TW201807175A - Liquid crystal composition and use thereof, and liquid crystal display device - Google Patents

Abstract

The subject is to provide a liquid crystal composition in which the vertical alignment alignment of liquid crystal molecules can be achieved by the action of a polymer, and a liquid crystal display device including this composition. The means concerns a nematic liquid crystal composition including at least one compound selected from the group of polar compounds represented by formula (1) as a first additive and having negative dielectric anisotropy, and concerns a liquid crystal display device including the composition. in formula (1), ring A and ring C are independently cyclohexylene, phenylene or the like; ring B is 1,4-cyclohexylene, 1,4-phenylene or the like; Z1 and Z2 are a single bond or the like; Sp1, Sp2 and Sp3 are independently a single bond, alkylene having 1 to 10 carbons or the like; P1, P2 and P3 are independently a polymerizable group; a is 0 to 3; b, c, and d are independently 0 to 4, and the sum of b, c and d is 2 or more.

Description

Liquid crystal composition and use thereof, and liquid crystal display element

The present invention relates to a liquid crystal composition having a negative dielectric anisotropy, a liquid crystal display element containing the composition, and the like. In particular, there is a liquid crystal composition containing a polar compound having a polymerizable group (or a polymer) and achieving vertical alignment of liquid crystal molecules by the action of the compound, and a liquid crystal display element.

In the liquid crystal display device, the classification based on the operation mode of the liquid crystal molecules is phase change (PC), twisted nematic (TN), super twisted nematic (STN), and electronically controlled birefringence ( Electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (FFS), Modes such as field-induced photo-reactive alignment (FPA). The component-based driving methods are classified into a passive matrix (PM) and an active matrix (AM). The PM is classified into a static type and a multiplex type, and the AM is classified into a thin film transistor (TFT), a metal insulator metal (MIM), or the like. The classification of TFTs is amorphous silicon and polycrystalline silicon. The latter are classified into a high temperature type and a low temperature type according to the manufacturing steps. The classification based on the light source is a reflection type using natural light, a transmission type using a backlight, and a semi-transmissive type using both natural light and a backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The correlation among these characteristics is summarized in Table 1 below. The characteristics of the composition will be further described based on commercially available AM elements. The temperature range of the nematic phase is related to the temperature range over which the component can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C or higher, and the preferred lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of the composition is related to the response time of the component. 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, it is preferred that the viscosity of the composition is small. It is especially preferred that the viscosity at low temperatures is small.

The optical anisotropy of the composition is related to the contrast ratio of the component. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy, is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The value of the appropriate product depends on the type of mode of operation. In the VA mode element, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode element, 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 preferable for an element having a small cell gap. The large dielectric anisotropy of the composition contributes to low threshold voltage, low power consumption and large contrast ratio in the component. Therefore, a large dielectric anisotropy is preferred. The large specific resistance of the composition contributes to the large voltage holding ratio of the element to a large contrast ratio. Therefore, a composition having a large specific resistance in the initial stage is preferred. A composition having a large specific resistance after long-term use is preferred. The stability of the composition to ultraviolet or heat is related to the life of the component. When the stability is high, the life of the component is long. Such characteristics are preferred for AM devices 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 using a specific polyimide film. In a polymer sustained alignment (PSA) type liquid crystal display device, a polymer and an alignment film are combined. First, a composition to which a small amount of a polymerizable compound is added is injected into the element. Then, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the element. The polymerizable compound is polymerized to form a network structure of the polymer in the composition. In this composition, the alignment of the liquid crystal molecules can be controlled by the polymer, so that the response time of the element is shortened and the afterimage of the image is improved. Such an effect of a polymer can be expected in an element having a mode such as TN, ECB, OCB, IPS, VA, FFS, or FPA.

On the other hand, a liquid crystal composition containing a polymer and a polar compound having no polymerizable group is used for a liquid crystal display device having no alignment film (Patent Documents 1 to 5). First, a composition to which a small amount of a polymerizable compound and a small amount of a polar compound are added is injected into the element. Here, the polar compound is adsorbed on the surface of the substrate and arranged. The liquid crystal molecules are aligned according to the arrangement. Then, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the element. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. In this composition, the alignment of the liquid crystal molecules can be controlled by the polymer and the polar compound, so that the response time of the element is shortened and the afterimage of the image is improved. Further, the step of forming the alignment film is not required in the element having no alignment film. Since the alignment film is not present, the resistance of the element is not lowered by the interaction of the alignment film and the composition. Such an effect of using a combination of a polymer and a polar compound can be expected in an element having a mode such as TN, ECB, OCB, IPS, VA, FFS, or FPA.

A composition having positive dielectric anisotropy is used in an AM device having a TN mode. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. A composition having positive or negative dielectric anisotropy is used in an AM device having an IPS mode or an FFS mode. A composition having positive or negative dielectric anisotropy is used in the polymer-stabilized alignment type AM device. Examples of the liquid crystal composition having negative dielectric anisotropy are disclosed in Patent Documents 1 to 6 below. In the present invention, a polar compound having a polymerizable group is combined with a liquid crystal compound instead of the polymerizable compound and the polar compound, and the composition is used for a liquid crystal display element having no alignment film. [Prior Art Document] [Patent Literature]

[Patent Document 1] International Publication No. 2014/090362 [Patent Document 2] International Publication No. 2014/094959 [Patent Document 3] International Publication No. 2013/004372 (Patent Document 4) International Publication No. 2012/104008 [Patent Document 5] International Publication No. 2012/038026 (Patent Document 6) Japanese Patent Laid-Open No. SHO-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 (or a polymer) having a polymerizable group, wherein the polar compound has high compatibility with a liquid crystal compound. Another object is to provide a liquid crystal composition which can achieve vertical alignment of liquid crystal molecules by the action of a polymer produced from the polar compound. Another object of the invention is to provide a liquid crystal composition which has a high upper limit temperature of a nematic phase, a low minimum temperature of a nematic phase, a small viscosity, an appropriate optical anisotropy, a large dielectric anisotropy, and a large specific resistance. At least one of characteristics such as high stability against ultraviolet light and high stability against heat. Another object is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another object is to provide a liquid crystal display element containing such a composition. Still another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life. [Means for solving the problem]

The present invention relates to a liquid crystal composition containing at least one compound selected from the group consisting of polar compounds represented by formula (1) as a first additive and having negative dielectric anisotropy, and containing the composition Liquid crystal display element. In the formula (1), Ring A and Ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxin An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Alkenyl having 2 to 12 carbon atoms, at least one alkyl group having 1 to 12 carbons substituted by fluorine or chlorine, or at least one hydrogen having 2 to 12 carbon atoms substituted by fluorine or chlorine; ring B Is 1,4-cyclohexylene, 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- a diradical or pyridine-2,5-diyl group, wherein at least one of the hydrogens may be fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and a carbon number of 2 to 12 Alkenyl group, at least one alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine, or at least one hydrogen group having 2 to 12 carbon atoms substituted by fluorine or chlorine Generation; Z ¹ and Z ^{2 are} independently a single bond or a C 1-10 alkylene group, which alkylene, at least one -CH ₂ - may be -O -, - CO -, - COO- , or - OCO-substituted, and at least one -CH ₂ CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C ( CH ₃ )-substituted, wherein at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, 2 or 3; b, c and d are independently 0, 1, 2, 3 or 4, and The sum of b, c and d is 2 or more; and Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be passed through the alkyl group. O-, -COO-, -OCO- or -OCOO-substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be Fluorine or chlorine substitution; P ¹ , P ² and P ^{3 are} independently a polymerizable group represented by the formula (PA), In the formula (PA), Sp ⁴ is a single bond or an alkylene group having 1 to 7 carbon atoms, and at least one of -CH ₂ - may be substituted with -O-, -COO- or -OCO-, at least One -CH ₂ CH ₂ - may be substituted by -CH=CH-, wherein at least one hydrogen may be substituted by fluorine; R ¹ is -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N ( a group represented by R ⁰ ) ₂ , wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; and M ⁴ and M ^{5 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one An alkyl group having 1 to 5 carbon atoms in which hydrogen is replaced by fluorine or chlorine. [Effects of the Invention]

An advantage of the present invention is to provide a liquid crystal composition containing a polar compound (or a polymer) having a polymerizable group, wherein the polar compound has high compatibility with a liquid crystalline compound. Another advantage is to provide a liquid crystal composition which can achieve vertical alignment of liquid crystal molecules by the action of a polymer produced from the polar compound. Another advantage is to provide a liquid crystal composition which satisfies the upper limit temperature of the nematic phase, the lower limit temperature of the nematic phase, the viscosity is small, the optical anisotropy is appropriate, the negative dielectric anisotropy is large, and the specific resistance is large. At least one of characteristics such as high stability against ultraviolet light and high stability against heat. Another advantage is to provide a liquid crystal composition having an appropriate balance between at least two of these characteristics. Another advantage is to provide a liquid crystal display element containing such a composition. Still another advantage is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life.

