ² or R ³ is an alkyl group having 1 to 12 carbon atoms. R ⁴ and R ^{5 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, or C 2-12 alkenyloxy. In order to improve the stability to ultraviolet rays or heat, the preferred R ⁴ or R ⁵ is an alkyl group having 1 to 12 carbon atoms. In order to increase the dielectric constant in the short axis direction, the preferred R ⁴ or R ⁵ is a carbon number. 1 to 12 alkoxy groups.

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 groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. In order to reduce the viscosity, the preferred alkoxy group is 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, the preferred alkenyl group 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. For reasons such as viscosity reduction, among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl, etc. are preferred Trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl groups, a cis configuration is preferred. Among these alkenyl groups, linear alkenyl groups are superior to branched alkenyl groups.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to reduce the viscosity, the preferred alkenyloxy group is allyloxy or 3-butenyloxy.

Preferred examples of alkyl groups 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 alkenyl 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 the 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. In order to reduce the viscosity, the preferred ring B or ring C is 1,4-cyclohexyl, or to increase 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, naphthalene-2,6-diyl, chromanane-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine Or at least one chroman-2,6-diyl substituted by fluorine or chlorine. In order to reduce the viscosity, the preferred ring D or ring F is 1,4-cyclohexyl, and in order to increase the dielectric constant in the short axis direction, the preferred ring D or ring F is tetrahydropyran-2,5- Diyl, in order to improve optical anisotropy, 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- Phenylphenyl, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. In order to increase the dielectric constant in the short axis direction, the preferred ring E is 2,3-difluoro-1,4-phenylene.

Z ¹ is a single bond, ethylidene, carbonyloxy, -CH = CF-, -CF = CF-, difluoromethyleneoxy, -CH = CF-CF ₂ O- or -CF = CF-CF ₂ O-. In order to reduce the viscosity, the preferred Z ¹ is a single bond, and in order to increase the dielectric anisotropy, the preferred Z ¹ is a difluoromethyleneoxy group. Z ² is a single bond, ethylidene, or carbonyloxy. In order to reduce the viscosity, the preferred Z ² is a single bond. Z ³ and Z ^{4 are} independently a single bond, ethylidene, carbonyloxy, or methyleneoxy. In order to reduce the viscosity, the preferred Z ³ or Z ⁴ is a single bond, and in order to increase the dielectric constant in the short axis direction, the preferred Z ³ or Z ⁴ is a methyleneoxy group.

X ¹ and X ^{2 are} independently hydrogen or fluorine. In order to increase the dielectric anisotropy, X ¹ or X ² is preferably fluorine.

Y ¹ is fluorine, chlorine, at least one hydrogen substituted with fluorine or chlorine, C 1-12 alkyl, at least one hydrogen substituted with fluorine or chlorine, C 1-12 alkoxy, or at least one hydrogen substituted with fluorine Or a C2-C12 alkenyloxy group substituted with chlorine. In order to lower the lower limit temperature, Y ¹ is preferably fluorine.

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

a is 1, 2, 3, or 4. In order to lower the lower limit temperature, the preferred a is 2, and in order to increase the dielectric anisotropy, the preferred a is 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 in order to reduce the lower limit temperature, the preferred d is 1.

In formula (4), P ¹ , P ² , and P ^{3 are} independently polymerizable groups. Preferably, P ¹ , P ² , or P ³ is a polymerizable group selected from the group represented by formula (P-1) to formula (P-5). More 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 are groups represented by formula (P-1) or formula (P-2). The most preferred P ¹ , P ² , or P ³ is the base represented by the formula (P-1). The preferred group represented by formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy line from formula (P-1) to formula (P-5) indicates the bonded part.

In formula (P-1) to formula (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 is substituted with fluorine or chlorine C1-C5 alkyl. In order to improve the reactivity, M ¹ , M ² or M ³ is preferably 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, in which at least one -CH ₂ -may be passed through -O-, -COO-, -OCO- , Or -OCOO- substitution, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferred Sp ¹ , Sp ² , or Sp ³ are single bonds, -CH ₂ -CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH- , Or -CH = CH-CO-. Furthermore, 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 pyrid-2-yl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy, or at least one The hydrogen is substituted with a C 1-12 alkyl group substituted with 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 through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen is substituted with fluorine or chlorine and a C 1-12 alkyl group. 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. In this alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO -Substitution, 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 ) -Substitution, in these groups, at least one hydrogen may be substituted by 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-. Furthermore, the preferred Z ⁶ or Z ⁷ is a single bond.

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

Fifth, the preferred component compounds are shown. The preferred alignment monomer as the first additive will be described. The alignment monomer preferably has at least one polymerizable group and a hydroxyl group. It is considered that the film (polymer) obtained by polymerizing an aligning monomer having one polymerizable group and having at least one hydroxyl group is soft, but due to the intermolecular force of the hydroxyl group and the substrate, the temperature at which the liquid crystal display element is driven Less distortion in the environment. Therefore, the effect of maintaining the alignment control force can be expected. It is considered that in the case of an aligning monomer having two or more polymerizable groups and having at least one hydroxyl group, the cross-link density of the film obtained after polymerization is increased to become a strong film, so it can be expected in a high temperature environment It also maintains alignment control. The part that produces dimerization or isomerization by polarized light is a part having a chalcone structure or a cinnamate structure. When there are a plurality of molecules, the same effect can be expected. When controlling the solubility in the liquid crystal compound, in order to improve the compatibility with the terminal chain of the liquid crystal compound, a spacer may be introduced between the polymerizable group and the cyclic structure. The spacer is preferably linear or branched. The length of the spacer is preferably 2 or more carbon atoms. The alignment monomer can be used alone or in combination of two or more. Specific examples exemplify preferred alignment monomers.

