TW201809235A - Liquid crystal composition and use thereof, liquid crystal display device, polymer sustained alignment type liquid crystal display device and liquid crystal display device without alignment film - Google Patents

Abstract

A nematic liquid-crystal composition which contains, as a first additive, at least one compound selected from among polar compounds represented by formula (1) and having a (meth)acrylamide group and which has negative dielectric anisotropy; and a liquid-crystal display element including the nematic liquid-crystal composition. In formula (1), R1 is a hydrogen atom, a halogen atom, a C1-12 alkyl, etc.; ring A and ring B are independently 1,4-cyclohexylene, 1,4-phenylene, etc.; Z1 is a single bond, etc.; Sp1 is a single bond, a C1-7 alkylene, etc.; a is 0 to 4; and R2 and R3 are independently a hydrogen atom or methyl.

Description

Liquid crystal composition and liquid crystal display element

The present invention relates to a liquid crystal composition containing a polar compound (or a polymer thereof) having a (meth) acrylamido group and having a negative dielectric anisotropy, and a liquid crystal display element containing the composition.

In liquid crystal display elements, the operation modes based on liquid crystal molecules are classified into phase change (PC), twisted nematic (TN), super twisted nematic (STN), and electrically controlled birefringence ( electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Field-induced photo-reactive alignment (FPA) and other modes. The component-based driving methods are classified into a passive matrix (PM) and an active matrix (AM). PM is classified as static, multiplex, etc. AM is classified as thin film transistor (TFT), metal-insulator-metal (MIM), and the like. TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified into a high temperature type and a low temperature type according to manufacturing steps. The 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 correlation between the two characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the element can be used. A preferred upper limit temperature of the nematic phase is about 70 ° C or higher, and a preferred lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of a composition is related to the response time of the element. In order to display a moving image as a component, it is preferable that the response time is short. Ideally a response time shorter than 1 millisecond. Therefore, the viscosity of the composition is preferably small. More preferably, the viscosity is low at low temperatures.

The optical anisotropy of the composition is related to the contrast of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy is required, that is, the optical anisotropy is appropriate. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast. The appropriate value of the product depends on the type of operation mode. In the VA mode device, 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, a composition having a large optical anisotropy is preferred for a device having a small cell gap. The large dielectric anisotropy of the composition contributes to a low threshold voltage, low power consumption, and large contrast in the device. Therefore, it is preferable that the dielectric anisotropy is large. A large specific resistance in the composition contributes to a large voltage holding ratio and a large contrast in the device. Therefore, a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage is preferred. Further, it is preferable that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition to ultraviolet rays and heat is related to the life of the device. When this stability is high, the life of the element is long. Such characteristics are preferable for AM elements used in liquid crystal projectors, liquid crystal televisions, and the like.

In a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules can be achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display device, the effect of a polymer is effectively used. First, a composition to which a small amount of a polymerizable compound is added is injected into a device. Then, 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, a polymer can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened, and the afterimage of the image is improved. Such an effect of a polymer can be expected in a device having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

On the other hand, in a liquid crystal display element having no alignment film, a liquid crystal composition containing a polymer and a polar compound having no polymerizable group is used (Patent Documents 1 to 5). First, a composition containing a small amount of a polymerizable compound and a small amount of a polar compound is injected into a device. Here, polar compounds are adsorbed and aligned on the substrate surface. According to this arrangement, the liquid crystal molecules are aligned. Then, while applying a voltage between the substrates of the element, the composition was irradiated with ultraviolet rays. Here, the polymerizable compound is polymerized and the alignment of the liquid crystal molecules is stabilized. In this composition, a polymer and a polar compound can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened, and the afterimage of the image is improved. Furthermore, an element without an alignment film does not require a step of forming an alignment film. Since there is no alignment film, there is no case where the resistance of the element is reduced due to the interaction between the alignment film and the composition. An element having a mode such as TN, ECB, OCB, IPS, VA, FFS, and FPA can be expected to have such an effect due to a combination of a polymer and a polar compound.

A composition having a positive dielectric anisotropy is used for an AM device having a TN mode. A composition having a negative dielectric anisotropy is used for an AM device having a VA mode. A composition having a positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode. A polymer stabilized alignment type AM device uses a composition having a positive or negative dielectric anisotropy. Examples of liquid crystal compositions having negative dielectric anisotropy are disclosed in Patent Documents 1 to 6 below. In the present invention, a polymer compound and a polar compound used previously are used in combination, or a polymer compound and a polar compound used previously are used in combination to prepare a combination of a polar compound having a (meth) acrylamido group and a liquid crystal compound. Composition. This composition can be used suitably for the liquid crystal display element which does not have an alignment film. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2014/090362 [Patent Literature 2] International Publication No. 2014/094959 [Patent Literature 3] International Publication No. 2013/004372 [Patent Literature 4] International Publication No. 2012/104008 No. [Patent Document 5] International Publication No. 2012/038026 [Patent Document 6] Japanese Patent Laid-Open No. 50-35076

[Problems to be Solved by the Invention] An object of the present invention is to provide a liquid crystal composition containing a polar compound having a (meth) acrylamide group represented by the formula (1). The fluorenamine-based polar compound has high compatibility with liquid crystal compounds. Another object is to provide a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer generated from the polar compound having a (meth) acrylamide group. Another object is to provide a liquid crystal composition having a high upper limit temperature in the nematic phase, a low lower limit temperature in the nematic phase, a low viscosity, a suitable optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a Among characteristics such as high ultraviolet stability and high thermal stability, at least one characteristic is sufficiently satisfied. Another object is to provide a liquid crystal composition having a proper balance between at least two characteristics. Another object is to provide a liquid crystal display element containing such a composition. Yet another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast, long life, and the like. [Means for solving problems]

The present invention relates to a liquid crystal composition and a liquid crystal display element containing the composition. The liquid crystal composition contains a group selected from the group consisting of a polar compound having a (meth) acrylamide group represented by formula (1). At least one of the compounds is used as the first additive, and has negative dielectric anisotropy. In formula (1), R ¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring A and ring B are independently 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, pyridine-2,5-diyl, pyrene -2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, at least one hydrogen of these rings may be fluorine, chlorine, alkyl having 1 to 12 carbons, Alkoxy having 1 to 12 carbons, or at least one hydrogen substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine; Z ¹ is a single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ¹ is a single bond or carbon Numbers 1 to 7 of alkylene groups At least one -CH ₂ - may be -O -, - COO-, -OCO- or substituted with at least one -CH ₂ CH ₂ - may be replaced by -CH = CH-, the plurality of groups, at least one hydrogen may be Fluorine substituted; a is 0, 1, 2, 3, or 4; R ² and R ^{3 are} independently hydrogen or methyl. [Effect of the invention]

An advantage of the present invention is to provide a liquid crystal composition containing a polar compound having a (meth) acrylamide group represented by formula (1). Here, the polar compound having a (meth) acrylamide group has High compatibility of liquid crystal compounds. Another advantage is to provide a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules by the action of a polymer generated from the polar compound having a (meth) acrylamide group. Another advantage is to provide a liquid crystal composition, which has a high upper limit temperature in the nematic phase, a low lower limit temperature in the nematic phase, low viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, and Among characteristics such as high ultraviolet stability and high thermal stability, at least one characteristic is sufficiently satisfied. Another advantage is to provide a liquid crystal composition having a proper balance between at least two characteristics. Another advantage is to provide a liquid crystal display element containing such a composition. Another advantage is to provide an AM device, which has the characteristics of short response time, large voltage holding ratio, low threshold voltage, large contrast, long life, and the like.

The terms used in this specification are described below. The terms "liquid crystal composition" and "liquid crystal display element" may be simply referred to as "composition" and "element", respectively. "Liquid crystal display device" is a generic term for a liquid crystal display panel and a liquid crystal display module. Liquid crystal compounds are compounds that have a nematic phase, a smectic phase, and a liquid crystal phase. They do not have a liquid crystal phase, but are mixed for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase. Generic term for compounds in a composition. This compound has, for example, a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in a composition. "(Meth) acrylamido" refers to one or both of "acrylamido" and "methacrylamido".

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

The "upper limit temperature of the nematic phase" may be simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" may be simply referred to as the "lower limit temperature". "High specific resistance" means that the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage. It also has a large specific resistance at temperatures close to the upper limit temperature. "Large voltage holding rate" means that the element has a large voltage holding rate not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after long-term use, not only at room temperature, but also It also has a large voltage holding ratio at a temperature close to the upper limit temperature. For a composition or an element, characteristics are sometimes studied before and after a change over time test (including an accelerated deterioration test). Regarding the expression "improving dielectric anisotropy", when a composition having a positive dielectric anisotropy means that its value increases positively, it refers to a composition having a negative dielectric anisotropy. The value increases negatively.