The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" are simply referred to as "composition" and "component", respectively. The "liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. The "liquid crystal compound" is a compound having a liquid crystal phase having a nematic phase and a smectic phase, and the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase without having a liquid crystal phase. A general term for the compounds mixed in the composition. The compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecular structure is rod like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystalline compound having an alkenyl group is not polymerizable in terms of its meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. An additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, or a polar compound is added to the liquid crystal composition as needed. In other words, when the additive is easily added, the ratio (content) of the liquid crystal compound is also represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. The ratio (addition amount) of the additive is represented by weight percentage (% by weight) based on the weight of the liquid crystal composition not containing the additive. Sometimes used in parts per million (ppm). The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

The "upper limit temperature of the nematic phase" is sometimes simply referred to as "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as "lower limit temperature". "Greater specific resistance" means that the composition has a large specific resistance in the initial stage, and has a large specific resistance even after long-term use. "High voltage holding ratio" means that the element has a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and is not only at room temperature after long-term use, but also It also has a large voltage holding ratio at a temperature close to the upper limit temperature. Among the compositions or components, the characteristics are sometimes studied before and after the time-varying test (including the accelerated deterioration test). The expression "increasing the dielectric anisotropy" means that the value of the positive dielectric anisotropy increases positively, and when the dielectric anisotropy is negative, the value is negative. Increase to the ground.

The compound represented by the formula (1) is sometimes simply referred to as "compound (1)". At least one compound selected from the group consisting of the compounds represented by the formula (1) may be simply referred to as "compound (1)". The "compound (1)" means a compound represented by the formula (1), a mixture of two compounds or a mixture of three or more compounds. The compounds represented by the other formulas are also the same. The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' can be replaced by 'B'" means that the position of 'A' is arbitrary when the number of 'A' is one, and the position of 'A' when the number of 'A' is two or more. You can also choose without restrictions. The rule also applies to the expression "at least one 'A' replaced by 'B'".

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

In the chemical formula of the component compound, the symbol of the terminal group R ² is used for a plurality of compounds. Among these compounds, the two groups represented by any two of R ² may be the same or different. For example, there is a case where R ² of the compound (1-1) is an ethyl group, and R ² of the compound (1-2) is an ethyl group. Also the compound (1-1) is ethyl and R ^2, and R of the compound (1-2) ² is propyl. This rule also applies to symbols such as other end groups. In the formula (1), when the subscript 'a' is 2, there are two loops B. In the compound, the two groups represented by the two rings B may be the same or different. This rule also applies to any two loops B when the subscript 'a' is greater than 2. This rule also applies to other tokens.

The symbols A, B, C, and D surrounded by a hexagon are respectively associated with rings such as ring A, ring B, ring C, and ring D, and represent rings such as a six-membered ring and a condensed ring. An oblique line transverse to one side of the hexagon indicates that any hydrogen on the ring may be substituted with a group such as -Sp ¹ -P ¹ . Subscripts such as 'c' indicate the number of substituted groups. When the subscript 'c' is 0, there is no such substitution. When the subscript 'c' is 2 or more, a plurality of -Sp ¹ -P ¹ are present on the ring A. The plurality of bases represented by -Sp ¹ -P ¹ may be the same or may be different. In the expression "ring A and ring C are independently X, Y or Z", since there are a plurality of subjects, "independent" is used. When the subject is "ring A", since the subject is singular, "independent" is not used. When "ring A" is used in multiple formulas, the rule "may be the same or may be different" applies to "ring A". The same is true for other bases.

The 2-fluoro-1,4-phenylene group means the two kinds of divalent groups described below. In the chemical formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric divalent radicals formed by the removal of two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule also applies to divalent bonding groups such as carbonyloxy (-COO- or -OCO-).

The alkyl group of the liquid crystalline compound is linear or branched, and does not contain a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. In these cases, the terminal groups such as alkoxy groups and alkenyl groups are also the same. In order to increase the upper limit temperature, the stereo configuration associated with 1,4-cyclohexylene is that the trans configuration is superior to the cis configuration.

The present invention is as follows.

Item 1. A liquid crystal composition containing at least one compound selected from the group consisting of polar compounds represented by formula (1) as a first additive and having a negative dielectric anisotropy, In the formula (1), Ring A and Ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxin An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Alkenyl having 2 to 12 carbon atoms, at least one alkyl group having 1 to 12 carbons substituted by fluorine or chlorine, or at least one hydrogen having 2 to 12 carbon atoms substituted by fluorine or chlorine; ring B Is 1,4-cyclohexylene, 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- a diradical or pyridine-2,5-diyl group, wherein at least one of the hydrogens may be fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and a carbon number of 2 to 12 Alkenyl group, at least one alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine, or at least one hydrogen group having 2 to 12 carbon atoms substituted by fluorine or chlorine Generation; Z ¹ and Z ^{2 are} independently a single bond or a C 1-10 alkylene group, which alkylene, at least one -CH ₂ - may be -O -, - CO -, - COO- , or - OCO-substituted, and at least one -CH ₂ CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C ( CH ₃ )-substituted, wherein at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, 2 or 3; b, c and d are independently 0, 1, 2, 3 or 4, and The sum of b, c and d is 2 or more; and Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be passed through the alkyl group. O-, -COO-, -OCO- or -OCOO-substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be Fluorine or chlorine substitution; P ¹ , P ² and P ^{3 are} independently a polymerizable group represented by the formula (PA), In the formula (PA), Sp ⁴ is a single bond or an alkylene group having 1 to 7 carbon atoms, and at least one of -CH ₂ - may be substituted with -O-, -COO- or -OCO-, at least One -CH ₂ CH ₂ - may be substituted by -CH=CH-, wherein at least one hydrogen may be substituted by fluorine; R ¹ is -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N ( a group represented by R ⁰ ) ₂ , wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; and M ⁴ and M ^{5 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one An alkyl group having 1 to 5 carbon atoms in which hydrogen is replaced by fluorine or chlorine.

The liquid crystal composition according to Item 1, wherein, in the formula (1) as described in the item 1, the ring A and the ring C are independently a cyclohexyl group, a phenyl group, a 1-naphthyl group or a 2-naphthyl group. In the rings, at least one hydrogen may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, at least one hydrogen via fluorine or chlorine. Substituted alkyl having 1 to 12 carbon atoms, or at least one hydrogen substituted by a fluorine or chlorine substituted 2 to 12 alkenyl group; ring B is 1,4-cyclohexylene, 1,4-phenylene, Naphthalene-1,2-diyl or naphthalene-2,6-diyl, wherein at least one of the hydrogens may be fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. An alkenyl group having 2 to 12 carbon atoms, an alkyl group having 1 to 12 carbons substituted with at least one hydrogen via fluorine or chlorine, or an alkenyl group having 2 to 12 carbons substituted with at least one hydrogen substituted by fluorine or chlorine; 0 or 1.

The liquid crystal composition according to Item 1, wherein the first additive is at least one selected from the group consisting of polar compounds represented by formula (1-1) to formula (1-13). Compound, In the formulae (1-1) to (1-13), R ¹ is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N(R ⁰ ) ₂ , where R ⁰ Is hydrogen or an alkyl group having 1 to 12 carbon atoms; R ² is hydrogen, fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least a C 1 to 12 alkyl group in which hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Z ¹ and Z ^{2 are} independently a single bond or a carbon number of 1 An alkylene group of up to 10, wherein at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and 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 which at least one hydrogen can pass Fluorine or chlorine substitution; Sp ¹ and Sp ^{3 are} independently a single bond or a C 1 to 10 alkyl group, and at least one of -CH ₂ - may be -O-, -COO-, -OCO - or -OCOO-substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be substituted by fluorine or chlorine; Sp ⁴ is a single a bond or an alkyl group having 1 to 7 carbon atoms, and at least one -CH ₂ - in the alkyl group; Substituting -O-, -COO- or -OCO-, at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, wherein at least one hydrogen may be substituted by fluorine; L ¹ , L ² And L ³ , L ⁴ , L ⁵ and L ^{6 are} independently hydrogen, fluorine, methyl or ethyl.

The liquid crystal composition according to any one of items 1 to 3, wherein the ratio of the first additive is in the range of 0.05% by weight to 10% by weight based on the weight of the liquid crystal composition.

The liquid crystal composition according to any one of items 1 to 4, which contains at least one compound selected from the group consisting of compounds represented by formula (2) as a first component, In the formula (2), R ³ and R ^{4 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 an oxyalkylene having 2 to 12 carbon atoms. Ring; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-extension of at least one hydrogen substituted by fluorine or chlorine Phenyl or tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6 -2,8-difluorochroman-2,6-diyl; Z ³ and Z ^{4 are} independently a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-;f is 1, 2 or 3, g is 0 or 1, and the sum of f and g is 3 or less.

The liquid crystal composition according to any one of the items 1 to 5, wherein at least one compound selected from the group consisting of compounds represented by formula (2-1) to formula (2-22) is used as First ingredient, In the formulae (2-1) to (2-22), R ³ and R ^{4 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 5 or Item 6, wherein the ratio of the first component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.