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

Preferred compound (1) is the compound (1-1) to compound (1-39) described in 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). Preferably, at least two of the first component 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 compound (2-1) to compound (2-13) described in 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) . Preferably, at least two of the second components are compound (2-1) and compound (2-5), compound (2-1) and compound (2-6), compound (2-1) and compound (2- 7), Compound (2-3) and Compound (2-5), Compound (2-3) and Compound (2-6), Compound (2-3) and Combination of Compound (2-7).

Preferred compound (3) is compound (3-1) to compound (3-22) described in 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). Preferably, at least two of the third components are compound (3-1) and compound (3-6), compound (3-3) and compound (3-6), compound (3-3) and compound (3- 10), 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, the 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. For the purpose of causing a helical structure of liquid crystal molecules to impart a torsion angle, an optically active compound is added to the composition. Examples of such compounds are compound (4-1) to compound (4-5). When the total amount of the liquid crystal compound is 100 parts by weight, the preferable ratio of the optically active compound is about 5 parts by weight or less. A further preferred ratio is in the range of about 0.01 parts 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 device for a long time, the antioxidant Add to the composition. Preferred examples of the antioxidant are compound (5) where n is an integer of 1 to 9, and the like.

In the compound (5), preferable n is 1, 3, 5, 7, or 9. Furthermore, the optimal n is 7. Since the compound (5) where n is 7 has low volatility, it is effective for maintaining a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. In order to obtain the above-mentioned effect, the preferable ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature or not to increase the lower limit temperature, the preferable 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 ultraviolet absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. In addition, light stabilizers such as amines having steric hindrance are also preferred. In order to obtain the above effect, the preferred ratio of these absorbents or stabilizers is about 50 ppm or more. Below ppm. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to be suitable for elements in the guest host (GH) mode, dichroic dyes such as azo pigments and anthraquinone pigments are added to the composition. The preferable ratio of the pigment is in the range of about 0.01 part by weight to about 10 parts by weight. In order to prevent foaming, antifoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the above-mentioned effect, the preferable ratio of the defoaming agent is about 1 ppm or more, and in order to prevent display defects, the preferable 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 PSA type elements, polymerizable compounds are 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 polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, allyl ethers, epoxy compounds (oxirane, oxetane), vinyl Ketones and other compounds. Further preferred examples are acrylate or methacrylate derivatives. By changing the type of compound (4), or by combining a polymerizable compound different from compound (4) in an appropriate ratio, the reactivity of the polymerizable compound or the pretilt angle of liquid crystal molecules can be adjusted. By optimizing the pretilt angle, a short response time of the device can be achieved. The alignment of the liquid crystal molecules is stabilized, so that large contrast or long life can be achieved.

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

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

Polar compounds are organic compounds with polarity. Here, the compound having an ionic bond is not included. Atoms such as oxygen, sulfur, and nitrogen tend to be negatively charged and tend to have a partially negative charge. Carbon and hydrogen are neutral or tend to have a partial positive charge. Polarity is caused by the uneven distribution of partial charge among different kinds of atoms in a compound. For example, the polar compound having _{-OH, -COOH, -SH, -NH 2} ,>NH,> N- least one partial structure or the like.

Seventh, the method of synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Exemplify the synthesis method. Compound (1-1) was synthesized by the method described in Japanese Patent Laid-Open No. 2-503441. Compound (2-5) is synthesized by the method described in Japanese Patent Laid-Open No. 57-165328. Compound (3-18) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. Antioxidants are already commercially available. The compound of formula (5) where n is 1 is available from Sigma-Aldrich Corporation. The compound (5) in which n is 7 is synthesized by the method described in the specification of US Patent No. 3660505. The compound having a cinnamate group, a chalcone group, a hydroxyl group and a polymerizable group as the first additive is a method described in Japanese Patent Laid-Open No. 2012-87286 and Japanese Patent Laid-Open No. 2012-107198 To synthesize. The polymerizable compound having an α-fluoroacrylate group is synthesized by referring to the method described in Japanese Patent Laid-Open No. 2005-112850.

Compounds not described in the synthesis method can be synthesized by the methods described in the following book: "Organic Synthesis (Organic Syntheses)" (John Wiley & Sons, Inc.), "Organic Reaction (Organic Reactions "(John Wiley & Sons, Inc.)," Comprehensive Organic Synthesis "(Pergamon Press)," New Experimental Chemistry Lecture "( Maruzen) etc. The composition is prepared from the compound obtained in the above-described manner by a known method. For example, the component compounds are mixed and then dissolved by heating.