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

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

In the chemical formula of the component compound, the symbol of the terminal group R ¹ is used for various compounds. In these compounds, the two groups represented by any two R ¹ may be the same or different. For example, there may be a case where R ¹ of the compound (1-1) is an ethyl group and R ¹ of the compound (1-2) is an ethyl group. In some cases, R ¹ of the compound (1-1) is an ethyl group, and R ¹ of the compound (1-2) is a propyl group. This rule also applies to other terminal group marks. In formula (1), when a is 2, there are two rings A. In this compound, the two groups represented by the two rings A may be the same or different. When a is greater than 2, this rule also applies to any two rings A. This rule also applies to other tokens. This rule also applies to the case of two -Sp ³ -P ² in compound (4-27).

Symbols A, B, C, and D surrounded by hexagons correspond to rings such as ring A, ring B, ring C, and ring D, respectively, and represent rings such as six-membered rings and condensed rings. An oblique line crossing the hexagon indicates that an arbitrary hydrogen on the ring may be substituted with a group such as -Sp ² -P ¹ . Subscripts such as 'j' indicate the number of substituted groups. When the subscript 'j' is 0, there is no such substitution. When the subscript 'j' is 2 or more, there are multiple -Sp ² -P ¹ on the ring J. A plurality of groups represented by -Sp ² -P ¹ may be the same or different.

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

The alkyl group of the liquid crystal compound is linear or branched, and does not include a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. For stereoconfigurations related to 1,4-cyclohexyl, the trans configuration is usually better than the cis configuration. Halogen means fluorine, chlorine, bromine, and iodine. The preferred halogen is fluorine or chlorine. A more preferred halogen is fluorine.

The present invention includes the following items.

Item 1. A liquid crystal composition containing at least one compound selected from the group consisting of a polar compound having a (meth) acrylamido group represented by the formula (1) as a first additive, and having a negative media Electrical anisotropy. In formula (1), R ¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring A and ring B are independently 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, pyridine-2,5-diyl, pyrene -2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, at least one hydrogen of these rings may be fluorine, chlorine, alkyl having 1 to 12 carbons, Alkoxy having 1 to 12 carbons, or at least one hydrogen substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine; Z ¹ is a single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ¹ is a single bond or carbon Numbers 1 to 7 of alkylene groups At least one -CH ₂ - may be -O -, - COO-, -OCO- or substituted with at least one -CH ₂ CH ₂ - may be replaced by -CH = CH-, the plurality of groups, at least one hydrogen may be Fluorine substituted; a is 0, 1, 2, 3, or 4; R ² and R ^{3 are} independently hydrogen or methyl.

Item 2. The liquid crystal composition according to Item 1, which contains a group selected from the group of polar compounds having a (meth) acrylamido group represented by formula (1-1) to formula (1-12). At least one compound is used as the first additive. In the formulae (1-1) to (1-12), R ¹ is hydrogen, halogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, At least one hydrogen with 1 to 12 carbons substituted with fluorine or chlorine, or at least one hydrogen with 2 to 12 carbons substituted with fluorine or chlorine; Z ¹ , Z ² , and Z ^{3 are} independently Single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ¹ is a single bond or an alkylene group having 1 to 7 carbon atoms. Among the alkylene groups, at least one -CH ₂ -may pass through -O-, -COO-, or -OCO- substituted, at least one -CH ₂ CH ₂ -can be substituted by -CH = CH-, in these groups, at least one hydrogen can be substituted by fluorine; L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ , and L ^{14 are} independently hydrogen, fluorine, methyl, or ethyl; R ² and R ^{3 are} independently Hydrogen or methyl.

Item 3. The liquid crystal composition according to Item 1 or 2, wherein the ratio of the first additive is in a range of 0.05% by weight to 10% by weight.

Item 4. The liquid crystal composition according to any one of Items 1 to 3, which contains, as a first component, at least one compound selected from the group of compounds represented by Formula (2). In formula (2), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an olefin having 2 to 12 carbons Oxygen; ring C and ring E are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, at least one hydrogen substituted with fluorine or chlorine 1,4 -Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene Base, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromogen- 2,6-diyl; Z ⁴ and Z ^{5 are} independently a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; b is 1, 2 , Or 3, c is 0 or 1, and the sum of b and c is 3 or less.

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

Item 6. The liquid crystal composition according to Item 4 or Item 5, wherein the ratio of the first component is in a range of 10% by weight to 90% by weight.

Item 7. The liquid crystal composition according to any one of Items 1 to 6, which contains, as a second component, at least one compound selected from the group of compounds represented by Formula (3). In the formula (3), R ⁶ and R ^{7 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and at least one hydrogen is subjected to fluorine or chlorine. Alkyl groups having 1 to 12 carbon atoms, or alkenyl groups having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexyl, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, -CH ₂ CH _2- , -CH ₂ O -, -OCH _2- , -COO-, or -OCO-; d is 1, 2, or 3.

Item 8. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as第二 组合。 The second component. In the formulae (3-1) to (3-13), R ⁶ and R ^{7 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , An alkyl group having 1 to 12 carbons substituted with at least one hydrogen with fluorine or chlorine, or an alkenyl group with 2 to 12 carbons substituted with at least one hydrogen with fluorine or chlorine.

Item 9. The liquid crystal composition according to Item 7 or 8, wherein the ratio of the second component is in a range of 10% by weight to 70% by weight.

Item 10. The liquid crystal composition according to any one of Items 1 to 9, comprising at least one compound selected from the group of polymerizable compounds represented by Formula (4) as a second additive. In formula (4), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Or at least one hydrogen is substituted by fluorine or chlorine alkyl having 1 to 12 carbons; ring K is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-benzene Naphthalene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1 , 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5 -Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen of these rings may be via fluorine, Chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen substituted with fluorine or chlorine and alkyl having 1 to 12 carbons; Z ⁷ and Z ^{8 are} independently a single bond or a C 1-10 alkylene group, said alkylene, at least one -CH ₂ - may be -O -, substituted or COO- -OCO-, and -, - CO -, At least one -CH ₂ CH ₂ - may be -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; P ¹ , P ² , and P ³ are polymerizable groups; Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or carbon number 1 To 10, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may Substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; q is 0, 1, or 2; j, k, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is 1 or more.

Item 11. The liquid crystal composition according to Item 10, wherein in Formula (4), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of Formulas (P-1) to (P-5) Group of polymerizable groups. In the formulae (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 5 carbons.

Item 12. The liquid crystal composition according to any one of Items 1 to 11, which contains at least one selected from the group of polymerizable compounds represented by the formula (4-1) to the formula (4-28) The compound acts as a second additive. In the formulae (4-1) to (4-28), P ¹ , P ² , and P ^{3 are} independently selected from the group of polymerizable groups represented by the formulae (P-1) to (P-3) A group in the group, where 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 atom having 1 to 5 carbon atoms substituted with fluorine or chlorine Alkyl Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the alkylene groups, at least one of -CH ₂ -may pass through -O-, -COO-, -OCO. -, Or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Item 13. The liquid crystal composition according to any one of Items 10 to 12, wherein the ratio of the second additive is in a range of 0.03% by weight to 10% by weight.

Item 14. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 13.

Item 15. The liquid crystal display element according to item 14, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 16. A polymer stabilized alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 13, and a first additive in the liquid crystal composition is polymerized, or The first additive and the second additive were polymerized.

Item 17. A liquid crystal display element without an alignment film, comprising the liquid crystal composition according to any one of items 1 to 13, and a first additive in the liquid crystal composition is polymerized, or The first additive and the second additive were polymerized.

Item 18. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of items 1 to 13, and is used in a liquid crystal display element.

Item 19. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 13, and is used in a polymer-stabilized alignment type liquid crystal display element.

Item 20. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 13, and is used in a liquid crystal display element without an alignment film.

The present invention also includes the following items. (A) The method for manufacturing a liquid crystal display element, wherein the liquid crystal composition is arranged between two substrates, and light is irradiated under a voltage applied to the composition, so that The polar compound having a (meth) acrylamide group is polymerized to produce the liquid crystal display element. (B) The liquid crystal composition has an upper limit temperature of a nematic phase of 70 ° C or higher, an optical anisotropy (measured at 25 ° C) at a wavelength of 589 nm of 0.08 or higher, and dielectric properties at a frequency of 1 kHz Anisotropy (measured at 25 ° C) is -2 or less.