The liquid crystal composition according to any one of items 1 to 7, which contains at least one compound selected from the group consisting of compounds represented by formula (3) as a second component, In the formula (3), R ⁵ and R ^{6 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 substituted by fluorine or chlorine. An alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbons substituted with at least one hydrogen via fluorine or chlorine; ring G and ring I are independently 1,4-cyclohexylene, 1,4-stretch Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, - OCH ₂ -, -COO- or -OCO-; h is 1, 2 or 3.

The liquid crystal composition according to any one of the items 1 to 8, wherein at least one compound selected from the group consisting of compounds represented by formula (3-1) to formula (3-13) is used as The second component, Formula (3-1) to (3-13), R ⁵ is and R ⁶ are independently alkyl alkoxycarbonyl, 1 to 12 carbon atoms, 1 to 12 carbons, alkenyl having 2 to 12 At least one alkyl group having 1 to 12 carbons substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbons substituted with at least one hydrogen via fluorine or chlorine.

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

The liquid crystal composition according to any one of the items 1 to 10, which contains at least one compound selected from the group consisting of the polymerizable compounds represented by the formula (4) as a second additive, In the formula (4), the ring J and the ring P are independently a cyclohexyl group, a cyclohexenyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tetrahydropyran-2-yl group, and a 1,3-dioxin. An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7 -diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-di a 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl group, wherein at least one hydrogen in the ring may be via fluorine, chlorine or carbon An alkyl group of 1 to 12, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ^{7 are} independently a single bond or carbon a number 1 to 10 alkylene group in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, in which At least one hydrogen may be substituted with fluorine or chlorine; P ⁴ , P ⁵ and P ⁶ are polymerizable groups different from the polymerizable group represented by the formula (PA) as described in Item 1; Sp ⁵ , Sp ⁶ and Sp ⁷ Independently a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be substituted by fluorine or chlorine; q is 0, 1 or 2; j, k and p are independent The ground is 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 11, wherein, in the formula (4), P ⁴ , P ⁵ and P ^{6 are} independently selected from the group consisting of the formula (P-1) to the formula (P-5). a group in a 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 a carbon in which at least one hydrogen is substituted by fluorine or chlorine. A number of 1 to 5 alkyl groups.

The liquid crystal composition according to Item 11, wherein the second additive is at least one selected from the group consisting of polymerizable compounds represented by formula (4-1) to formula (4-28). a compound, In the formulae (4-1) to (4-28), P ⁴ , P ⁵ and P ^{6 are} independently a group selected from the group consisting of the polymerizable groups represented by the formulae (P-1) to (P-3). Base, Here, M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Sp ⁵ , Sp ⁶ and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-. And at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one of the hydrogens may be substituted with fluorine or chlorine.

The liquid crystal composition according to any one of items 11 to 13, wherein the ratio of the second additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition.

Item 15. A liquid crystal display element comprising the liquid crystal composition according to any one of items 1 to 14.

The liquid crystal display device of item 15, 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 mode of the liquid crystal display element is an active matrix mode.

Item 17. A polymer-stabilized alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 10, wherein the first additive contained in the liquid crystal composition is polymerized.

Item 18. A polymer-stabilized alignment type liquid crystal display device, comprising the liquid crystal composition according to any one of items 11 to 14, wherein the first additive and the second additive contained in the liquid crystal composition The substance is polymerized.

Item 19. A liquid crystal display element having no alignment film, comprising the liquid crystal composition according to any one of items 1 to 10, wherein the first additive contained in the liquid crystal composition is polymerized.

Item 20. A liquid crystal display element having no alignment film, comprising the liquid crystal composition according to any one of items 11 to 14, wherein the first additive and the second additive contained in the liquid crystal composition Perform polymerization.

The use of the liquid crystal composition according to any one of items 1 to 14, which is used in a liquid crystal display element.

The use of the liquid crystal composition according to any one of items 1 to 14, which is used in a polymer-stabilized alignment type liquid crystal display element.

The use of the liquid crystal composition according to any one of items 1 to 14, which is for use in a liquid crystal display element having no alignment film.

The invention also includes the following items. (a) A method of producing a liquid crystal display device, wherein the liquid crystal composition is disposed between two substrates, and light is applied while a voltage is applied to the composition to impart polymerizability in the composition. The base compound is polymerized to produce the above liquid crystal display element. (b) The liquid crystal composition, wherein the upper limit temperature of the nematic phase is 70 ° C or higher, the optical anisotropy at a wavelength of 589 nm (measured at 25 ° C) is 0.08 or more, and the dielectric orientation at a frequency of 1 kHz The opposite sex (measured at 25 ° C) was -2 or less.

The invention also includes the following items. (c) The compound (5) to the compound (7) described in JP-A-2006-199941 are liquid crystal compounds having a positive dielectric anisotropy, but the composition contains the selected one. At least one compound of the group of compounds. (d) The above composition containing at least two of the above polar compounds. (e) The above composition further containing a polar compound different from the above polar compound. (f) the above composition comprising one, two or at least three optically active compounds, an antioxidant, an ultraviolet absorber, a pigment, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound or the like Additives. The additive may be the same as the first additive or the second additive or may be different. (g) An AM device containing the above composition. (h) An element containing the above composition and having a TN mode, an ECB mode, an OCB mode, an IPS mode, an FFS mode, a VA mode, or an FPA mode. (i) a transmissive element containing the above composition. (j) The above composition is used as a composition having a nematic phase. (k) A composition prepared by adding an optically active compound to the above composition is used as an optically active 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 compound and the main effects of the compound on the properties of the composition will be described. Third, the combination of the components in the composition, the preferred ratio of the components, and the basis thereof will be described. Fourth, a preferred embodiment of the component compound will be described. Fifth, a preferred component compound is shown. Sixth, an additive which can be added to the composition will be described. Seventh, a method of synthesizing a component compound 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 Composition A and Composition B. In addition to the liquid crystalline compound selected from the compound (2) and the compound (3), the composition A may further contain other liquid crystal compounds, additives, and the like. The "other liquid crystal compound" is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed in the composition for the purpose of further adjusting the properties. The additive is an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, a polymerization inhibitor, a polar compound, and the like.

The composition B contains substantially only the liquid crystalline compound selected from the compound (2) and the compound (3). "Substantially" means that the composition B may contain an additive, but does not contain other liquid crystal compounds. The amount of the component of the composition B was small as compared with the composition A. Composition B is superior to composition A from the viewpoint of cost reduction. The composition A is superior to the composition B from the viewpoint of further adjusting the characteristics by mixing other liquid crystal compounds.

Second, the main characteristics of the component compound and the main effects of the compound on the properties 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 of Table 2, L means large or high, M means medium, and S means small or low. The notation L, M, S is a classification based on a qualitative comparison between the constituent compounds, and the symbol 0 means that the value is zero, or close to zero.

When the component compound is mixed in the composition, the main effects of the component compound on the properties of the composition are as follows. The compound (1) is adsorbed to the surface of the substrate by the action of a polar group, and controls the alignment of the liquid crystal molecules. In order to obtain the desired effect, the compound (1) must have high compatibility with the liquid crystalline compound. The compound (1) has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and is most suitable for this purpose because its molecular structure is rod-shaped. The compound (1) forms a polymer by polymerization. Since the polymer stabilizes the alignment of the liquid crystal molecules, the response time of the element is shortened, and the afterimage of the image is improved. Compound (2) increases dielectric anisotropy and lowers the minimum temperature. Compound (3) lowers the viscosity, raises the upper limit temperature or lowers the lower limit temperature. The compound (4) is added to the composition for the purpose of further suitable for the element of the polymer stable alignment type. The compound (4) forms a polymer by polymerization. Since the polymer stabilizes the alignment of the liquid crystal molecules, the response time of the element is shortened, and the afterimage of the image is improved. From the viewpoint of the alignment of the liquid crystal molecules, since the polymer of the compound (1) has an interaction with the surface of the substrate, it is estimated that it is more effective than the polymer of the compound (4).

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

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

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

A preferred ratio of the compound (3) is about 10% by weight or more for increasing the maximum temperature or lowering the lower limit temperature, and a ratio of the compound (3) is preferably about 70% by weight or less for increasing the dielectric anisotropy. A more desirable ratio is in the range of from about 15% by weight to about 65% by weight. A particularly preferred ratio is in the range of from about 20% by weight to about 60% by weight.

In order to improve the long-term reliability of the element, a preferred ratio of the compound (4) is about 0.03% by weight or more, and a ratio of the compound (4) is preferably about 10% by weight or less in order to prevent display defects of the element. A more desirable ratio is in the range of from about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of from about 0.2% by weight to about 1.0% by weight.