Eighth, the use of the composition will be described. Most 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 the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 can be prepared by controlling the ratio of component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in the 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 retention rate. This composition is suitable for AM devices. This composition is particularly suitable for transmission-type AM devices. 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 AM devices. Furthermore, it can also be used for PM elements. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Especially good for AM components with VA mode, OCB mode, IPS mode or FFS mode. In an AM device having an IPS mode or FFS mode, when no voltage is applied, the arrangement of liquid crystal molecules may be parallel to the glass substrate, or may be vertical. The elements can be reflective, transmissive or semi-transmissive. It is preferably used for a transmission type element. It can also be used for amorphous silicon-TFT devices or polysilicon-TFT devices. It can also be used in a nematic curvilinear aligned phase (NCAP) type device made by microencapsulating the composition or a polymer dispersed (polymer dispersed) formed by forming a three-dimensional network polymer in the composition , PD) type components.

Ninth, the method of manufacturing the element will be described. The first step is to add the first additive to the liquid crystal composition and heat the composition at a temperature higher than the upper limit temperature to dissolve it. The second step is to inject the composition into the 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 polarized ultraviolet rays while heating the liquid crystal composition to a temperature higher than the upper limit temperature. The first additive undergoes dimerization or isomerization by linear polarized light, and also undergoes polymerization. The preferable cumulative light quantity (J / cm ² ) of linearly polarized ultraviolet rays is 0.1 J / cm ² to 20 J / cm ² when it reaches the surface of the element. The preferable range of the accumulated light amount is 0.1 J / cm ² to 10 J / cm ² , and the more preferable range is 0.1 J / cm ² to 7 J / cm ² . The cumulative light quantity (J / cm ² ) can be obtained by using the illuminance of ultraviolet rays (unit: mW / cm ² ) × irradiation time (unit: sec). The temperature conditions during linear polarized ultraviolet irradiation are preferably set in the same manner as the heat treatment temperature. The time of linearly polarized ultraviolet irradiation is calculated based on the lamp illuminance, so from the viewpoint of production efficiency, it is preferable to perform the illuminance as high as possible. The polymer including the first additive is formed as a thin film on the substrate and fixed. The polymer is aligned in a fixed direction at the molecular level, so the thin film has a function as a liquid crystal alignment film. This method can be used to produce a liquid crystal display device that does not have an alignment film such as polyimide. [Example]

The present invention will be further described in detail by examples. The present invention is not limited by these embodiments. 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 nuclear magnetic resonance (NMR) analysis and other methods. The characteristics of the compound, composition and device are measured by the method 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 under the conditions of room temperature, 500 MHz, and the number of accumulations 16 times. Use tetramethylsilane as an internal standard. ^In the measurement of ¹⁹ F-NMR, CFCl _{3 was} used as an internal standard, and the total number of times was 24. In the description of NMR spectroscopy, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet (Quintet), sex refers to sixt (sextet), m refers to multiplet (multiplet), br refers to broad peak (broad).

Gas chromatography analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas is 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 the component compounds, the capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; manufactured by Agilent Technologies Inc.) was used; the fixed liquid phase was dimethyl polysilicon Oxane; non-polar). After the column was kept at 200 ° C for 2 minutes, the temperature was raised to 280 ° C at a rate of 5 ° C / min. After preparing the sample as an acetone solution (0.1% by weight), 1 μL of it was injected into the sample gasification chamber. The record meter is the C-R5A chromatograph module (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the retention time of the peak corresponding to the component compounds and the area of the peak.

The solvent used to dilute the sample can be chloroform, hexane, etc. In order to separate the component compounds, the following capillary columns can be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner) manufactured by Restek Corporation 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. For the purpose of preventing overlapping of compound peaks, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, 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 the mixture of liquid crystal compounds. The area ratio of the peak in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystal compound. When using the capillary column described above, the correction coefficients of various liquid crystal compounds can be regarded as 1. Therefore, the ratio (wt%) of the liquid crystal compound can be calculated from the area ratio of the peak.

Measurement sample: When measuring the characteristics of the composition and components, the composition is used directly as the sample. When measuring the characteristics of the compound, a sample for measurement was prepared by mixing the compound (15% by weight) in the mother liquid crystal (85% by weight). Based on the value obtained by the measurement, the property value of the compound is calculated by extrapolation. (Extrapolated value) = {(measured value of sample)-0.85 × (measured value of mother liquid crystal)} / 0.15. At this ratio, when the smectic phase (or crystal) is precipitated at 25 ° C, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% % Order changed. Using this extrapolation method, the values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound are obtained.

Use the following mother liquid crystal. The proportion of component compounds is expressed in% by weight.

Measurement method: The characteristics are measured by the following method. Most of these methods are the methods described in the JEITA standard (JEITA · ED-2521B) reviewed and formulated by Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA) or modified by it Cheng's method. No thin film transistor (TFT) was installed in the TN device used in the measurement.

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

(2) lower limit temperature (T _C; ℃) nematic phase: A sample having a nematic phase into glass vials, at 0 ℃, -10 ℃, -20 ℃ , -30 ℃, and -40 ℃ After storing in the freezer for 10 days, observe the liquid crystal phase. 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. Sometimes the lower limit temperature of the nematic phase is simply referred to as "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s): based on M. Imai et al. “Molecular Crystals and Liquid Crystals” No. 259 The method described in page 37 (1995) was used for the measurement. A sample was placed in a TN device with a twist angle of 0 ° and a gap (cell gap) between two glass substrates of 5 μm. To this element, a voltage is applied stepwise in the range of 16 V to 19.5 V in units of 0.5 V. After no voltage was applied for 0.2 seconds, it was applied repeatedly under the condition that only one rectangular wave (rectangular pulse; 0.2 seconds) and no voltage (2 seconds) were applied. The peak current and peak time of the transient current generated by this application are measured. Based on these measured values and the calculation formula (8) described on page 40 of the paper by M. Imai et al., The value of the rotational viscosity is obtained. The value of the dielectric anisotropy required for this calculation is measured using item (6) using the element that measures the rotational viscosity.