The present invention also includes the following items. (C) In the composition, although compounds (5) to (7) described in Japanese Patent Laid-Open No. 2006-199941 are liquid crystal compounds having a positive dielectric anisotropy, the composition contains At least one compound selected from the group of these compounds. (D) The composition containing at least two of the polar compounds. (E) The composition further contains a polar compound different from the polar compound. (F) The composition, which contains one of additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, and a polar compound, Two, or at least three. The additive may be the same as the first additive or the second additive, or may be different. (G) An AM device containing the composition. (H) An element containing the composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (I) A transmissive element containing the composition. (J) Use of the composition as a composition having a nematic phase. (K) Use as an optically active composition by adding an optically active compound to the composition.

The composition of the present invention will be described in the following order. First, the composition of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be described. Third, a combination of components in the composition, a preferred ratio of the components, and its basis will be described. Fourth, a preferred embodiment of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, a method for synthesizing the component compounds will be described. Finally, the use of the composition will be described.

First, the composition of the composition will be described. The composition of the present invention is classified into a composition A and a composition B. The composition A may contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compounds selected from the compounds (2) and (3). The "other liquid crystal compound" is a liquid crystal compound different from the compound (2) and the compound (3). Such a compound is mixed in the composition for the purpose of further adjusting the characteristics. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like.

The composition B contains substantially only a liquid crystal compound selected from the compound (2) and the compound (3). "Substantially" means that the composition B may contain additives, but does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. From the viewpoint of cost reduction, the composition B is superior to the composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, the composition A is superior to the composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L is large or high, M is medium, and S is small or low. Symbols L, M, and S are classifications based on qualitative comparisons among component compounds, and symbol 0 means that the value is zero, or close to zero.

1) The value of the dielectric anisotropy is negative, and the sign indicates the magnitude of the absolute value

When the component compounds are mixed in the composition, the main effects of the component compounds on the characteristics of the composition are as follows. The compound (1) as a first additive is adsorbed on the substrate surface by the action of a polar group, and controls the alignment of liquid crystal molecules. In order to obtain a desired effect, the compound (1) must have high compatibility with a liquid crystal compound. Compound (1) has a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-shaped, so it is most suitable for this purpose. Compound (1) is polymerized to form a polymer. This polymer stabilizes the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the afterimage of the image. The compound (2) as the first component increases the dielectric anisotropy and lowers the lower limit temperature. The compound (3) as the second component lowers the viscosity, increases the upper limit temperature, or lowers the lower limit temperature. The compound (4) as a second additive is added to the composition for the purpose of making it more suitable for a polymer-stabilized alignment element. Compound (4) is polymerized to form a polymer. This polymer stabilizes the alignment of liquid crystal molecules, thereby reducing the response time of the device and improving the afterimage of the image. From the viewpoint of the alignment of the liquid crystal molecules, the polymer of the compound (1) has an interaction with the surface of the substrate, so it is inferred that it is more effective than the polymer of the compound (4).

Third, a combination of components in the composition, a preferred ratio of the components, and its basis will be described. A preferable combination of the components in the composition is compound (1) + compound (2) + compound (3), or compound (1) + compound (2) + compound (3) + compound (4).

The compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. In order to align the liquid crystal molecules, a preferred ratio of the compound (1) is about 0.05% by weight or more. In order to prevent display failure of the device, a preferred ratio of the compound (1) is about 10% by weight or less. A more preferred ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferred ratio is in the range of about 0.5% by weight to about 5% by weight.

The compound (1) is preferably stable because it is added to the composition. When the compound (1) is added to the composition, it is preferred that the compound does not reduce the voltage retention of the device. The compound (1) preferably has low volatility. The preferred molar mass is 130 g / mol or more. A more preferred molar mass is in the range of 150 g / mol to 500 g / mol.

In order to increase the dielectric anisotropy, a preferable ratio of the compound (2) is about 10% by weight or more. In order to lower the lower limit temperature, a preferable ratio of the compound (2) is about 90% by weight or less. A more preferred ratio is in the range of about 20% by weight to about 85% by weight. A particularly preferred ratio is in the range of about 30% by weight to about 85% by weight.

In order to reduce the viscosity, to increase the upper limit temperature, or to lower the lower limit temperature, the preferred ratio of the compound (3) is about 10% by weight or more. In order to improve the dielectric anisotropy, the preferred ratio of the compound (3) is about 70% by weight or less. A more preferred ratio is in the range of about 15% by weight to about 65% by weight. A particularly preferred ratio is in the range of about 20% by weight to about 60% by weight.

In order to improve the long-term reliability of the device, the preferred ratio of the compound (4) is about 0.03% by weight or more. In order to prevent display failure of the device, the preferred ratio of the compound (4) is about 10% by weight or less. A more preferred ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1% by weight.

Fourth, a preferred embodiment of the component compound will be described. In Formula (1), Formula (1-1) to Formula (1-12), R ¹ is hydrogen, halogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, and 2 to 2 carbon atoms. An alkenyl group of 12, an alkyl group of 1 to 12 carbons, at least one hydrogen of which is replaced by fluorine or chlorine, or an alkenyl group of 2 to 12 carbons, of which at least one hydrogen is replaced by fluorine or chlorine. In order to achieve high compatibility with a liquid crystal compound, R ¹ is preferably an alkyl group having 1 to 12 carbon atoms. R ² and R ^{3 are} independently hydrogen or methyl. In order to achieve high compatibility with a liquid crystal compound, R ² is preferably a methyl group. To increase the polymerization rate, preferred R ³ is hydrogen.

Ring A and Ring B are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-di Naphthalene, 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, pyridine-2,5-diyl, pyrene-2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, these rings At least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen substituted with an alkyl group having 1 to 12 carbons with fluorine or chlorine. . Preferred ring A or ring B is 1,4-cyclohexyl, 1,4-phenylene, or 2-fluoro-1,4-phenylene.

Z ¹ , Z ² , and Z ^{3 are} independently a single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-. Preferably, Z ¹ , Z ² , or Z ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. More preferably, Z ¹ , Z ² , or Z ³ is a single bond.

Sp ¹ is a single bond or an alkylene group having 1 to 7 carbon atoms. Among the alkylene groups, at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-, and at least one -CH ₂ CH ₂ -may be substituted by -CH = CH-, and among these groups, at least one hydrogen may be substituted by fluorine. The preferred Sp ¹ is a single bond.

a is 0, 1, 2, 3, or 4. Preferred a is 1, 2, or 3.

L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ , and L ^{14 are} independently hydrogen, fluorine, or methyl Or ethyl. Preferred L ¹ to L ¹⁴ are hydrogen, fluorine, or methyl. More preferred L ¹ to L ¹⁴ are hydrogen or fluorine.

In formulas (2) and (3), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon number 2 to 12 alkenyloxy. For increasing the stability to ultraviolet light or heat, preferably R ⁴ or R ⁵ is alkyl having 1 to 12, for increasing the dielectric anisotropy, preferred R ⁴ or R ⁵ having 1 to 12 carbon atoms Alkoxy. R ⁶ and R ^{7 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, at least one hydrogen having 1 to 12 carbon atoms substituted with fluorine or chlorine 12 alkyl groups, or at least one hydrogen alkenyl group having 2 to 12 carbon atoms substituted with fluorine or chlorine. In order to reduce the viscosity, preferred R ⁶ or R ⁷ is an alkenyl group having 2 to 12 carbons. In order to improve the stability to ultraviolet rays or heat, preferred R ⁶ or R ⁷ is an alkyl group having 1 to 12 carbon numbers.

For R ¹ , R ⁴ , R ⁵ , and R ⁶ , a preferred alkyl group, a preferred alkoxy group, a preferred alkenyl group, a preferred alkenyl group, and at least one hydrogen are replaced by fluorine or chlorine. The alkyl group and the alkenyl group in which at least one hydrogen is substituted with fluorine or chlorine will be described.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. To reduce viscosity, more preferred alkyl groups are ethyl, propyl, butyl, pentyl, or heptyl.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, or heptyloxy. To reduce viscosity, a more 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. To reduce viscosity, more preferred alkenyl groups are 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 reducing viscosity, it compares with alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl It is preferably a trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

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

Preferred examples of the alkyl group in which at least one hydrogen is replaced by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl, or 8-fluorooctyl. To increase the dielectric anisotropy, more preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.

Preferred examples of alkenyl in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butene Group, 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, more preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring C and ring E are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine Or tetrahydropyran-2,5-diyl. Preferable examples of "the 1,4-phenylene substituted with at least one hydrogen by fluorine or chlorine" are: 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene Phenyl, or 2-chloro-3-fluoro-1,4-phenylene. In order to reduce the viscosity, the preferred ring C or ring E is 1,4-cyclohexyl. In order to improve the dielectric anisotropy, the preferred ring C or ring E is tetrahydropyran-2,5-diyl. In order to improve the optical anisotropy, the preferred ring C or ring E is 1,4-phenylene. In order to increase the upper limit temperature, the trans configuration is better than the cis configuration for the stereo configuration related to 1,4-cyclohexyl. Tetrahydropyran-2,5-diyl is or , Preferably .

Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromogen-2,6-diyl. To reduce viscosity, the preferred ring D is 2,3-difluoro-1,4-phenylene. To reduce the optical anisotropy, the preferred ring D is 2-chloro-3-fluoro-1,4- In order to increase the dielectric anisotropy of phenylene, the preferred ring D is 7,8-difluorochroman-2,6-diyl.

Ring F and Ring G 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 viscosity or to increase the upper limit temperature, the preferred ring F or ring G is 1,4-cyclohexyl. To increase the optical anisotropy or to lower the lower limit temperature, the preferred ring F or ring G is 1,4. -Phenylene. In order to increase the upper limit temperature, the trans configuration is better than the cis configuration for the stereo configuration related to 1,4-cyclohexyl.

Z ⁴ and Z ^{5 are} independently a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z ⁴ or Z ⁵ is a single bond. In order to reduce the lower limit temperature, the preferred Z ⁴ or Z ⁵ is -CH ₂ CH _2- . In order to improve the dielectric anisotropy, the preferred Z ⁴ Or Z ⁵ is -CH ₂ O- or -OCH _2- . Z ⁶ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z ⁶ is a single bond, to reduce the lower limit temperature, the preferred Z ⁶ is -CH ₂ CH _2- , and to increase the upper limit temperature, the preferred Z ⁶ is -COO- or -OCO-.

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

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

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

Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the alkylene groups, at least one of -CH ₂ -may pass through -O-, -COO-, -OCO. -, Or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferably, Sp ² , Sp ³ , or Sp ⁴ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, Or -CH = CH-CO-. More preferably, Sp ² , Sp ³ , or Sp ⁴ is a single bond.

Ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Substituted by an alkyl group having 1 to 12 carbon atoms substituted with fluorine or chlorine. Preferred ring J or ring P is phenyl. Ring K is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 , 4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl Naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be passed through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen is substituted by a C1-C12 alkyl group substituted by fluorine or chlorine. The preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the alkylene groups, at least one -CH ₂ -can pass through -O-, -CO-, -COO-, or- OCO- substituted, and at least one -CH ₂ CH ₂ -can be via -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ ) -substituted, in which at least one hydrogen may be substituted with fluorine or chlorine. Preferably, Z ⁷ or Z ⁸ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. More preferred Z ⁷ or Z ⁸ are single bonds.

q is 0, 1, or 2. The preferred q is 0 or 1. j, k, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is 1 or more. Preferably, j, k, or p is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to compound (1-12) as described in item 2. It is preferred that at least two of the first additives are a compound (1-1) and a compound (1-2), or a combination of a compound (1-1) and a compound (1-4).

Preferred compound (2) is the compound (2-1) to compound (2-22) according to item 5. Among these compounds, it is preferred that at least one of the first components is compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8), Or compound (2-10). It is preferable that at least two of the first components are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2- 6) Compound (2-3) and compound (2-10), compound (2-4) and compound (2-6), or a combination of compound (2-4) and compound (2-8).

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

Preferred compound (4) is the compound (4-1) to compound (4-28) as described in item 12. Among these compounds, it is preferred that at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26) , Or compound (4-27). It is preferred that at least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4 -24), compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4 -18) and compound (4-24).

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. An optically active compound is added to the composition for the purpose of giving a torsion angle to the helical structure of the liquid crystal molecules. Examples of such compounds are compound (5-1) to compound (5-5). The preferable ratio of an optically active compound is about 5 weight% or less. A more preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

In order to prevent the decrease in specific resistance caused by heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long time, antioxidants are used Added to the composition. Preferable examples of the antioxidant include a compound (6) in which n is an integer of 1 to 9, and the like.

In the compound (6), preferred n is 1, 3, 5, 7, or 9. More preferably n is 7. The compound (6) in which n is 7 is small in volatility, and is therefore effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after a long-term use of the device. In order to obtain the effect, a preferred ratio of the antioxidant is about 50 ppm or more, and in order not to lower the upper limit temperature or not to raise the lower limit temperature, the preferred ratio of the antioxidant is about 600 ppm or less. A better ratio is in the range of about 100 ppm to about 300 ppm.

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

In order to be suitable for a device in a guest host (GH) mode, a dichroic dye such as an azo pigment, an anthraquinone pigment, or the like is added to the composition. A preferred ratio of the pigment is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition. In order to obtain the effect, a preferable ratio of the defoaming agent is about 1 ppm or more, and in order to prevent display failure, a preferable ratio of the defoaming agent is about 1,000 ppm or less. A more preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for a polymer stabilized alignment (PSA) type device, a polymerizable compound is used. Compound (1) and compound (4) are suitable for this purpose. Other polymerizable compounds different from the compound (1) and the compound (4) and the compound (1) and the compound (4) may be added to the composition together. Preferable examples of the other polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxetane, oxetane), and vinyl ketone. And other compounds. More preferred examples are acrylates or methacrylates. A preferable ratio of the compound (1) and the compound (4) is about 10% by weight or more based on the total weight of the polymerizable compound. A more preferred ratio is about 50% by weight or more. A particularly preferred ratio is about 80% by weight or more. A particularly good ratio is also 100% by weight. By changing the kind of the compound (1) and the compound (4), or by combining other polymerizable compounds with the compound (1) and the compound (4) at an appropriate ratio, the reactivity of the polymerizable compound or the liquid crystal molecules can be adjusted. Pretilt angle. By optimizing the pretilt angle, a short response time of the element can be achieved. Since the alignment of the liquid crystal molecules is stabilized, a large contrast or a long life can be achieved.

This polymerizable compound is polymerized by ultraviolet irradiation. Polymerization may be performed in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization, suitable types of initiators, and appropriate amounts are known to those skilled in the art and are described in the literature. For example, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered) as a light initiator Trademark; BASF) is suitable for free radical polymerization. A preferred ratio of the photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight based on the total weight of the polymerizable compound. A more preferred ratio is in the range of about 1% to about 3% by weight.

When the polymerizable compound is stored, a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor are hydroquinone, a hydroquinone derivative such as methyl hydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.

Seventh, a method for synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Illustrative synthesis methods. The synthesis method of the compound (1) is described in the item of an Example. Compound (2-1) is synthesized by a method described in Japanese Patent Application Publication No. Hei 2-503441. Compound (3-5) is synthesized by a method described in Japanese Patent Laid-Open No. 57-165328. Compound (4-18) is synthesized by a method described in Japanese Patent Laid-Open No. 7-101900. Some compounds (6) are commercially available products. The compound of formula (6) where n is 1 is available from Sigma-Aldrich Corporation. Compound (6) and the like in which n is 7 are synthesized by a method described in US Pat. No. 3,660,505.

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

Finally, the use of the composition will be described. Most of the compositions have a lower limit temperature of about -10 ° C or lower, an upper limit temperature of about 70 ° C or higher, and optical anisotropy in a range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 can also be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having an optical anisotropy in a range of about 0.10 to about 0.30 can also be prepared by trial and error. The device containing this composition has a large voltage holding ratio. This composition is suitable for an AM device. This composition is particularly suitable for a transmissive AM device. This composition can be used as a composition having a nematic phase, and can be used as an optically active composition by adding an optically active compound.

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

An example of a conventional method of manufacturing a polymer-stabilized alignment element is described below. Assemble an element with two substrates, which are called an array substrate and a color filter substrate. The substrate has an alignment film. At least one piece of the substrate has an electrode layer. A liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Additives can be added if necessary. This composition is injected into a device. Light irradiation is performed in a state where a voltage is applied to the element. Preferred is ultraviolet light. The polymerizable compound is polymerized by light irradiation. A polymer-containing composition is produced by this polymerization. The polymer stabilized alignment type element is manufactured by such a procedure.

In this procedure, when a voltage is applied, liquid crystal molecules are aligned by the action of an alignment film and an electric field. According to this alignment, the molecules of the polymerizable compound are also aligned. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. The effect of this polymer shortens the response time of the device. Since the residual image of the image is a poor operation of the liquid crystal molecules, the effect of the polymer also improves the residual image. In addition, the polymerizable compound in the composition may be polymerized in advance, and the composition may be disposed between the substrates of the liquid crystal display element.

When the compound (1), that is, a polar compound having a (meth) acrylamido group is used as the polymerizable compound, an alignment film is not required on the substrate of the device. An element without an alignment film is manufactured from a substrate without an alignment film according to the procedures described in the previous two paragraphs.