Fourth, a preferred embodiment of the component compound will be described. In the formula (PA), R ¹ is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N(R ⁰ ) ₂ , where R ⁰ is hydrogen or a carbon number of 1 to 12. alkyl. The polar group has an interaction with a non-covalent bond of the surface of the glass substrate or the metal oxide film. From the viewpoint of high solubility in the liquid crystal composition, R ^{1 is} particularly preferably -OH or -NH ₂ . -OH is superior to -O-, -CO- or -COO- because of its high anchoring force. Particularly preferred is a group having a plurality of hetero atoms (nitrogen, oxygen). A compound having such a polar group is effective even at a low concentration. The compound (1) is preferably stable to ultraviolet rays or heat. When the compound (1) is added to the composition, it is preferred that the compound does not lower the voltage holding ratio of the element. The compound (1) preferably has a low volatility. A preferred molar mass is 130 g/mol or more. A particularly preferred molar mass is in the range of from 150 g/mol to 500 g/mol.

In the formula (1), Ring A and Ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxin An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. An alkenyl group having 2 to 12 carbon atoms, an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. Preferred ring A or ring C is cyclohexyl or phenyl. Ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl or pyridinyl-2,5-diyl, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and a carbon number of 2 An alkenyl group of 12, an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine is substituted. Preferred ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹ and Z ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -CO-, -COO- or -OCO-. Substituted, and at least one -CH ₂ CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ And substituted, at least one of the hydrogens may be substituted by fluorine or chlorine. Desirable Z ¹ or Z ² is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. Particularly preferred Z ¹ or Z ² is a single bond.

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

Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be -O-, -COO-, -OCO- or -OCOO-substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be substituted by fluorine or chlorine. Desirable Sp ¹ or Sp ² is a single bond and at least one -CH ₂ -O-substituted-alkylene group having 1 to 10 carbon atoms. Sp ⁴ is a single bond or an alkylene group having 1 to 7 carbon atoms, and at least one of -CH ₂ - may be substituted by -O-, -COO- or -OCO-, at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, in which at least one hydrogen may be substituted by fluorine.

P ¹ , P ² and P ^{3 are} independently a polymerizable group represented by the formula (PA).

M ⁴ and M ^{5 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine. Desirable M ⁴ or M ⁵ is hydrogen or methyl to increase the reactivity. More preferably M ⁴ or M ⁵ is hydrogen.

In the formula (1-1) to the formula (1-13), R ² is hydrogen, fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkene having 2 to 12 carbon atoms. a C. 1 to 12 alkyl group substituted with at least one hydrogen via fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms substituted with at least one hydrogen via fluorine or chlorine. Desirable R ² is an alkyl group having 1 to 12 carbon atoms.

L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ^{6 are} independently hydrogen, fluorine, methyl or ethyl. Preferred L ¹ to L ⁶ are hydrogen, fluorine or methyl. More preferably, L ¹ to L ⁶ are hydrogen or fluorine.

In the formulae (2) and (3), R ³ and R ^{4 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 of 2 Alkenyloxy group up to 12. For increasing the stability to ultraviolet light or heat, preferably R ³ or R ⁴ is alkyl having 1 to 12, for increasing the dielectric anisotropy, preferred R ³ or R ⁴ is from 1 to 12 carbon atoms, Alkoxy group. R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and at least one hydrogen having 1 to 12 carbon atoms substituted by fluorine or chlorine. An alkyl group, or an alkenyl group having 2 to 12 carbons, substituted with at least one hydrogen or fluorine or chlorine. Desirable R ⁵ or R ⁶ is an alkenyl group having 2 to 12 carbons for decreasing the viscosity. In order to improve the stability against ultraviolet rays or heat, R ⁵ or R ⁶ is preferably an alkyl group having 1 to 12 carbon atoms.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to lower the viscosity, a preferred alkyl group is an ethyl group, a propyl group, a butyl group, a pentyl group or a heptyl group.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. In order to lower the viscosity, a more preferred alkoxy group is a methoxy group or an ethoxy group.

Preferred alkenyl groups are ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3 -pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. In order to lower the viscosity, a preferred alkenyl group is a vinyl group, a 1-propenyl group, a 3-butenyl group or a 3-pentenyl group. The preferred stereo configuration of -CH=CH- in the alkenyl groups depends on the position of the double bond. In order to lower the viscosity and the like, an alkenyl group such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl or 3-hexenyl is preferred. Trans configuration. The alkenyl group such as 2-butenyl, 2-pentenyl or 2-hexenyl is preferably a cis configuration.

Preferred alkenyloxy groups are ethyleneoxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. In order to lower the viscosity, a more preferred alkenyloxy group is an allyloxy group or a 3-butenyloxy group.

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

Preferred examples of the alkenyl group in which at least one hydrogen is substituted by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-Difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. In order to lower the viscosity, a 2,2-difluorovinyl group or a 4,4-difluoro-3-butenyl group is particularly preferred.

Ring D and ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene substituted with at least one hydrogen via fluorine or chlorine. Or tetrahydropyran-2,5-diyl. Preferred examples of "at least one 1,4-phenylene group in which hydrogen is substituted by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-Chloro-3-fluoro-1,4-phenylene. In order to lower the viscosity, preferred ring D or ring F is 1,4-cyclohexylene. In order to increase dielectric anisotropy, preferred ring D or ring F is tetrahydropyran-2,5-diyl. In order to enhance optical anisotropy, preferred ring D or ring F is a 1,4-phenylene group. Tetrahydropyran-2,5-diyl is or , preferably .

Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenyl, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6-diyl. In order to lower the viscosity, the preferred ring E is 2,3-difluoro-1,4-phenylene. In order to reduce the optical anisotropy, the preferred ring E is 2-chloro-3-fluoro-1,4- In order to increase the dielectric anisotropy, a preferred ring E is a 7,8-difluorochroman-2,6-diyl group.

Ring G and Ring I are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene . Desirable ring G or ring I is 1,4-cyclohexylene for decreasing the viscosity or for increasing the upper limit temperature. In order to lower the lower limit temperature, preferred ring G or ring I is 1,4-phenylene.

Z ³ and Z ^{4 are} independently a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. In order to lower the viscosity, it is preferred that Z ³ or Z ⁴ is a single bond. In order to lower the lower limit temperature, Z ³ or Z ⁴ is preferably -CH ₂ CH ₂ -, and in order to improve dielectric anisotropy, Z ^{3 is} preferred. Or Z ⁴ is -CH ₂ O- or -OCH ₂ -. Z ⁵ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. In order to lower the viscosity, Z ⁵ is preferably a single bond. In order to lower the lower limit temperature, Z ⁵ is preferably -CH ₂ CH ₂ -, and in order to increase the upper limit temperature, Z ⁵ is preferably -COO- or -OCO-.

f is 1, 2 or 3, g is 0 or 1, and the sum of f and g is 3 or less. In order to lower the viscosity, it is preferable that f is 1, and in order to increase the upper limit temperature, it is preferable that f is 2 or 3. In order to lower the viscosity, g is preferably 0, and in order to lower the lower limit temperature, g is preferably 1. h is 1, 2 or 3. In order to lower the viscosity, it is preferable that h is 1, and in order to increase the upper limit temperature, it is preferable that h is 2 or 3.

In the formula (4), P ⁴ , P ⁵ and P ^{6 are each} independently a polymerizable group different from the polymerizable group represented by the formula (PA) as described in the above item 1. The polymerizable group does not have a polar group such as -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N(R ⁰ ) ₂ . Here, here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms. Desirable P ⁴ , P ⁵ or P ⁶ is a group selected from the group consisting of the polymerizable groups represented by the formulae (P-1) to (P-5). More preferably, P ⁴ , P ⁵ or P ⁶ is a group represented by the formula (P-1), the formula (P-2) or the formula (P-3). Particularly preferred P ⁴ , P ⁵ or P ⁶ is a group represented by the formula (P-1) or the formula (P-2). The most preferred P ⁴ , P ⁵ or P ⁶ is a group represented by the formula (P-1). A preferred group represented by the formula (P-1) is an acryloxy group (-OCO-CH=CH ₂ ) or a methacryloxy group (-OCO-C(CH ₃ )C=CH ₂ ). The wavy line of the formula (P-1) to the formula (P-5) indicates the portion of the bond.

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 a carbon in which at least one hydrogen is substituted by fluorine or chlorine. A number of 1 to 5 alkyl groups. Desirable M ¹ , M ² or M ³ is hydrogen or methyl in order to increase the reactivity. More preferably, M ¹ is hydrogen or methyl, and more preferably M ² or M ³ is hydrogen.