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C): using light with a wavelength of 589 nm, an Abbe refractometer with a polarizing plate attached to the eyepiece was used for measurement. After rubbing the surface of the main prism in one direction, add the sample dropwise to the main prism. 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 optical anisotropy value is calculated according to 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) of 9 μm and a twist angle of 80 degrees between two glass substrates. A sine wave (10 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecule 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 short-axis direction of the liquid crystal molecule was measured after 2 seconds. The value of dielectric anisotropy is calculated according to the formula of Δε = ε∥-ε⊥.

(7) Threshold voltage (Vth; measured at 25 ° C; V): 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 distance (cell gap) of two glass substrates of 0.45 / Δn (μm) and a twist angle of 80 degrees. The voltage applied to this element (32 Hz, rectangular wave) is in units of 0.02 V, and increases from 0 V to 10 V in steps. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. A voltage-transmittance curve is prepared in which the transmittance is 100% when the light amount reaches the maximum, and the transmittance is 0% when the light amount is the smallest. The threshold voltage is represented by the voltage when the transmittance reaches 90%.

(8) Voltage retention rate (VHR-1; measured at 25 ° C;%): The TN device used in the measurement has a polyimide alignment film, and the distance between two glass substrates (cell gap) is 5 μm. After inserting the sample, the element is sealed with an adhesive hardened with ultraviolet light. A pulse voltage (5 V, 60 microseconds) was applied to the TN element 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 the unit cycle was obtained. Area B is the area without attenuation. The voltage retention rate is expressed by the percentage of area A relative to area B.

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

(10) Voltage retention rate (VHR-3; measured at 25 ° C;%): After ultraviolet irradiation, the voltage retention rate was measured, and the stability to ultraviolet rays was evaluated. The TN device used in the measurement had a polyimide alignment film, and the cell gap was 5 μm. A sample was injected into the device, and light was irradiated for 20 minutes. The light source is the ultra-high pressure mercury lamp USH-500D (manufactured 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. The 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 retention rate (VHR-4; measured at 25 ° C;%): After heating the TN element injected with the sample in a constant temperature bath at 80 ° C for 500 hours, the voltage retention rate was measured and the evaluation of heat stability. In the measurement of VHR-4, the attenuated voltage was measured during 16.7 milliseconds. The composition having a large VHR-4 has a large stability to heat.

(12) Response time (τ; measured at 25 ° C; ms): 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 (60 Hz, 5 V, 0.5 seconds) was applied to this element. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the smallest, the transmittance is regarded as 0%. 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 expressed by the sum of the rise time and fall time determined in the above manner.

(13) Elastic constant (K; measured at 25 ° C; pN): In the measurement, HP4284A LCR tester manufactured by Hewlett-Packard Co., Ltd. was used. A sample is placed in a horizontally aligned element with a gap (cell gap) of two glass substrates of 20 μm. A charge of 0 to 20 volts was applied to the device, and the electrostatic capacitance and applied voltage were measured. Using the formula (2.98) and formula (2.101) on page 75 of the “Liquid Crystal Device Manual” (Nikkei Industry News Corporation), the measured capacitance (C) and the applied voltage (V) are fitted according to the formula ( 2.99) to obtain the values of K11 and K33. Next, K22 is calculated using the previously obtained values of K11 and K33 in the formula (3.18) on page 171 of the "Liquid Crystal Device Manual" (Nikkei Industry News Corporation). The elastic constant is expressed by the average value of K11, K22, and K33 obtained as described above.

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

(15) Helical pitch (P; measured at room temperature; μm): The spiral pitch is measured using the wedge method. Refer to page 196 of the "LCD Fact Sheet" (released in 2000, Maruzen). After injecting the sample into the wedge-shaped unit and allowing it to stand for 2 hours at room temperature, observe the interval of the staggered line (d2-d1) with a polarizing microscope (Nikon (share), trade name MM40 / 60 series) . The spiral pitch (P) is calculated based on the following formula which represents 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 the trans configuration. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, summarize the characteristic values of the composition.

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

Example of element 1. Raw material A composition in which an alignment monomer is added is injected into an element that does not have an alignment film. After irradiating linearly polarized light, the alignment of the liquid crystal molecules in the device was confirmed. First, the raw materials will be described. The raw materials are composition such as alignment monomer and composition (M1) to composition (M20). The alignment monomer is appropriately selected from the compounds described below. The composition is as follows.