In this procedure, the compound (1) is aligned on the substrate due to interaction between the polar group and the surface of the substrate. According to this arrangement, the liquid crystal molecules are aligned. When a voltage is applied, the alignment of the liquid crystal molecules is further promoted. Since the polymerizable group is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. By the effect of this polymer, the alignment of liquid crystal molecules is further stabilized, and the response time of the device is shortened. Since the residual image of the image is a poor operation of the liquid crystal molecules, the effect of the polymer also improves the residual image. [Example]

The present invention will be further described in detail through examples. The invention is not limited by these examples. The present invention includes a mixture of the composition M1 and the composition M2. The present invention also includes a mixture obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of compounds, compositions, and devices were measured by the following methods.

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

Gas chromatographic analysis: The 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 separation of component compounds, a 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 dimethylpolysiloxane Alkane; non-polar). After the column was held at 200 ° C for 2 minutes, the temperature was raised to 280 ° C at a rate of 5 ° C / min. After preparing a sample as an acetone solution (0.1% by weight), 1 μl of the sample was injected into the sample gasification chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed a retention time of a peak and an area of the peak corresponding to the component compounds.

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

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

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

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

Measurement method: The characteristics were measured by the following method. Most of these methods are methods described or modified in the JEITA standard (JEITA · ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA). Methods. The thin-film transistor (TFT) was not mounted on the TN element used for the measurement.

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

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

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s): According to "Molecular Crystals and Liquid Crystals" by M. Imai et al. The measurement is described in the method described on page 37 (1995). A sample was injected into a VA device having a distance (cell gap) between two glass substrates of 20 μm. A voltage is applied to the element in a range of 39 to 50 volts in steps of 1 volt. 0.2 seconds after no voltage was applied, it was repeatedly applied under the conditions of applying only one rectangular wave (rectangular pulse; 0.2 second) and no voltage (2 seconds). The peak current and peak time of the transient current generated by the application were measured. The values of rotational viscosity were obtained from these measured values and calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for this calculation is measured by the method described in Measurement (6).

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

(6) Dielectric anisotropy (Δε; measured at 25 ° C): The value of dielectric anisotropy is calculated according to the formula of Δε = ε∥-ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows. 1) Measurement of dielectric constant (ε∥): A fully washed glass substrate was coated with a solution of octadecyltriethoxysilane (0.16 ml) in ethanol (20 ml). After the glass substrate was rotated by a spinner, it was heated at 150 ° C for 1 hour. A sample was placed in a VA device having a distance (cell gap) between two glass substrates of 4 μm, and the device was sealed with an adhesive hardened by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the major axis direction of the liquid crystal molecules was measured after 2 seconds. 2) Measurement of dielectric constant (ε⊥): A polyimide solution is coated on a sufficiently washed glass substrate. After the glass substrate is fired, the obtained alignment film is subjected to a rubbing treatment. A sample was injected into a TN device having a distance (cell gap) between two glass substrates of 9 μm and a twist angle of 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured 2 seconds later.

(7) Threshold voltage (Vth; measured at 25 ° C; V): The LCD5100 brightness 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 black mode VA device with a gap (cell gap) of two glass substrates of 4 μm and a rubbing direction in antiparallel, and the adhesive was hardened by ultraviolet rays. Component sealed. The voltage (60 Hz, rectangular wave) applied to the device is increased stepwise from 0 V to 20 V at 0.02 V each time. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was prepared with a transmittance of 100% when the light amount reached the maximum and a transmittance of 0% when the light amount reached the minimum. The threshold voltage is expressed by the voltage when the transmittance reaches 10%.

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

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

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

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

(12) Response time (τ; measured at 25 ° C; ms): LCD5100 type brightness meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a VA device having a distance (cell gap) between two glass substrates of 3.5 μm without an alignment film. This element was sealed with an adhesive hardened with ultraviolet rays. While applying a voltage of 30 V to the device, it was irradiated with ultraviolet light of 78 mW / cm ² (405 nm) for 449 seconds (35 J). For ultraviolet irradiation, a multi-metal lamp M04-L41 for ultraviolet curing manufactured by EYE GRAPHICS Co., Ltd. was used. A rectangular wave (120 Hz) was applied to the element. At this time, the element was irradiated with light from a vertical direction, and the amount of light transmitted through the element was measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the minimum, the transmittance is regarded as 0%. The maximum voltage of the rectangular wave is set so that the transmittance becomes 90%. The minimum voltage of the rectangular wave is set to 2.5 V with a transmittance of 0%. Response time is represented by the time (rise time; milliseconds) required for the transmittance to change from 10% to 90%.

(13) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ° C; pN): The measurement was made by Toyo Technica Co., Ltd. EC-1 type elastic constant tester. A sample was injected into a vertical alignment element having a distance (cell gap) between two glass substrates of 20 μm. A charge of 20 volts to 0 volts was applied to the device, and the capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), the measured capacitance (C) and the applied voltage (V) are fitted, and the equation ( 2.100) to obtain the value of the elastic constant.

(14) Specific resistance (ρ; measured at 25 ° C; Ωcm): Put a sample of 1.0 ml in a container provided with an electrode. A DC voltage (10 V) was applied to the container, and a DC current after 10 seconds was measured. The specific resistance is calculated from the following formula. (Specific resistance) = ｛(voltage) × (capacitance of the container)｝ / ｛(DC current) × (dielectric constant of the vacuum)｝. (Formula 1)

(15) Pretilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.) was used for the measurement of the pretilt angle.

(16) Alignment stability (stability of liquid crystal alignment axis): Changes in the liquid crystal alignment axis on the electrode side of the liquid crystal display element were evaluated. Measure the liquid crystal alignment angle f (before) on the electrode side before stress application, and then apply a rectangular wave 4.5 V, 60 Hz to the device for 20 minutes, short-circuit for 1 second, and measure the electrode side again after 1 second and 5 minutes. LCD alignment angle f (after). From these values, the change Δf (deg.) Of the liquid crystal alignment angle after 1 second and after 5 minutes was calculated using the following formula. Δf (deg.) = F (after) -f (before) (Equation 2) These measurements are based on J. Hilfiker, B. Johs, C. Hessinger (C. Herzinger), JF Elman, E. Montbach, D. Bryant and PJ Bos' "Thin Solid Film (Thin Solid Films) "455-456 (2004) 596-600. The change rate of the liquid crystal alignment axis with a small Δf is small, and it can be said that the stability of the liquid crystal alignment axis is good.

Synthesis Example 1 Compound (1-1) was synthesized by the following method.

Step 1 The compound (T-1) (25.0 g), triethylamine (16.65 ml), and THF (300 ml) were placed in a reactor and cooled to 0 ° C. Acrylic acid chloride (9.7 ml) was slowly added dropwise thereto, and the mixture was returned to room temperature while stirring for 6 hours. After the insoluble matter was filtered off, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 9: 1) to obtain compound (T-2) (16.4 g; 54%).

Step 2 Place sodium hydride (2.57 g) and THF (300 ml) into the reactor and cool to 0 ° C. A solution of the compound (T-2) (16.4 g) in THF (100 ml) was slowly added dropwise thereto, and stirred for 1 hour. Slowly dropwise add methyl iodide (3.7 ml), and return to room temperature while stirring for 3 hours. After the insoluble matter was filtered off, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 4: 1). Further, it was purified by recrystallization from heptane to obtain compound (1-1) (14.2 g; 83%).

Compound (1-1) ¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.56 (m, 1H), 6.27 (t, 1H), 5.65 (t, 1H), 4.45 (m, 1H), 2.90 (s, 3H), 1.83-1.52 (m, 8H), 1.43-1.20 (m, 8H), 1.18-0.92 (m, 9H), 0.89-0.80 (m, 5H).

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is a trans configuration. The number in parentheses after the marked compound indicates the chemical formula to which the compound belongs. The symbol (-) means another liquid crystal compound. The ratio (percentage) of the liquid crystalline compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized.

Example of device 1. Raw material A device to which a polar compound having a (meth) acrylamido group represented by formula (1) is added to a device having no alignment film is added. After irradiating ultraviolet rays, the vertical alignment of liquid crystal molecules in the device was investigated. First, the raw materials will be described. The raw materials are from the composition (M1) to the composition (M18), a polar compound (PC-1) having a (meth) acrylamido group, a polar compound (PC-13), and a polymerizable compound (RM-1) to The polymerizable compound (RM-8) is appropriately selected. The composition is as follows.