Sp ⁵ , Sp ⁶ and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be -O-, -COO-, -OCO- or -OCOO-substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be substituted by fluorine or chlorine. Desirable Sp ⁵ , Sp ⁶ or Sp ⁷ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH- or - CH=CH-CO-. Particularly preferred Sp ⁵ , Sp ⁶ or Sp ⁷ 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 which at least one hydrogen may be via fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen Fluorine or chlorine substituted alkyl substituted with 1 to 12 carbon atoms. Preferred ring J or ring P is phenyl. Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl or pyridinyl-2,5-diyl, wherein at least one hydrogen in the rings may be fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one Hydrogen is substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms. Preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁶ and Z ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -CO-, -COO- or -OCO-. Substituted, and at least one -CH ₂ CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ And substituted, at least one of the hydrogens may be substituted by fluorine or chlorine. Desirable Z ⁶ or Z ⁷ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. A particularly good Z ⁶ or Z ⁷ is a single bond.

q is 0, 1, or 2. Preferably 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, a preferred component compound is shown. Desirable compound (1) is the compound (1-1) to the compound (1-13) according to item 3. Among these compounds, at least one of the first additives is preferably a compound (1-1), a compound (1-3), a compound (1-5), a compound (1-6), and a compound (1-7). , the compound (1-9), the compound (1-10) or the compound (1-11). Preferably, at least two of the first additives are the compound (1-1) and the compound (1-5), the compound (1-3), and the compound (1-5) or the compound (1-10) and the compound (1). -11) combination.

Desirable compound (2) is the compound (2-1) to the compound (2-22) according to item 6. Among these compounds, at least one of the first components is preferably compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8) or Compound (2-10). Preferably, at least two of the first components are the compound (2-1) and the compound (2-6), the compound (2-1), the compound (2-10), the compound (2-3), and the compound (2- 6) A combination of the compound (2-3) and the compound (2-10), the compound (2-4), and the compound (2-6) or the compound (2-4) and the compound (2-8).

Desirable compound (3) is the compound (3-1) to the compound (3-13) according to item 9. Among these compounds, at least one of the second components is preferably compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8) or Compound (3-9). Preferably, at least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5) or compound (3-1) and compound (3- 6) combination.

Desirable compound (4) is the compound (4-1) to the compound (4-28) according to item 13. Among these compounds, at least one of the second additives is preferably compound (4-1), compound (4-2), compound (4-24), compound (4-25), and compound (4-26). Or compound (4-27). Preferably, at least two of the second additives are the compound (4-1) and the compound (4-2), the compound (4-1), and the compound (4-18), the compound (4-2), and the 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 a combination of compounds (4-24).

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

In order to prevent a 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 long-term use of the element, An antioxidant is added to the composition. A preferred example of the antioxidant is a compound (6) wherein n is an integer of from 1 to 9.

In the compound (6), preferred n is 1, 3, 5, 7 or 9. The better n is 7. Since the compound (6) having n of 7 has a small volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the element is used for a long period of time. In order to obtain the above effect, a preferred ratio of the antioxidant is about 50 ppm or more, and a preferred ratio of the antioxidant is about 600 ppm or less in order not to lower the upper limit temperature or to increase the lower limit temperature. A particularly preferred ratio is in the range of from 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. Further, a light stabilizer such as an amine having steric hindrance is also preferred. In order to obtain the effect, a preferred ratio of the absorbent or stabilizer is about 50 ppm or more, and a preferred ratio of the absorbent or stabilizer is about 10,000 in order not to lower the upper limit temperature or to increase the minimum temperature. Below ppm. A particularly preferred ratio is in the range of from about 100 ppm to about 10,000 ppm.

A dichroic dye such as an azo dye or an anthraquinone dye is added to the composition in order to be suitable for a guest host (GH) mode element. A preferred ratio of pigments is in the range of from about 0.01% by weight to about 10% by weight. In order to prevent foaming, an antifoaming agent such as dimethyl fluorenone oil or methyl phenyl fluorenone oil is added to the composition. In order to obtain the above effect, a preferred ratio of the antifoaming agent is about 1 ppm or more, and a preferable ratio of the antifoaming agent is about 1000 ppm or less in order to prevent display defects. A particularly preferred ratio is in the range of from about 1 ppm to about 500 ppm.

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

The polymerizable compound is polymerized by ultraviolet irradiation. The polymerization can also be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Suitable conditions for carrying out the polymerization, suitable types of initiators, and suitable 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 trademark; BASF) is suitable for free radical polymerization. A preferred ratio of the photopolymerization initiator is in the range of from about 0.1% by weight to about 5% by weight based on the total mass of the polymerizable compound. A more desirable ratio is in the range of from about 1% by weight to about 3% by weight.

When the polymerizable compound is stored, a polymerization inhibitor may be added in order to prevent polymerization. The polymerizable compound is usually added to the composition in a state where the polymerization inhibitor is not removed. Examples of the polymerization inhibitor are hydroquinone derivatives such as hydroquinone and methyl hydroquinone, 4-tert-butyl catechol, 4-methoxyphenol, phenothiazine and the like.

The polar compound is an organic compound having polarity. Here, the compound having an ionic bond is not contained. Atoms such as oxygen, sulfur, and nitrogen are electrically negative and have a tendency to have a partial negative charge. Carbon and hydrogen are neutral or have a tendency to have a partial positive charge. Polarity is caused by the uneven distribution of partial charges between atoms of different species in the compound. For example, the polar compound has at least one of partial structures such as -OH, -COOH, -SH, -NH ₂ , >NH, >N-.

Seventh, a method of synthesizing a component compound will be described. These compounds can be synthesized by a known method. An exemplified synthesis method. The method for synthesizing the compound (1) is described in the examples. The compound (2-1) is synthesized by the method described in JP-A-2-503441. The compound (3-5) is synthesized by the method described in JP-A-57-165328. The compound (4-18) is synthesized by the method described in JP-A-7-101900. A part of the compound (6) is commercially available. A compound of formula (6) wherein n is 1 is available from Sigma-Aldrich Corporation. The compound (6) wherein n is 7 or the like is synthesized by the method described in the specification of U.S. Patent No. 3,660,505.

Compounds not described in the synthesis method can be synthesized by the methods described in the following book: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" (Organic Reactions) , John Wiley & Sons Publishing Company, "Comprehensive Organic Synthesis" (Pergamon Press), New Experimental Chemistry Lecture (Maruzen). The composition is prepared from the compound obtained in the manner described by a known method. For example, the component compounds are mixed and then dissolved 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 an optical anisotropy in the range of about 0.07 to about 0.20. The composition having an optical anisotropy in the range of about 0.08 to about 0.25 can be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Further, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 can be prepared by attempting an error. The element containing the 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. The 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. Further, it can also be used for a PM element. The composition can be used for an AM device and a PM device having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. It is particularly preferable for an AM device having a TN, OCB, IPS mode or FFS mode. In an AM device having an IPS mode or an FFS mode, the alignment of the liquid crystal molecules may be parallel to the glass substrate or may be vertical when no voltage is applied. The elements can be reflective, transmissive or semi-transmissive. It is preferably used for a transmissive element. It can also be used for amorphous germanium-TFT elements or polysilicon-TFT elements. The composition may be used for a nematic curvilinear aligned phase (NCAP) type element produced by microencapsulation or a polymer formed by forming a three-dimensional network polymer in the composition. A polymer dispersed (PD) type component.

An example of a method of producing a conventional polymer stable alignment type element is as follows. An assembly comprising two substrates is referred to as an array substrate and a color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition was prepared by mixing liquid crystal compounds. A polymerizable compound is added to the composition. Additives can be added as needed. This composition is injected into the component. Light irradiation is performed in a state where a voltage is applied to the element. It is preferably ultraviolet light. The polymerizable compound is polymerized by light irradiation. A polymer-containing composition is produced by the polymerization. Polymer stabilized alignment type elements are manufactured in the order described above.

In this order, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. According to this alignment, the molecules of the polymerizable compound are also aligned. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer which maintains the alignment is formed. By the effect of the polymer, the response time of the element is shortened. Since the afterimage of the image is a malfunction of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. Further, 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 device.

When a polar compound having a polymerizable group such as the compound (1) is used as the polymerizable compound, an alignment film is not required on the substrate of the element. An element having no alignment film is fabricated from a substrate having no alignment film in accordance with the order described in the previous two paragraphs.

In this order, the compound (1) is aligned on the substrate due to the interaction of the polar group with the surface of the substrate. According to this arrangement, the liquid crystal molecules are aligned. When the 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 which maintains the alignment is formed. By the effect of the polymer, the alignment of the liquid crystal molecules is additionally stabilized, and the response time of the element is shortened. Since the afterimage of the image is a malfunction of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. [Examples]

The invention will be further described in detail by way of examples. The invention is not limited by the embodiments. The present invention comprises a mixture of the composition (M1) and the composition (M2). The present invention also encompasses a mixture of at least two of the compositions of the examples. The synthesized compound is identified by a method such as nuclear magnetic resonance (NMR) analysis. The properties of the compounds, compositions and elements were determined by the following methods.

NMR analysis: DRX-500 manufactured by Bruker BioSpin Co., Ltd. was used for the measurement. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _{3 ,} and the measurement was carried out at room temperature at 500 MHz and the cumulative number of times was 16 times. Tetramethyl decane was used as an internal standard. ^In the measurement of ¹⁹ F-NMR, CFCl _{3 was} used as an internal standard, and the cumulative number of times was 24 times. In the description of nuclear magnetic resonance spectroscopy, s refers to a single peak, d refers to a doublet, t refers to a triplet, q refers to a quartet, and quin refers to a quintuple. (quintet), sex refers to the six-point (sextet), m refers to the multiplet (multiplet), and br refers to the broad peak (broad).