[Composition (M1)] 3-HHXB (F, F) -F (1-4) 6% 3-BB (F, F) XB (F, F) -F (1-18) 13% 3-HHBB (F, F) -F (1-19) 4% 4-HHBB (F, F) -F (1-19) 5% 3-HBBXB (F, F) -F (1-23) 3% 3- BB (F) B (F, F) XB (F) -F (1-28) 2% 4-BB (F) B (F, F) XB (F, F) -F (1-29) 8% 5-BB (F) B (F, F) XB (F, F) -F (1-29) 7% 3-HH-V (2-1) 44% V-HHB-1 (2-5) 6 % 2-BB (F) B-3 (2-8) 2% NI = 79.8 ℃; 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 (1-28) 3% 3-BB (F) B (F, F) XB (F) -F (1-28) 3% 4-BB (F) B (F, F) XB (F)- F (1-28) 4% 5-HB-CL (1) 5% 2-HH-5 (2-1) 8% 3-HH-V (2-1) 10% 3-HH-V1 (2- 1) 7% 4-HH-V (2-1) 10% 4-HH-V1 (2-1) 8% 5-HB-O2 (2-2) 7% 4- HHEH-3 (2-4) 3% 1-BB (F) B-2V (2-8) 3% 1O1-HBBH-3 (-) 5% NI = 78.5 ℃; 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 ℃; 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-HHEBH- 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-B B (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 <-2 0 ℃; Δn = 0.091; Δε = 5.7; Vth = 1.83 V; η = 14.9 mPa · s; γ1 = 69.3 mPa · s.

The aligning monomer as the first additive is the following compound.

2. Alignment of liquid crystal molecules <Polarized exposure conditions> 250 W ultra-high pressure mercury lamp (Multi-Light lamp manufactured by Ushio Motor Co., Ltd.) and wire grid polarizer (Mott) ProFlux (UVT-260A) manufactured by MOXTEK company, and irradiated with 3 mW / cm ² (Ushio UTI-150 and UVD-S313 manufactured by Ushio Motor Co., Ltd. were used to measure the wavelength of 313 nm Illumination) intensity of light. Example 1 The compound (A-1-1-1) as the first additive was added to the composition (M15) at a ratio of 0.3 parts by weight. The mixture was injected into an IPS device without an alignment film at 90 ° C (above the upper limit temperature of the nematic phase). While heating the IPS element at 90 ° C, the element was irradiated with linearly polarized ultraviolet rays (313 nm, 5.0 J / cm ² ) from the normal direction to obtain an element with an alignment control layer formed. The irradiated ultraviolet rays pass through the polarizer, thereby becoming linearly polarized light. Next, the element formed with the alignment control layer was placed on a polarizing microscope to observe the alignment state of the liquid crystal. The polarizer and the analyzer of the polarizing microscope are arranged so that their transmission axes are orthogonal to each other. First, the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope become parallel, that is, the angle between the alignment direction of the liquid crystal molecules and the transmission axis of the polarizer of the polarizing microscope becomes 0 degrees, The element is arranged on the horizontal rotating platform of the polarizing microscope. Light is irradiated from the lower side of the device, that is, the polarizer side, and observe whether there is light passing through the analyzer. Since the light transmitted through the analyzer is not observed, the alignment is judged to be "good". In addition, in the same observation, when light passing through the analyzer is observed, the alignment is determined to be "defective". Next, the element is rotated on the horizontal rotating 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 increased as the angle formed by the polarization axis of the polarizing microscope and the alignment direction of the liquid crystal molecules became larger, and became approximately the maximum when the angle was 45 degrees. In the device obtained as described above, the liquid crystal molecules are aligned in a substantially horizontal direction with respect to the main surface of the substrate of the device, and it is determined as "horizontal alignment". In this Example 1, no light leakage was observed, so the alignment was good. In addition, the liquid crystal molecules are aligned horizontally.

Example 2 The compound (B-1-2-1) as the first additive was added to the composition (M1). Using this mixture, an element was produced in the same manner as in Example 1. The same method as in Example 1 was used to observe the presence or absence of light leakage. As a result, no light leakage was observed, so the alignment was good.

Example 3 The compound (B-1-3-1) as the first additive was added to the composition (M11) at a ratio of 0.5 parts by weight. The mixture was injected into an IPS element without an alignment film at 95 ° C (above the upper limit temperature of the nematic phase). Linearly polarized light (313 nm, 2.0 J / cm ² ) was irradiated to the device from the normal direction at 100 ° C (above the upper limit temperature). The same method as in Example 1 was used to observe the presence or absence of light leakage. As a result, no light leakage was observed, so the alignment was good.

Example 4 The compound (A-1-1-1) as the first additive was added to the composition (M18) at a ratio of 0.5 parts by weight. The mixture was injected into an IPS device without an alignment film at 90 ° C (above the upper limit temperature of the nematic phase). Linearly polarized light (313 nm, 2.0 J / cm ² ) was irradiated to the device from the normal direction at 90 ° C (above the upper limit temperature). The same method as in Example 1 was used to observe the presence or absence of light leakage. As a result, no light leakage was observed, so the alignment was good.

Example 5 The compound (B-1-2-1) as the first additive was added to the composition (M19) at a ratio of 0.5 parts by weight. The mixture was injected into an IPS device without an alignment film at 90 ° C (above the upper limit temperature of the nematic phase). Linearly polarized light (313 nm, 2.0 J / cm ² ) was irradiated to the device from the normal direction at 90 ° C (above the upper limit temperature). The same method as in Example 1 was used to observe the presence or absence of light leakage. As a result, no light leakage was observed, so the alignment was good.

Example 6 The compound (A-1-1-1) as the first additive was added to the composition (M20) at a ratio of 0.5 parts by weight. The mixture was injected into an IPS device without an alignment film at 90 ° C (above the upper limit temperature of the nematic phase). Linearly polarized light (313 nm, 2.0 J / cm ² ) was irradiated to the device from the normal direction at 90 ° C (above the upper limit temperature). The same method as in Example 1 was used to observe the presence or absence of light leakage. As a result, no light leakage was observed, so the alignment was good.