[Composition M1] 3-HB (2F, 3F) -O2 (2-1) 10% 5-HB (2F, 3F) -O2 (2-1) 7% 2-BB (2F, 3F) -O2 ( 2-4) 7% 3-BB (2F, 3F) -O2 (2-4) 7% 3-B (2F, 3F) B (2F, 3F) -O2 (2-5) 3% 2-HHB ( 2F, 3F) -O2 (2-6) 5% 3-HHB (2F, 3F) -O2 (2-6) 10% 2-HBB (2F, 3F) -O2 (2-10) 8% 3-HBB (2F, 3F) -O2 (2-10) 10% 2-HH-3 (3-1) 14% 3-HB-O1 (3-2) 5% 3-HHB-1 (3-5) 3% 3-HHB-O1 (3-5) 3% 3-HHB-3 (3-5) 4% 2-BB (F) B-3 (3-8) 4% NI = 73.2 ℃; Tc <-20 ℃; Δn = 0.113; Δε = -4.0; Vth = 2.18 V; η = 22.6 mPa · s.

[Composition M2] 3-HB (2F, 3F) -O4 (2-1) 6% 3-H2B (2F, 3F) -O2 (2-2) 8% 3-H1OB (2F, 3F) -O2 ( 2-3) 4% 3-BB (2F, 3F) -O2 (2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH2B (2F, 3F) -O2 (2-7) 7% 5-HH2B (2F, 3F) -O2 (2-7) 4% 2-HBB (2F, 3F)- O2 (2-10) 5% 3-HBB (2F, 3F) -O2 (2-10) 5% 4-HBB (2F, 3F) -O2 (2-10) 6% 2-HH-3 (3- 1) 12% 1-BB-5 (3-3) 12% 3-HHB-1 3-5) 4% 3-HHB-O1 (3-5) 3% 3-HBB-2 (3-6) 3% NI = 82.8 ℃; Tc <-30 ℃; Δn = 0.118; Δε = -4.4; Vth = 2.13 V; η = 22.5 mPa · s.

[Composition M3] 3-HB (2F, 3F) -O2 (2-1) 7% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 5% 5-HHB (2F, 3F) -O2 (2-6) 4% 3-HH1OB (2F, 3F) -O2 (2-8) 4% 2-BB (2F, 3F) B-3 (2-9) 5% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10 8% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3- 1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 3-5) 3% NI = 78.1 ℃; Tc <-30 ℃; Δn = 0.107; Δε = -3.2; Vth = 2.02 V; η = 15.9 mPa · s.

[Composition M4] 3-HB (2F, 3F) -O2 (2-1) 10% 5-HB (2F, 3F) -O2 (2-1) 10% 3-H2B (2F, 3F) -O2 ( 2-2) 8% 5-H2B (2F, 3F) -O2 (2-2) 8% 2-HBB (2F, 3F) -O2 (2-10) 6% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 7% 3-HDhB (2F, 3F)- O2 (2-16) 5% 3-HH-4 (3-1) 14% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 7% NI = 88.5 ℃; Tc <-30 ℃; Δn = 0.108; Δε = -3.8; Vth = 2.25 V; η = 24.6 mPa · s; VHR-1 = 99.1%; VHR-2 = 98.2% VHR-3 = 97.8%.

[Composition M5] 3-HB (2F, 3F) -O2 (2-1) 7% 3-HB (2F, 3F) -O4 (2-1) 8% 3-H2B (2F, 3F) -O2 ( 2-2) 8% 3-BB (2F, 3F) -O2 (2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 4% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -1 (2-6) 6% 2-HBB (2F, 3F) -O2 (2-10) 6% 3-HBB (2F, 3F)- O2 (2-10) 6% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 4% 3-HEB (2F, 3F) B (2F, 3F) -O2 (2-11) 3% 3-H1OCro (7F, 8F) -5 (2-14) 3% 3-HDhB (2F, 3F) -O2 (2-16) 5% 3-HH-O1 (3-1) 5% 1-BB-5 (3-3) 4% V-HHB-1 (3-5) 4% 5-HB (F) BH-3 (3- 12) 5% NI = 81.1 ℃; Tc <-30 ℃; Δn = 0.119; Δε = -4.5; Vth = 1.69 V; η = 31.4 mPa · s.

[Composition M6] 3-HB (2F, 3F) -O4 (2-1) 15% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 ( 2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 7% 3-dhBB (2F, 3F) -O2 (2-17) 5% 3-chB (2F, 3F) -O2 (2-18) 7% 2-HchB (2F, 3F) -O2 (2-19) 8% 5-HH-V (3-1) 18% 7-HB-1 (3-2) 5% V- HHB-1 (3-5) 7% V2-HHB-1 (3-5) 7% 3-HBB (F) B-3 (3-13) 8% NI = 98.8 ℃; Tc <-30 ℃; Δn = 0.111; Δε = -3.2; Vth = 2.47 V; η = 23.9 mPa · s.

[Composition M7] 3-H2B (2F, 3F) -O2 (2-2) 18% 5-H2B (2F, 3F) -O2 (2-2) 17% 3-HHB (2F, 3Cl) -O2 ( 2-12) 5% 3-HBB (2F, 3Cl) -O2 (2-13) 8% 5-HBB (2F, 3Cl) -O2 (2-13) 7% 3-HDhB (2F, 3F) -O2 (2-16) 5% 3-HH-V (3-1) 11% 3-HH-VFF (3-1) 7% F3-HH-V (3-1) 10% 3-HHEH-3 (3 -4) 4% 3-HB (F) HH-2 (3-10) 4% 3-HHEBH-3 (3-11) 4% NI = 77.5 ℃; Tc <-30 ℃; Δn = 0.084; Δε = -2.6; Vth = 2.43 V; η = 22.8 mPa · s.

[Composition M8] 3-HB (2F, 3F) -O2 (2-1) 8% 3-H2B (2F, 3F) -O2 (2-2) 10% 3-BB (2F, 3F) -O2 ( 2-4) 10% 2O-BB (2F, 3F) -O2 (2-4) 3% 2-HHB (2F, 3F) -O2 (2-6) 4% 3-HHB (2F, 3F) -O2 (2-6) 7% 2-HHB (2F, 3F) -1 (2-6) 5% 2-BB (2F, 3F) B-3 (2-9) 6% 2-BB (2F, 3F) B-4 (2-9) 6% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F) -O2 (2-10) 7% 3-HH1OCro (7F, 8F) -5 (2-15) 4% 3-HDhB (2F, 3F) -O2 (2-16) 6% 3-dhBB (2F, 3F) -O2 (2-17) 4% 3-HH-V (3-1) 11% 1-BB-5 (3-3) 5% NI = 70.6 ℃; Tc <-20 ℃; Δn = 0.129; Δε = -4.3; Vth = 1.69 V ; Η = 27.0 mPa · s.

[Composition M9] 3-HB (2F, 3F) -O4 (2-1) 14% 3-H1OB (2F, 3F) -O2 (2-3) 3% 3-BB (2F, 3F) -O2 ( 2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH1OB (2F, 3F) -O2 (2-8) 6% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F) -O2 (2-10) 6% 4-HBB (2F, 3F)- O2 (2-10) 4% 3-HH-V (3-1) 14% 1-BB-3 (3-3) 3% 3-HHB-1 (3-5) 4% 3-HHB-O1 ( 3-5) 4% V-HBB-2 (3-6) 4% 1-BB (F) B-2V (3-8) 6% 5-HBBH-1O1 (-) 4% NI = 93.0 ℃; Tc <-30 ℃; Δn = 0.123; Δε = -4.0; Vth = 2.27 V; η = 29.6 mPa · s.

[Composition M10] 3-HB (2F, 3F) -O4 (2-1) 6% 3-H2B (2F, 3F) -O2 (2-2) 8% 3-H1OB (2F, 3F) -O2 ( 2-3) 5% 3-BB (2F, 3F) -O2 (2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 5-HHB (2F, 3F) -O2 (2-6) 7% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F)- O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 6% 3-HH-V (3-1) 11% 1-BB-3 (3-3) 6% 3 -HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 4% 3-B (F) BB-2 (3-7) 4% NI = 87.6 ℃; Tc <-30 ℃; Δn = 0.126; Δε = -4.5; Vth = 2.21 V; η = 25.3 mPa · s.

[Composition M11] 3-HB (2F, 3F) -O4 (2-1) 6% 3-H2B (2F, 3F) -O2 (2-2) 8% 3-H1OB (2F, 3F) -O2 ( 2-3) 4% 3-BB (2F, 3F) -O2 (2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 6% 3-HHB (2F, 3F) -O2 (2-6) 10% 5-HHB (2F, 3F) -O2 (2-6) 8% 2-HBB (2F, 3F) -O2 (2-10) 5% 3-HBB (2F, 3F)- O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 5% 2-HH-3 (3-1) 12% 1-BB-3 (3-3) 6% 3 -HHB-1 (3-5) 3% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 6% 3-B (F) BB-2 (3-7) 3% NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.124; Δε = -4.5; Vth = 2.22 V; η = 25.0 mPa · s.