Gas Chromatography Analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set to 280 ° C, and the detector (flame ionization detector (FID)) was set to 300 ° C. For the separation of the component compounds, 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 dimethyl polyoxyalkylene. ; no polarity). The column was held at 200 ° C for 2 minutes and then heated to 280 ° C at a rate of 5 ° C / min. After the sample was prepared into an acetone solution (0.1% by weight), 1 μL of the sample was injected into the sample gasification chamber. The record is a C-R5A type chromatograph module (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the retention time of the peak corresponding to the component compound and the area of the peak.

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

The ratio of the liquid crystalline compound contained in the composition can be calculated by the method described below. A mixture of liquid crystal compounds was analyzed by a gas chromatograph (FID). 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 1. Therefore, the ratio (% by weight) of the liquid crystalline compound can be calculated from the area ratio of the peak.

Measurement sample: When the properties of the composition and the element were measured, the composition was directly used as a sample. When the properties of the compound were measured, a sample for measurement was prepared by mixing the compound (15% by weight) in a mother liquid crystal (85% by weight). The characteristic value of the compound was calculated by an extrapolation method based on the value obtained by the measurement. (Extrapolation value) = {(measured value of sample) - 0.85 × (measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) is precipitated at 25 ° C at this ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% by weight The order of % changes. The extrapolation method was used to determine the values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy associated with the compound.

The following mother liquid crystal was used. The proportion of the constituent compounds is expressed in % by weight.

Measurement method: The measurement of the characteristics was carried out by the following method. Most of these methods are methods described in the Japanese JEITA specification (JEITA ED-2521B) by the Japan Electronics and Information Technology Industries Association (JEITA), or a method of modifying them. A thin film transistor (TFT) was not mounted on the TN device used for the measurement.

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

(2) Lower limit temperature of nematic phase (TC; °C): The sample with the nematic phase is placed in a glass bottle and frozen at 0 ° C, -10 ° C, -20 ° C, -30 ° C and -40 ° C. After storage for 10 days in the apparatus, the liquid crystal phase was observed. For example, when the sample is maintained in a nematic phase at -20 ° C and changed to a crystal or a smectic phase at -30 ° C, T _{C is} described as < -20 ° C. The lower limit temperature of the nematic phase is sometimes simply referred to as "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa·s): According to M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259 The method described in 37 (1995) was carried out. A sample was injected into a VA element having a glass substrate with a cell gap of 20 μm. The voltage is applied stepwise in units of 1 volt in the range of 39 volts to 50 volts for the device. After the voltage was not applied for 0.2 seconds, the voltage was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 second) and no application (2 seconds). A peak current and a peak time of a transient current generated by the application were measured. The values of the rotational viscosity were obtained from these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for this calculation was measured by the method described in the measurement (6).

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

(6) Dielectric Anisotropy (Δε; measured at 25 ° C): The value of dielectric anisotropy was calculated from the equation of Δ ε = ε ∥ - ε 。 . The dielectric constants (ε∥ and ε⊥) were measured in the following manner. 1) Measurement of dielectric constant (ε∥): A solution of octadecyl triethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-washed glass substrate. 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 element having a distance (cell gap) of 4 μm between two glass substrates, and the element was sealed by an adhesive which was cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and after 2 seconds, the dielectric constant ε (∥) in the long-axis direction of the liquid crystal molecules was measured. 2) Measurement of dielectric constant (ε⊥): A polyimide solution was coated on a sufficiently cleaned glass substrate. After the glass substrate was calcined, the obtained alignment film was subjected to a rubbing treatment. A sample was injected into a TN device in which the distance between the two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to the device, and after 2 seconds, the dielectric constant (ε⊥) of the liquid crystal molecule in the short-axis direction was measured.

(7) Threshold voltage (Vth; measured at 25 ° C; V): An LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample is placed in a normally black mode VA element in which the distance between the two glass substrates (cell gap) is 4 μm and the rubbing direction is anti-parallel, and the adhesive is cured using ultraviolet rays. The component is sealed. The voltage applied to the device (60 Hz, rectangular wave) is stepwise increased from 0 V to 20 V in units of 0.02 V. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve having a transmittance of 100% when the amount of light reaches a maximum and a transmittance of 0% when the amount of light is minimum. The threshold voltage is expressed by the voltage at which the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-1; measured at 25 ° C; %): The TN element used for the measurement had a polyimide film, and the interval (cell gap) between the two glass substrates was 5 μm. After the component is injected, the component is sealed with an ultraviolet-curable adhesive. A pulse voltage (5 V, 60 microseconds) was applied to the TN device for charging. The attenuated voltage was measured by a high-speed voltmeter over a period of 16.7 msec, and the area A between the voltage curve per unit period and the horizontal axis was obtained. Area B is the area when the voltage is not attenuated. The voltage holding ratio is expressed by the percentage of the area A with respect to the area B.

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

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

(11) Voltage holding ratio (VHR-4; measured at 25 ° C; %): After the TN device in which the sample was injected was heated in a constant temperature bath at 80 ° C for 500 hours, the voltage holding ratio was measured to evaluate the stability to heat. . In the measurement of VHR-4, the attenuated voltage was measured during 16.7 msec. The composition having a large VHR-4 has great stability to heat.

(12) Response time (τ; measured at 25 ° C; ms): An LCD 5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a VA device in which the interval (cell gap) between the two glass substrates was 3.5 μm and the alignment film was not provided. The element is sealed with an adhesive that is cured by ultraviolet light. While applying a voltage of 30 V to the device, ultraviolet rays of 78 mW/cm ² (405 nm) were irradiated for 449 seconds (35 J). A multi-metal lamp M04-L41 for ultraviolet curing manufactured by EYE GRAPHICS Co., Ltd. was used for the irradiation of ultraviolet rays. A rectangular wave (120 Hz) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. When the amount of light reaches the maximum, it is regarded as a transmittance of 100%, and when the amount of light is the smallest, it is regarded as a transmittance of 0%. The maximum voltage of the rectangular wave is set such that the transmittance becomes 90%. The lowest voltage of the rectangular wave is set to 2.5 V with a transmittance of 0%. The response time is expressed by the time (rise 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): EC-made by Toyo Corporation (TOYO Corporation) Type 1 elastic constant tester. A sample was injected into a vertical alignment member having a glass substrate with a cell gap (cell gap) of 20 μm. A charge of 20 volts to 0 volts was applied to the device, and the electrostatic capacitance and the applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) using equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkei Industry News), according to The value of the elastic constant is obtained by the formula (2.100).

(14) Specific resistance (ρ; measured at 25 ° C; Ω cm): 1.0 mL of a sample was placed in a container equipped 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 by the following formula. (specific resistance) = {(voltage) × (capacitance of the container)} / {(direct current) × (dielectric constant of vacuum)} (Equation 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) Orientation stability (liquid crystal alignment axis stability): The change of the liquid crystal alignment axis on the electrode side of the liquid crystal display element was evaluated. The liquid crystal alignment angle f of the electrode side before the stress was applied was measured, and then a rectangular wave of 4.5 V and 60 Hz was applied to the device for 20 minutes, and then buffered for 1 second, and the electrode side was measured again after 1 second and 5 minutes. The liquid crystal alignment angle f (after). From these values, the change Δf (deg.) of the liquid crystal alignment angle after 1 second and 5 minutes was calculated using the following formula. Δf(deg.)=f(after)-f(before) (Equation 2) J. Hilfik, B. Jensen, C. Hesseger, JF Elman, E. Montbach, D. B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos, Thin Solid Films, 455-456 (2004) 596-600 refer to these measurements. It can be said that the smaller the Δf is, the smaller the rate of change of the liquid crystal alignment axis is, and the better the stability of the liquid crystal alignment axis is.

[Synthesis Example 1] Synthesis of Compound (1-7) First, the synthesis of the compound (T-4) will be described.

In the first step, paraformaldehyde (60.0 g), 1,4-diazabicyclo[2.2.2]octane (DABCO (1,4-diazabicyclo [2.2.2] octane); 56.0 g) and water (200 ml) was placed in the reactor and stirred at room temperature for 15 minutes. A solution of the compound (T-1) (50.0 g) in tetrahydrofuran (THF) (400 ml) was added dropwise. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (yield: toluene: ethyl acetate = 2:1) to afford compound (T-2) (44.1 g; 68%).

Second step Compound (T-2) (44.1 g), imidazole (25.0 g) and dichloromethane (400 ml) were placed in a reactor and cooled to 0 °C. A dichloromethane solution (200 ml) of tributyldimethylchloromethane (TBSCl; 53 g) was added dropwise, and the mixture was stirred for 4 hours while warming to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (hexane, ethyl acetate = 9:1) to afford compound (T-3) (69.6 g; 84%) .

Step 3 Compound (T-3) (69.6 g), THF (600 ml), methanol (150 ml) and water (100 ml) were placed in the reactor and cooled to 0 °C. Lithium hydroxide monohydrate (23.9 g) was added thereto, returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, and after 6 N hydrochloric acid (20 ml) was slowly added to form acidic, the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to give Compound (T-4) (21.6 g; 35%).