Example 7 The compound (A-1-1-1) and the compound (A-1-7-1) as the first additive were added to the composition (M20) at a ratio of 0.5 parts by weight, respectively. The mixture was injected into an IPS device without an alignment film at 90 ° C (above the upper limit temperature of the nematic phase). Linearly polarized light (313 nm, 2.0 J / cm ² ) was irradiated to the device from the normal direction at 90 ° C (above the upper limit temperature). The same method as in Example 1 was used to observe the presence or absence of light leakage. As a result, no light leakage was observed, so the alignment was good.

3. Compatibility of the alignment monomer and the liquid crystal composition The stability of the mixture of the liquid crystal composition and the alignment monomer obtained in the above examples at room temperature was evaluated. After mixing, change to an isotropic liquid at 100 ° C and leave 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 7, and the compatibility of any of the alignment monomers was good.

Comparative Example 1 Only the composition (M15) was injected into the IPS element without the alignment film. The same method as in Example 1 was used to observe the presence or absence of light leakage, and as a result, light leakage was observed, so the alignment was poor.

Comparative Examples 2 to 6 Inject only the composition (M1), only the composition (M11), only the composition (M18), only the composition (M19), or only the composition (M20) to In the IPS element having an alignment film, the same method as in Example 1 was used to observe the presence or absence of light leakage. As a result, light leakage was observed, and therefore the alignment was poor.

In Examples 1 to 6, although the type and amount of the composition or the first additive and the heating temperature during polarized light exposure were changed, no light leakage was observed. This result indicates that even if there is no alignment film such as polyimide in the device, alignment is good, and all liquid crystal molecules are aligned in a fixed direction. Even if a variety of aligning monomers are used, it is the same tendency. On the other hand, in Comparative Examples 1 to 6 that did not contain the first additive, light leakage was observed. From the above results, it can be seen that the thin film formed from the first additive plays an important role in the alignment of liquid crystal molecules. In addition, it is understood that the compatibility with the liquid crystal composition is also good. The effect of such an alignment monomer can be obtained in the same manner except for the combination of other liquid crystal compositions disclosed in the above examples. In the case of other alignment monomers (for example, compound (A-1-1) to compound (A-1-9), compound (B-1-1) to compound (B-1-8)), The same effect can be expected. 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 the usable element, a short response time, a high voltage retention rate, a low threshold voltage, a large contrast, and a long life can be obtained . Furthermore, a liquid crystal display element having a liquid crystal composition having a high maximum temperature in the nematic phase, a low minimum temperature in the nematic phase, a low viscosity, an appropriate optical anisotropy, and a positive dielectric can be obtained Among characteristics such as high anisotropy, large specific resistance, high stability to ultraviolet rays, and high stability to heat, at least one characteristic is satisfied. [Industry availability]

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

no

Claims (26)