[Composition M12] 3-HB (2F, 3F) -O2 (2-1) 7% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 4% 5-HHB (2F, 3F) -O2 (2-6) 5% 3-HH1OB (2F, 3F) -O2 (2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 33% V-HHB-1 (3-5) 3% NI = 76.4 ℃; Tc <-30 ℃; Δn = 0.104; Δε = -3.2; Vth = 2.06 V; η = 15.6 mPa · s.

[Composition M13] 2-H1OB (2F, 3F) -O2 (2-3) 6% 3-H1OB (2F, 3F) -O2 (2-3) 4% 3-BB (2F, 3F) -O2 ( 2-4) 3% 2-HH1OB (2F, 3F) -O2 (2-8) 14% 2-HBB (2F, 3F) -O2 (2-10) 7% 3-HBB (2F, 3F) -O2 (2-10) 11% 5-HBB (2F, 3F) -O2 (2-10) 9% 2-HH-3 (3-1) 5% 3-HH-VFF (3-1) 30% 1- BB-3 (3-3) 5% 3-HHB-1 (3-5) 3% 3-HBB-2 (3-6) 3% NI = 78.3 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -3.2; Vth = 2.17 V; η = 17.7 mPa · s.

[Composition M14] 3-HB (2F, 3F) -O2 (2-1) 5% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 5% 5-HHB (2F, 3F) -O2 (2-6) 4% 3-HH1OB (2F, 3F) -O2 (2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 9% 4-HBB (2F, 3F) -O2 (2-10) 4% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 3-5) 5% NI = 81.2 ℃; Tc <-20 ℃; Δn = 0.107; Δε = -3.2; Vth = 2.11 V; η = 15.5 mPa · s.

[Composition M15] 3-H2B (2F, 3F) -O2 (2-2) 7% 3-HHB (2F, 3F) -O2 (2-6) 8% 3-HH1OB (2F, 3F) -O2 ( 2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 7% 2-BB (2F, 3F) B-4 (2-9) 7% 3-HDhB (2F, 3F) -O2 (2-16) 3% 5-HDhB (2F, 3F) -O2 (2-16) 4% 2-HchB (2F, 3F) -O2 (2-19) 8% 4-HH-V (3 -1) 15% 3-HH-V1 (3-1) 6% 1-HH-2V1 (3-1) 6% 3-HH-2V1 (3-1) 4% V2-BB-1 (3-3 ) 5% 1V2-BB-1 (3-3) 5% 3-HHB-1 (3-5) 6% 3-HB (F) BH-3 (3-12) 4% NI = 88.7 ℃; Tc <-30 ℃; Δn = 0.115; Δε = -1.9; Vth = 2.82 V; η = 17.3 mPa · s.

[Composition M16] V2-H2B (2F, 3F) -O2 (2-2) 8% V2-H1OB (2F, 3F) -O4 (2-3) 4% 3-BB (2F, 3F) -O2 ( 2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH2B (2F, 3F) -O2 (2-7) 7% 5-HH2B (2F, 3F) -O2 (2-7) 4% V-HH2B (2F, 3F) -O2 (2-7) 6% V2-HBB (2F, 3F)- O2 (2-10) 5% V-HBB (2F, 3F) -O2 (2-10) 5% V-HBB (2F, 3F) -O4 (2-10) 6% 2-HH-3 (3- 1) 12% 1-BB-5 (3-3) 12% 3-HHB-1 (3-5 4% 3-HHB-O1 (3-5) 3% 3-HBB-2 (3-6) 3% NI = 89.9 ℃; Tc <-20 ℃; Δn = 0.122; Δε = -4.2; Vth = 2.16 V ; Η = 23.4 mPa · s.

[Composition M17] 3-HB (2F, 3F) -O2 (2-1) 3% V-HB (2F, 3F) -O2 (2-1) 3% V2-HB (2F, 3F) -O2 ( 2-1) 5% 5-H2B (2F, 3F) -O2 (2-2) 5% V2-BB (2F, 3F) -O2 (2-4) 3% 1V2-BB (2F, 3F) -O2 (2-4) 3% 3-HHB (2F, 3F) -O2 (2-6) 6% V-HHB (2F, 3F) -O2 (2-6) 6% V-HHB (2F, 3F)- O4 (2-6) 5% V2-HHB (2F, 3F) -O2 (2-6) 4% V2-BB (2F, 3F) B-1 (2-9) 4% V2-HBB (2F, 3F ) -O2 (2-10) 5% V-HBB (2F, 3F) -O2 (2-10) 4% V-HBB (2F, 3F) -O4 (2-10) 5% V-HHB (2F, 3Cl) -O2 (2-12) 3% 3-HH-V (3-1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 (3 -5) 3% NI = 77.1 ℃; Tc <-20 ℃; Δn = 0.101; Δε = -3.0; Vth = 2.04 V; η = 13.9 mPa · s.

[Composition M18] V-HB (2F, 3F) -O2 (2-1) 10% V2-HB (2F, 3F) -O2 (2-1) 10% 2-H1OB (2F, 3F) -O2 ( 2-3) 3% 3-H1OB (2F, 3F) -O2 (2-3) 3% 2O-BB (2F, 3F) -O2 (2-4) 3% V2-BB (2F, 3F) -O2 (2-4) 8% V2-HHB (2F, 3F) -O2 (2-6) 5% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F)- O2 (2-10) 3% V-HBB (2F, 3F) -O2 (2-10) 6% V-HBB (2F, 3F) -O4 (2-10) 8% V-HHB (2F, 3Cl) -O2 (2-12) 7% 3-HH-4 (3-1) 14% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 7% NI = 75.9 ℃; Tc <-20 ℃; Δn = 0.114; Δε = -3.9; Vth = 2.20 V; η = 24.7 mPa · s.

The first additive is a polar compound (PC-1) to a polar compound (PC-13) having a (meth) acrylamido group. Furthermore, only in the case of having hydrogen directly bonded to nitrogen, that is, only when R ² in formula (1) is hydrogen, in order to clarify the structure of the (meth) acrylamide group, it is described in the structural formula The expression of NH is performed.

The second additive is a polymerizable compound (RM-1) to a polymerizable compound (RM-8).

2. Vertical alignment of liquid crystal molecules Example 1 A polar compound (PC-1) having a (meth) acrylamide group was added to the composition M1 in a proportion of 5% by weight. This mixture was injected on a hot stage at 100 ° C. into a device having an interval (cell gap) between two glass substrates of 4.0 μm without an alignment film. A polar compound (PC-1) having a (meth) acrylamido group was polymerized by irradiating the device with ultraviolet (28 J) by using an ultrahigh-pressure mercury lamp USH-250-BY (manufactured by Ushio Electric). . This element was placed in a polarizing microscope in which a polarizing element and an analyzer were orthogonally arranged, and the element was irradiated with light from below to observe the presence or absence of light leakage. When the liquid crystal molecules are sufficiently aligned and light does not pass through the device, the vertical alignment is judged to be "good". When the light transmitted through the device was observed, it was judged as "defective".

Examples 2 to 19 and Comparative Example 1 In Examples 2 to 19, a mixture prepared by adding a polar compound having a (meth) acrylamido group to the composition was used to produce a film without an alignment film. element. The same method as in Example 1 was used to observe the presence or absence of light leakage. The results are summarized in Table 4. In Example 19, a polymerizable compound (RM-1) was also added in a proportion of 0.5% by weight. In Comparative Example 1, for comparison, the following polar compound (PC-14) was selected. This compound is different from the compound (1) because it does not have a polymerizable group.

As can be seen from Table 4, although the composition or the type of the polar compound having a (meth) acrylamido group was changed in Examples 1 to 18, no light leakage was observed. This result indicates that even if there is no alignment film in the device, the vertical alignment is good, and the liquid crystal molecules are stably aligned. In Example 19, a polymerizable compound (RM-1) was further added, but the same results were obtained. On the other hand, in Comparative Example 1, light leakage was observed. This result indicates that the vertical alignment is not good. Therefore, it is understood that a polymer produced from a polar compound having a (meth) acrylamide group plays an important role in vertical alignment of liquid crystal molecules.