Next, a method of synthesizing the compound (1-7) will be described.

Step 4 The compound (T-5) was synthesized according to a usual method. Compound (T-5) (7.5 g), tetrakis(triphenylphosphine)palladium (1.3 g), tetrabutylammonium bromide (TBAB), potassium carbonate (6.4 g), 1 -Bromo-3,5-dimethoxybenzene (5 g), toluene (200 ml), 2-propanol (IPA; 80 ml), pure water (20 ml), placed in the reactor at 90 ° C Stir under. The reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The organic layer produced together was washed with water and dried with 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), and the solvent mixture (volume ratio from heptane to toluene). Recrystallization from 1:1) was carried out to obtain Compound (T-6) (7.18 g; 85%).

Step 5 Compound (T-6) (7.18 g) and dichloromethane (200 ml) were placed in a reactor and cooled to -50 °C. Boron tribromide (2.1 ml) was added dropwise. The mixture was stirred for 5 hours while warming to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (yield: toluene: ethyl acetate = 1:1) to afford compound (T-7) (5.3 g; 80%).

Step 6: Compound (T-7) (5.3 g), ethyl carbonate (3.0 g), potassium carbonate (6.5 g) and dimethylformamide (DMF) (200 ml) were placed. In the reactor, stirring was carried out at 100 °C. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (yield: toluene: ethyl acetate = 1:1) to afford compound (T-8) (5.5 g; 83%).

Step 7: Compound (T-8) (5.3 g), Compound (T-4) (5.9 g), N,N-dimethyl-4-aminopyridine (DMAP (N, N-dimethyl-4-) Aminopyridine); 1.52 g) and dichloromethane (150 ml) were placed in the reactor and cooled to 0 °C. A solution of N,N'-dicyclohexylcarbodiimide (DCC (N, N'-dicyclohexyl carbodiimide; 7.7 g) in dichloromethane (50 ml) was added dropwise. The mixture was stirred for 5 hours while warming to room temperature. The reaction mixture was poured into water and the aqueous layer was extracted with dichloromethane. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (yield: toluene: heptane = 1:1) to afford compound (T-9) (8.3 g; 81%).

Step 8 Compound (T-9) (8.3 g) and THF (100 ml) were placed in a reactor and cooled to 0 °C. Tetrabutylammonium fluoride (TBAF (Tetrabutylammonium Fluoride); 2.9 g) was added dropwise, and the mixture was stirred for 3 hours while warming to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The organic layer produced together was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene: ethyl acetate = 1:1), and then purified by recrystallization from heptane to obtain a compound ( 1-7) (4.5 g; 75%).

¹ H-NMR (ppm; CDCl ₃ ) of the compound (1-7): δ 7.48-7.46 (m, 2H), 7.27-7.26 (m, 2H), 6.75 (d, J = 2.3 Hz, 2H), 6.47 -6.46 (m, 1H), 6.30 (s, 2H), 5.86 (d, J=1.1 Hz, 2H), 4.54 (t, J=4.4 Hz, 4H), 4.33 (s, 4H), 4.27-4.25 ( m, 4H), 2.52-2.47 (m, 1H), 2.34 (s, 2H), 1.90 (t, J=14 Hz, 4H), 1.51-1.44 (m, 2H), 1.35-1.20 (m, 9H) , 1.09-1.02 (m, 2H), 0.90 (t, J=6.9 Hz, 3H)

The examples of the composition are shown below. The component compounds are indicated by symbols based on the definitions of Table 3 below. In Table 3, the stereo configuration associated with 1,4-cyclohexylene is the trans configuration. The numbering in parentheses after the symbolized compound indicates the chemical formula to which the compound belongs. The symbol of (-) 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 additive. Finally, the characteristic values of the composition are summarized.

Example of Element 1. Raw material A composition to which a polar compound was added was injected into an element having no alignment film. After the ultraviolet ray was irradiated, the vertical alignment of the liquid crystal molecules in the element was investigated. First, the raw materials will be explained. The raw material is suitable from the composition (M1) to the composition (M18), the polar compound (PC-1) to the polar compound (PC-5), the polymerizable compound (RM-1) to the polymerizable compound (RM-9). select. 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°C; Tc<- 20 ° C; Δn = 0.113; Δ ε = -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°C; Tc<-30°C; 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°C; Tc<-30°C; 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°C Tc<-30°C; 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°C; Tc<-30°C; 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°C; Tc<-30°C ; Δn = 0.111; Δ ε = -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°C; Tc<-30°C; 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°C; Tc<-20°C; 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°C ; Tc < -30 ° C; Δn = 0.123; Δ ε = -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°C; Tc<-30°C; 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°C; Tc<-20°C; 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°C; Tc<-30°C; 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°C; Tc<-20°C; Δn=0.103 ; Δ ε = -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°C; Tc<-20°C; 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°C; Tc<-30°C; 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°C; Tc<-20°C; 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 ° C; Tc < -20 ° C; Δn = 0.101; Δ ε = -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 °C; Tc<-20°C; 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-5).

The second additive is a polymerizable compound (RM-1) to a polymerizable compound (RM-9).

2. Vertical alignment of liquid crystal molecules Example 1 A polar compound (PC-1) was added to the composition (M1) at a ratio of 5% by weight. This mixture was injected onto a hot stage at 100 ° C into an element in which the interval (cell gap) of the two glass substrates was 4.0 μm and there was no alignment film. The polar compound (PC-1) was polymerized by irradiating the device with ultraviolet rays (28 J) using an ultrahigh pressure mercury lamp USH-250-BY (manufactured by Ushio Motor). This element was placed in a polarizing microscope in which the polarizing element and the analyzer were arranged orthogonally, and the element was irradiated with light from below to observe the presence or absence of light leakage. When the light is not transmitted through the element, it is judged that the vertical alignment is "good". This is because it is inferred that the liquid crystal molecules are sufficiently aligned. When the light transmitted through the element is observed, it is expressed as "poor".

Example 2 to Example 18 and Comparative Example 1 An element prepared by adding a polar compound having a polymerizable group to a composition was used to produce an element having no alignment film. The presence or absence of light leakage was observed in the same manner as in Example 1. The results are summarized in Table 4. In Example 18, the polymerizable compound (RM-1) was also added in a ratio of 0.5% by weight. In Comparative Example 1, for comparison, the following polar compound (PC-11) was selected. This is because the compound does not have a polymerizable group and is different from the compound (1).

Table 4. Vertical alignment of liquid crystal molecules

As is clear from Table 4, in Examples 1 to 18, although the type of the composition or the polar compound was changed, 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 18, the polymerizable compound (RM-1) was further added, but the same result was obtained. On the other hand, light leakage was observed in Comparative Example 1. This result indicates that the vertical alignment is not good. Therefore, it is understood that a polymer produced from a polar compound having a polymerizable group plays an important role in the vertical alignment of liquid crystal molecules. [Industrial availability]

The liquid crystal composition of the present invention can be used for a liquid crystal projector, a liquid crystal television, or the like.

no

no

Claims (20)