A liquid crystal display element which sandwiches a liquid crystal layer between a pair of substrates arranged oppositely and bonded via a sealant, and has an alignment control between the pair of substrates and the liquid crystal layer to control alignment of liquid crystal molecules A liquid crystal layer comprising a liquid crystal composition having a positive dielectric anisotropy, the liquid crystal composition comprising a formula selected from formula (A-1), formula (A-2), formula (B-1) and formula (B-2) at least one compound in the group of compounds represented as a first additive and as an alignment monomer and a liquid crystal compound, the alignment control layer includes by polymerizing the first additive And the resulting polymer, In formula (A-1) and formula (A-2), P ^{10 is} independently a group selected from the groups represented by formula (Q-1) to formula (Q-5); formula (Q-1) to In formula (Q-5), M ¹⁰ , M ²⁰ , and M ^{30 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine In the formula (A-1) and formula (A-2), Sp ¹⁰ and Sp ^{11 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 fluorinated , Chlorine 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- or -C≡C- substitution; In formula (Q-6), M ¹¹ , M ²¹ , and M ^{31 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with 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 by fluorine or chlorine, and at least one -CH ₂ -may be substituted by -O-, -CO -, -COO-, or -OCO- substitution; in formula (A-1), formula (A-2), formula (B-1) and formula (B-2), ring A ¹⁰ , ring A ²⁰ , ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-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, stilbene-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-Tetrahydrocyclopenta [a] phenanthrene-3,17-diyl, the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO -, -OCO-C≡C-, -CH = CH-, -CF = CF-, or -C≡C-, 1,4-phenylene, 4,4'-biphenylene, Naphthalene-2,6-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, stilbene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2, 6-diyl, in these rings, at least one hydrogen may be through fluorine, hydroxyl, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 11 carbons, or Alkenyloxy substituted with 2 to 11 carbons, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; in formula (A-1) and formula (A-2), Z ^{10 is} independently a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; In formula (A-2), Z ¹¹ is -CH = CH-CO- or -CO- CH = CH-; in formula (A-1) and formula (A-2), n ¹⁰ is an integer from 0 to 4; in formula (B-1) and formula (B-2), R ²⁰ is hydrogen and fluorine , Chlorine, hydroxyl, cyano, nitro, Trifluoromethyl, C 1-10 alkyl or C 1-10 alkoxy; Sp ²⁰ and Sp ^{21 are} independently a single bond or C 1-12 alkylene, the alkylene At least one hydrogen can be substituted by fluorine, at least one -CH ₂ -can be substituted by -O-, -COO-, or -OCO-, at least one -CH ₂ -CH ₂ -can be substituted by -CH = CH- or -C ≡C- substitution; Z ^{20 is} independently a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO- ,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; n ²⁰ is an integer from 0 to 3. The liquid crystal display element as described in item 1 of the patent application range, wherein in formula (A-1) and formula (A-2) as described in item 1 of the patent application range, P ^{10 is} independently the formula (Q-1 ); In formula (Q-1), M ^{10 is} independently hydrogen, fluorine, methyl, or trifluoromethyl; M ²⁰ and M ³⁰ are hydrogen; Sp ¹⁰ and Sp ^{11 are} independently a single bond or carbon number 2 Alkylene to 12, at least one hydrogen of said alkylene can be substituted by fluorine, chlorine or formula (Q-6), at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, Or -OCO- substitution, at least one -CH ₂ -CH ₂ -may be substituted by -CH = CH- or -C≡C-; in formula (Q-6), M ^{11 is} independently hydrogen, fluorine, methyl, Or trifluoromethyl; M ²¹ and M ³¹ are hydrogen; Sp ^{41 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one hydrogen of the alkyl group may be substituted by fluorine, and at least one -CH ₂ -Can be substituted by -O-, -CO-, -COO-, or -OCO-; in formula (A-1), formula (A-2), formula (B-1), and formula (B-2) , Ring A ¹⁰ , Ring A ²⁰ , Ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-cyclohexyl, 1,4-phenylene, 4,4′-biphenylene, naphthalene -2,6-diyl, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, the adjacent structure is -CH = CH-COO-, -OCO-CH = CH-, -C ≡C-COO-, -OCO-C≡C-, -CH = CH-, -CF = CF- or -C≡C-, 1,4-extended phenyl, 4,4'-extended Biphenyl, or naphthalene-2,6-diyl, in these rings, at least one hydrogen can be through fluorine, hydroxyl, trifluoromethyl, C 1-5 alkyl, or C 1-5 alkyl Oxygen substitution; in formula (A-1) and formula (A-2), Z ^{10 is} independently a single bond, -COO-, -OCO-, -CH = CH-COO-, -OCO-CH = CH- , -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO-C≡C-, -CH ₂ O-, -OCH _2- , -CF ₂ O -, -OCF _2- , -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or- C≡C-; In formula (A-2), Z ¹¹ is -CH = CH-CO- or -CO-CH = CH-; In formula (A-1) and formula (A-2), n ¹⁰ is Integers from 0 to 4; in formula (B-1) and formula (B-2), R ²⁰ is hydrogen, fluorine, hydroxyl, C 1-5 alkyl or C 1-5 alkoxy; Sp ²⁰ and Sp ^{21 are} independently a single bond or an alkylene group having 1 to 12 carbons, At least one -CH ₂ -of the alkylene group may be substituted by -O-; n ^{2 0} is an integer of 0 to 3. The liquid crystal display element as described in the first or second patent application scope, wherein in formula (A-1) and (A-2) as described in the first patent application scope, P ^{10 is} independently the formula (Q-1); In formula (Q-1), M ^{10 is} independently hydrogen or methyl; M ²⁰ and M ³⁰ are hydrogen; Sp ¹⁰ and Sp ^{11 are} independently single bonds or carbon number 2 to 12 extensions Alkyl group, at least one hydrogen of the alkylene group may be substituted by formula (Q-6), 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- or -C≡C-; In formula (A-1) and formula (A-2), Z ^{10 is} independently a single bond, -COO-,- OCO-, -CH = CH-COO-, -OCO-CH = CH-, -OCO-CH ₂ CH _2- , -CH ₂ CH ₂ -COO-, -C≡C-COO-, -OCO-C≡ C-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CONH-, -NHCO-,-(CH ₂ ) _4- , -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF- or -C≡C-; In formula (A-2), Z ¹¹ is -CH = CH-CO- or -CO-CH = CH-; Ring A ¹⁰ , Ring A ²⁰ , Ring A ³⁰ , Ring A ⁴⁰ and Ring A ^{50 are} independently 1,4-phenylene, 1,4-cyclohexyl, naphthalene-2,6-diyl, or tetrahydro Naphthalene-2,6-diyl, adjacent structures are -CH = CH-COO-, -OCO-CH = CH-, -C≡C-COO-, -OCO-C≡C-, -CH = CH- , -CF = CF- or -C≡C-, it is 1,4-phenylene or naphthalene-2,6-diyl. In the 1,4-phenylene, any hydrogen can pass through Fluorine, hydroxyl, trifluoromethyl, C 1-3 alkyl, or C 1-3 alkoxy substitution; in formula (A-1) and formula (A-2), n ¹⁰ is from 0 to Integer of 2; in formula (B-1) and formula (B-2), R ²⁰ is hydrogen, fluorine, hydroxyl, C 1-5 alkyl or C 1-5 alkoxy; Sp ²⁰ and Sp ^{21 is} independently a single bond or an alkylene group having 1 to 12 carbon atoms, at least one of which -CH ₂ -may be substituted with -O-; n ²⁰ is an integer of 0 to 3. The liquid crystal display element of claim 1 or claim 2, wherein when the total amount of liquid crystal compounds is 100 parts by weight, the ratio of the alignment monomer as the first additive is 0.1 The range