3. Compatibility of polar compound and liquid crystal composition Example 20 A polar compound (PC-1) having a (meth) acrylamido group was added to the composition M1 in a proportion of 5 wt%. After heating to 100 ° C to change it into an isotropic liquid, it was left to cool to 25 ° C. After one day at room temperature, the presence or absence of precipitates was confirmed. When a precipitate is confirmed, it is judged as "precipitation exists", and when a precipitate is not confirmed, it is judged as "no precipitation".

Examples 21 to 22 and Comparative Examples 2 to 4 In Examples 21 and 22, the compatibility of the polar compound and the liquid crystal composition was evaluated by the same method as in Example 20. The results are summarized in Table 5. In Comparative Examples 2 to 4, for comparison, the following polar compounds (PC-15 to PC-17) were selected. These compounds are different from the compound (1) because they do not have a polymerizable group.

As can be seen from Table 5, no precipitates were confirmed in Examples 20 to 22. On the other hand, in Comparative Examples 2 to 3, precipitates were confirmed. This result indicates that the polar compound having a (meth) acrylamido group is more compatible with the liquid crystal composition than the polar compound having a hydroxyl group. [Industrial availability]

The liquid crystal composition of the present invention can control the alignment of liquid crystal molecules in an element without an alignment film. The liquid crystal display element containing the composition has characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast, long life, and the like. Therefore, it can be used in liquid crystal projectors and liquid crystal televisions.

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Claims (20)

A liquid crystal composition containing at least one compound selected from the group of polar compounds having a (meth) acrylamido group represented by formula (1) as a first additive, and having a negative dielectric anisotropy opposite sex: In formula (1), R ¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and at least one hydrogen is replaced by fluorine or chlorine Alkyl group having 1 to 12 carbon atoms, or alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring A and ring B are independently 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, pyridine-2,5-diyl, pyrene -2,7-diyl, phenanthrene-2,7-diyl, or anthracene-2,6-diyl, at least one hydrogen of these rings may be fluorine, chlorine, alkyl having 1 to 12 carbons, Alkoxy having 1 to 12 carbons, or at least one hydrogen substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine; Z ¹ is a single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ¹ is a single bond or carbon Numbers 1 to 7 of alkylene groups At least one -CH ₂ - may be -O -, - COO-, -OCO- or substituted with at least one -CH ₂ CH ₂ - may be replaced by -CH = CH-, the plurality of groups, at least one hydrogen may be Fluorine substituted; a is 0, 1, 2, 3, or 4; R ² and R ^{3 are} independently hydrogen or methyl. The liquid crystal composition according to item 1 of the scope of patent application, which contains a group selected from the group of polar compounds having a (meth) acrylamido group represented by formula (1-1) to formula (1-12). At least one compound as the first additive: In the formulae (1-1) to (1-12), R ¹ is hydrogen, halogen, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, At least one hydrogen with 1 to 12 carbons substituted with fluorine or chlorine, or at least one hydrogen with 2 to 12 carbons substituted with fluorine or chlorine; Z ¹ , Z ² , and Z ^{3 are} independently Single bond, -CH ₂ CH _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ¹ is a single bond or an alkylene group having 1 to 7 carbon atoms. Among the alkylene groups, at least one -CH ₂ -may pass through -O-, -COO-, or -OCO- substituted, at least one -CH ₂ CH ₂ -can be substituted by -CH = CH-, in these groups, at least one hydrogen can be substituted by fluorine; L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , L ¹² , L ¹³ , and L ^{14 are} independently hydrogen, fluorine, methyl, or ethyl; R ² and R ^{3 are} independently Hydrogen, or methyl. The liquid crystal composition according to item 1 of the patent application range, wherein the proportion of the first additive is in a range of 0.05% by weight to 10% by weight. The liquid crystal composition according to item 1 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (2) as a first component, In formula (2), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an olefin having 2 to 12 carbons Oxygen; ring C and ring E are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, at least one hydrogen substituted with fluorine or chlorine 1,4 -Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene Base, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochromogen- 2,6-diyl; Z ⁴ and Z ^{5 are} independently a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; b is 1, 2 , Or 3, c is 0 or 1, and the sum of b and c is 3 or less. The liquid crystal composition according to item 4 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-22) as a first component: In the formulae (2-1) to (2-22), R ⁴ and R ^{5 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. Or an alkenyloxy group having 2 to 12 carbon atoms. The liquid crystal composition according to item 4 of the scope of patent application, wherein the ratio of the first component is in a range of 10% by weight to 90% by weight. The liquid crystal composition according to item 1 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (3) as a second component: In the formula (3), R ⁶ and R ^{7 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and at least one hydrogen is subjected to fluorine or chlorine. Alkyl groups having 1 to 12 carbon atoms, or alkenyl groups having 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexyl, 1,4 -Phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, -CH ₂ CH _2- , -CH ₂ O -, -OCH _2- , -COO-, or -OCO-; d is 1, 2, or 3. The liquid crystal composition according to item 7 of the scope of patent application, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as a second component: In the formulae (3-1) to (3-13), R ⁶ and R ^{7 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. , An alkyl group having 1 to 12 carbons substituted with at least one hydrogen with fluorine or chlorine, or an alkenyl group with 2 to 12 carbons substituted with at least one hydrogen with fluorine or chlorine. The liquid crystal composition according to item 7 of the scope of patent application, wherein the ratio of the second component is in a range of 10% by weight to 70% by weight. The liquid crystal composition according to item 1 of the scope of patent application, which contains at least one compound selected from the group of polymerizable compounds represented by formula (4) as a second additive: In formula (4), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in which at least one hydrogen may pass through fluorine, chlorine, alkyl having 1 to 12 carbons, and alkoxy having 1 to 12 carbons Or at least one hydrogen is substituted by fluorine or chlorine alkyl having 1 to 12 carbons; ring K is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-benzene Naphthalene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1 , 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5 -Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, at least one hydrogen of these rings may be via fluorine, Chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen substituted with fluorine or chlorine and alkyl having 1 to 12 carbons; Z ⁷ and Z ^{8 are} independently a single bond or a C 1-10 alkylene group, said alkylene, at least one -CH ₂ - may be -O -, substituted or COO- -OCO-, and -, - CO -, At least one -CH ₂ CH ₂ - may be -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; P ¹ , P ² , and P ³ are polymerizable groups; Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or carbon number 1 To 10, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may Substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; q is 0, 1, or 2; j, k, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is 1 or more. The liquid crystal composition according to item 10 of the scope of patent application, wherein in formula (4), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of formulas (P-1) to (P-5) Groups in the group of polymerizable groups represented by: In the formulae (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is replaced by fluorine or chlorine Alkyl having 1 to 5 carbons. The liquid crystal composition according to item 10 of the scope of patent application, which contains at least one compound selected from the group of polymerizable compounds represented by formula (4-1) to formula (4-28) as a second additive. : In the formulae (4-1) to (4-28), P ¹ , P ² , and P ^{3 are} independently selected from the group of polymerizable groups represented by the formulae (P-1) to (P-3) A group in the group, where 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 atom having 1 to 5 carbon atoms substituted with fluorine or chlorine Alkyl Sp ² , Sp ³ , and Sp ^{4 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the alkylene groups, at least one of -CH ₂ -may pass through -O-, -COO-, -OCO. -, Or -OCOO-, and at least one -CH ₂ CH ₂ -may be substituted with -CH = CH- or -C≡C-. Among these groups, at least one hydrogen may be substituted with fluorine or chlorine. The liquid crystal composition according to item 10 of the scope of patent application, wherein the ratio of the second additive is in a range of 0.03% by weight to 10% by weight. A liquid crystal display element includes the liquid crystal composition according to item 1 of the scope of patent application. The liquid crystal display element according to item 14 of the scope of patent application, wherein the operation mode of the liquid crystal display element is an in-plane switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced light reaction alignment mode, and the driving of the liquid crystal display element The method is an active matrix method. A polymer stabilized alignment type liquid crystal display device includes the liquid crystal composition according to item 1 of the scope of patent application, and the first additive in the liquid crystal composition is polymerized, or the first additive and the first additive are polymerized. The two additives were polymerized. A liquid crystal display element without an alignment film, comprising the liquid crystal composition according to item 1 of the scope of patent application, and the first additive in the liquid crystal composition is polymerized, or the first additive and the second additive are polymerized. The additives were polymerized. A use of a liquid crystal composition, wherein the liquid crystal composition is the liquid crystal composition described in item 1 of the scope of patent application, and is used in a liquid crystal display element. A use of a liquid crystal composition, wherein the liquid crystal composition is the liquid crystal composition described in item 1 of the scope of patent application, and is used in a polymer-stable alignment type liquid crystal display element. A use of a liquid crystal composition. The liquid crystal composition is the liquid crystal composition described in item 1 of the scope of patent application, and is used in a liquid crystal display element without an alignment film.