A liquid crystal composition containing at least one compound selected from the group consisting of polar compounds represented by formula (1) as a first additive and having a negative dielectric anisotropy, In the formula (1), Ring A and Ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxin An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Alkenyl having 2 to 12 carbon atoms, at least one alkyl group having 1 to 12 carbons substituted by fluorine or chlorine, or at least one hydrogen having 2 to 12 carbon atoms substituted by fluorine or chlorine; ring B Is 1,4-cyclohexylene, 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- a diradical or pyridine-2,5-diyl group, wherein at least one of the hydrogens may be fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and a carbon number of 2 to 12 Alkenyl group, at least one alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine, or at least one hydrogen group having 2 to 12 carbon atoms substituted by fluorine or chlorine Generation; Z ¹ and Z ^{2 are} independently a single bond or an alkylene group having 1 to 10 carbons, said alkylene, at least one -CH ₂ - may be -O -, - CO -, - COO- , or -OCO-substituted, and at least one -CH ₂ CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C (CH ₃ )-substituted, wherein at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, 2 or 3; b, c and d are independently 0, 1, 2, 3 or 4, Further, the sum of b, c and d is 2 or more; Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one -CH ₂ - may be in the alkylene group. Substituted by -O-, -COO-, -OCO- or -OCOO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, of which at least one hydrogen It may be substituted by fluorine or chlorine; P ¹ , P ² and P ^{3 are} independently a polymerizable group represented by the formula (PA), In the formula (PA), Sp ⁴ is a single bond or an alkylene group having 1 to 7 carbon atoms, and at least one of -CH ₂ - may be substituted by -O-, -COO- or -OCO-. At least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, wherein at least one hydrogen may be substituted by fluorine; R ¹ is -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N a group represented by (R ⁰ ) ₂ , wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; and M ⁴ and M ^{5 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least An alkyl group having 1 to 5 carbon atoms in which hydrogen is substituted by fluorine or chlorine. The liquid crystal composition according to claim 1, wherein, in the formula (1) according to the first aspect of the patent application, the ring A and the ring C are independently a cyclohexyl group, a phenyl group, a 1-naphthyl group. Or 2-naphthyl, in which at least one hydrogen may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, at least one Hydrogen is substituted with fluorine or chlorine substituted alkyl having 1 to 12 carbon atoms, or at least one hydrogen is substituted by fluorine or chlorine with 2 to 12 carbon atoms; ring B is 1,4-cyclohexylene, 1,4 - a phenyl, naphthalene-1,2-diyl or naphthalene-2,6-diyl group, wherein at least one of the hydrogens may be through fluorine, chlorine, an alkyl group having from 1 to 12 carbons, and a carbon number of from 1 to An alkoxy group of 12, an alkenyl group having 2 to 12 carbons, an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine, or an alkene having 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. Base substitution; a is 0 or 1. The liquid crystal composition according to claim 1, wherein the first additive is at least one compound selected from the group consisting of polar compounds represented by formula (1-1) to formula (1-13), In the formulae (1-1) to (1-13), R ¹ is a group represented by -OH, -OR ⁰ , -NH ₂ , -NHR ⁰ or -N(R ⁰ ) ₂ , where R ⁰ Is hydrogen or an alkyl group having 1 to 12 carbon atoms; R ² is hydrogen, fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or at least a C 1 to 12 alkyl group in which hydrogen is substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Z ¹ and Z ^{2 are} independently a single bond or a carbon number of 1 And an alkylene group of 10, wherein at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and 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 which at least one hydrogen can be Substituted by fluorine or chlorine; Sp ¹ and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be -O-, -COO-, -OCO- or -OCOO-substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be substituted by fluorine or chlorine; Sp ⁴ a single bond or an alkylene group having 1 to 7 carbon atoms, at least one of the alkylene groups -CH ₂ - may be -O -, - COO- or -OCO-, at least one -CH ₂ CH ₂ - may be replaced by -CH = CH-, the plurality of groups, at least one hydrogen may be replaced by fluorine; L ¹ , L ² , L ³ , L ⁴ , L ⁵ and L ^{6 are} independently hydrogen, fluorine, methyl or ethyl. The liquid crystal composition according to claim 1, wherein the ratio of the first additive is in the range of 0.05% by weight to 10% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group consisting of compounds represented by formula (2) as a first component, In the formula (2), R ³ and R ^{4 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 an oxyalkylene having 2 to 12 carbon atoms. Ring; Ring D and Ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-extension of at least one hydrogen substituted by fluorine or chlorine Phenyl or tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl or 7,8-difluorochroman-2,6 -diyl; Z ³ and Z ^{4 are} independently a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-; f is 1, 2 or 3, g It is 0 or 1, and the sum of f and g is 3 or less. The liquid crystal composition according to claim 5, which contains at least one compound selected from the group consisting of compounds represented by formula (2-1) to formula (2-22) as a first component, In the formulae (2-1) to (2-22), R ³ and R ^{4 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 claim 5, wherein the ratio of the first component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group consisting of compounds represented by formula (3) as a second component, In the formula (3), R ⁵ and R ^{6 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 substituted by fluorine or chlorine. An alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbons substituted with at least one hydrogen via fluorine or chlorine; ring G and ring I are independently 1,4-cyclohexylene, 1,4-stretch Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, - OCH ₂ -, -COO- or -OCO-; h is 1, 2 or 3. The liquid crystal composition according to claim 8, which contains at least one compound selected from the group consisting of compounds represented by formula (3-1) to formula (3-13) as a second component, Formula (3-1) to (3-13), R ⁵ is and R ⁶ are independently alkyl alkoxycarbonyl, 1 to 12 carbon atoms, 1 to 12 carbons, alkenyl having 2 to 12 At least one alkyl group having 1 to 12 carbons substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbons substituted with at least one hydrogen via fluorine or chlorine. The liquid crystal composition according to claim 5, which contains at least one compound selected from the group consisting of compounds represented by formula (3) as a second component, In the formula (3), R ⁵ and R ^{6 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 substituted by fluorine or chlorine. An alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbons substituted with at least one hydrogen via fluorine or chlorine; ring G and ring I are independently 1,4-cyclohexylene, 1,4-stretch Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, - OCH ₂ -, -COO- or -OCO-; h is 1, 2 or 3. The liquid crystal composition according to claim 8, wherein the ratio of the second component is in the range of 10% by weight to 70% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group consisting of polymerizable compounds represented by formula (4) as a second additive, In the formula (4), the ring J and the ring P are independently a cyclohexyl group, a cyclohexenyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tetrahydropyran-2-yl group, and a 1,3-dioxin. An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7 -diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-di a 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl group, wherein at least one hydrogen in the ring may be via fluorine, chlorine or carbon An alkyl group of 1 to 12, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ^{7 are} independently a single bond or carbon a number 1 to 10 alkylene group in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, in these groups At least one hydrogen may be substituted with fluorine or chlorine; and P ⁴ , P ⁵ and P ⁶ are polymerizable groups different from the polymerizable group represented by the formula (PA) described in the first aspect of the patent application; Sp ⁵ , Sp ⁶ and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -COO-, -OCO- or -OCOO. Substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein 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 claim 12, wherein the second additive is at least one compound selected from the group consisting of polymerizable compounds represented by formula (4-1) to formula (4-28). , In the formulae (4-1) to (4-28), P ⁴ , P ⁵ and P ^{6 are} independently a group selected from the group consisting of the polymerizable groups represented by the formulae (P-1) to (P-3). Base, Here, M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Sp ⁵ , Sp ⁶ and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -COO-, -OCO- or -OCOO-. Substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be substituted by fluorine or chlorine. The liquid crystal composition according to claim 5, which contains at least one compound selected from the group consisting of polymerizable compounds represented by formula (4) as a second additive, In the formula (4), the ring J and the ring P are independently a cyclohexyl group, a cyclohexenyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tetrahydropyran-2-yl group, and a 1,3-dioxin. An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7 -diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-di a 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl group, wherein at least one hydrogen in the ring may be via fluorine, chlorine or carbon An alkyl group of 1 to 12, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ^{7 are} independently a single bond or carbon a number 1 to 10 alkylene group in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, in these groups At least one hydrogen may be substituted with fluorine or chlorine; and P ⁴ , P ⁵ and P ⁶ are polymerizable groups different from the polymerizable group represented by the formula (PA) described in the first aspect of the patent application; Sp ⁵ , Sp ⁶ and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -COO-, -OCO- or -OCOO. Substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein 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 claim 8, which contains at least one compound selected from the group consisting of polymerizable compounds represented by formula (4) as a second additive, In the formula (4), the ring J and the ring P are independently a cyclohexyl group, a cyclohexenyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tetrahydropyran-2-yl group, and a 1,3-dioxin. An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7 -diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-di a 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl group, wherein at least one hydrogen in the ring may be via fluorine, chlorine or carbon An alkyl group of 1 to 12, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ^{7 are} independently a single bond or carbon a number 1 to 10 alkylene group in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, in these groups At least one hydrogen may be substituted with fluorine or chlorine; and P ⁴ , P ⁵ and P ⁶ are polymerizable groups different from the polymerizable group represented by the formula (PA) described in the first aspect of the patent application; Sp ⁵ , Sp ⁶ and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -COO-, -OCO- or -OCOO. Substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein 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 claim 10, which contains at least one compound selected from the group consisting of polymerizable compounds represented by formula (4) as a second additive, In the formula (4), the ring J and the ring P are independently a cyclohexyl group, a cyclohexenyl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tetrahydropyran-2-yl group, and a 1,3-dioxin. An alk-2-yl, pyrimidin-2-yl or pyridin-2-yl group, wherein at least one hydrogen in the rings may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms. Or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7 -diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-di a 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl group, wherein at least one hydrogen in the ring may be via fluorine, chlorine or carbon An alkyl group of 1 to 12, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁶ and Z ^{7 are} independently a single bond or carbon a number 1 to 10 alkylene group in which at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )-, in these groups At least one hydrogen may be substituted with fluorine or chlorine; and P ⁴ , P ⁵ and P ⁶ are polymerizable groups different from the polymerizable group represented by the formula (PA) described in the first aspect of the patent application; Sp ⁵ , Sp ⁶ and Sp ^{7 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -COO-, -OCO- or -OCOO. Substituted, and at least one -CH ₂ CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein 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 claim 12, wherein the ratio of the second additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition. A liquid crystal display element which does not have an alignment film, which comprises the liquid crystal composition according to claim 1, wherein the first additive contained in the liquid crystal composition is polymerized. A liquid crystal display element which does not have an alignment film, which comprises the liquid crystal composition according to claim 12, wherein the first additive and the second additive contained in the liquid crystal composition are polymerized. A liquid crystal composition which is a liquid crystal composition as described in claim 1, which is used in a liquid crystal display element which does not have an alignment film.