is from 10 parts by weight to 10 parts by weight. The liquid crystal display element according to item 1 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (1) as the first component, In formula (1), R ¹ is C 1-12 alkyl, C 1-12 alkoxy, or C 2-12 alkenyl; 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; Z ¹ is a single bond, ethylidene, 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 substituted with fluorine or chlorine, a C 1-12 alkyl group, at least one hydrogen substituted with fluorine or chlorine, a C 1-12 alkoxy group, or at least one hydrogen Alkenyloxy having 2 to 12 carbons substituted with fluorine or chlorine; a is 1, 2, 3, or 4. The liquid crystal display element according to item 5 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (1-1) to formula (1-39) as the first component, In formula (1-1) to formula (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 6 of the patent application range, wherein the proportion of the first component is in the range of 10% by weight to 85% by weight relative to the total amount of the liquid crystal compound. The liquid crystal display element according to item 1 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (2) as the second component, In formula (2), R ² and R ^{3 are} independently a C 1-12 alkyl group, a C 1-12 alkoxy group, a C 2-12 alkenyl group, or at least one hydrogen group 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, ethyl ester, or carbonyloxy; b is 1, 2, or 3. The liquid crystal display element according to item 8 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-13) as the second component, In formula (2-1) to formula (2-13), R ² and R ^{3 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons Or at least one alkenyl group having 2 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine. The liquid crystal display element according to item 8 or 9 of the patent application range, wherein the proportion of the second component is in the range of 10% by weight to 85% by weight relative to the total amount of the liquid crystal compound. The liquid crystal display element according to item 1 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (3) as the third component, In formula (3), R ⁴ and R ^{5 are} independently a C 1-12 alkyl group, a C 1-12 alkoxy group, a C 2-12 alkenyl group, or a C 2-12 alkenyl group Yloxy; 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 substituted with at least one hydrogen by fluorine or chlorine, naphthalene-2,6-diyl substituted by at least one hydrogen by fluorine or chlorine, chroman-2, 6-diyl, or chroman-2,6-diyl with at least one hydrogen substituted with 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, ethylidene, 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 patent application range, 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 formula (3-1) to formula (3-22), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons , Or an alkenyloxy group having 2 to 12 carbon atoms. The liquid crystal display element according to claim 11 or claim 12, wherein the ratio of the third component to the total amount of the liquid crystal compound is in the range of 3% by weight to 25% by weight. The liquid crystal display element according to item 1 of the patent application scope, which further contains at least one compound selected from the group of polymerizable compounds represented by formula (4) as the second additive, In formula (4), ring F ³ and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-di Oxane-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in these rings, at least one hydrogen can be substituted by fluorine, chlorine, C 1-12 alkyl, C 1-12 alkyl Oxygen, or at least one hydrogen substituted with fluorine or chlorine, C 1-12 alkyl; ring G is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene Group, 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 can be Chlorine, C 1-12 alkyl, C 1-12 alkoxy, or C 1-12 alkyl substituted with at least one hydrogen by 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 substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )-, these In the group, 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 an alkylene group having 1 to 10 carbon atoms In the alkyl group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted by -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 as described in item 14 of the patent application range, wherein in formula (4), P ¹ , P ² , and P ^{3 are} independently selected from formula (P-1) to formula (P-5) The group in the group of polymerizable groups, In formula (P-1) to formula (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 is substituted with fluorine or chlorine C1-C5 alkyl. The liquid crystal display element according to item 14 of the patent application scope, which contains at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-27) as a second additive , In formula (4-1) to formula (4-27), P ⁴ , P ⁵ , and P ^{6 are} independently selected from the group of polymerizable groups represented by formula (P-1) to formula (P-3) The base in the 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 substituted 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. In the alkylene group, at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO- substitution, at least one -CH ₂ CH ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine. The liquid crystal display element according to any one of claims 14 to 16, wherein when the total amount of the liquid crystal compound is 100 parts by weight, the ratio of the second additive is 0.03 parts by weight to 10 The range of parts by weight. The liquid crystal display element as described in item 1 of the patent application range, wherein the upper limit temperature of the nematic phase is 70 ° C or higher, the optical anisotropy at wavelength 589 nm (measured at 25 ° C) is 0.07 or higher, 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 the liquid crystal display element as described in any one of claims 1 to 18 between a pair of substrates, and by irradiating linearly polarized light, The first additive in the liquid crystal composition reacts. The liquid crystal display element as described in item 19 of the patent application range, 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 response alignment mode, and a driving method of the liquid crystal display element Active matrix method. The liquid crystal display element as described in Item 19 of the patent application range, 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, which contains the liquid crystal composition in the liquid crystal display element according to any one of claims 1 to 17, and the polymerizability in the liquid crystal composition The compound is polymerized. 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, which is used in a liquid crystal display element. Use of a liquid crystal composition, which is a liquid crystal composition in a liquid crystal display element as described in any one of patent application items 1 to 17, which is used in a polymer-stabilized alignment type liquid crystal In the display element. Use of a compound of formula (A-1), formula (A-2), formula (B-) in the liquid crystal display element according to any one of claims 1 to 3 1) The compound represented by formula (B-2) is used as a monomer for forming an alignment control layer. 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.