TW201627409A - Liquid crystal composition, use thereof, and liquid crystal display device - Google Patents

Abstract

The subject is to provide a liquid crystal composition that includes a polymerizable compound (or polymer) and a polar compound, where the homeotropic alignment of liquid crystal molecules can be achieved by the action of these compounds, and a liquid crystal display device including this composition. The means concerns a nematic liquid crystal composition that has negative dielectric anisotropy and that includes a polymerizable compound as an first additive and a polar compound as a second additive, and the composition may include a specific liquid crystal compound having a large negative dielectric anisotropy and a specific liquid crystal compound having a high maximum temperature or a small viscosity, and concerns a liquid crystal display device including the composition.

Description

Liquid crystal composition and liquid crystal display element

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, there is a liquid crystal composition containing a polar compound and a polymerizable compound (or a polymer thereof) and having a negative dielectric anisotropy of liquid crystal molecules by the action of the compounds, 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 the characteristics of the two 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, it is preferred to have a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase in the initial stage. It is preferably a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. 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 the polymer sustained alignment (PSA) type liquid crystal display device, the effect of the polymer is effectively used. 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 is used for a liquid crystal display element which does not have an alignment film. 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 3 below. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

[Problems to be solved by the invention]

An object of the present invention is a liquid crystal composition comprising a polymerizable compound (or a polymer thereof) and a polar compound, and which can achieve vertical alignment of liquid crystal molecules by the action of the compounds. Another object is a liquid crystal composition having a high upper limit temperature in a nematic phase, a low lower limit temperature of a nematic phase, a small viscosity, an appropriate optical anisotropy, a negative large dielectric anisotropy, and a large At least one characteristic is satisfied among characteristics such as specific resistance, high stability against ultraviolet rays, and high stability against heat. Another object is a liquid crystal composition having an appropriate balance between at least two characteristics. Another object is a liquid crystal display element containing such a composition. Still another object is 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 is at least one polymerizable compound containing a group selected from the group consisting of compounds represented by formula (1) as a first additive, at least one polar compound as a second additive, and having a negative dielectric orientation A liquid crystal composition having an opposite polarity and a liquid crystal display element containing the composition. 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 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. a group, or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring B is a 1,4-cyclohexylene group, a 1,4-cyclohexene group, a 1,4-phenylene group , naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen can pass fluorine, chlorine , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; Z ¹ and Z ^{2 are} 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-, -CO-, -COO-, or -OCO-, and at least one -C H 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 the group, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; and Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or a carbon number of 1 to 10. An alkyl group in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be - CH=CH- or -C≡C-substituted, wherein at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, or 2; b, c, and d are independently 0, 1, 2 3, or 4; wherein, when ring A and ring C are phenyl groups, a is 1 or 2, and when a is 1, Sp ¹ and Sp ³ are single bonds. [Effects of the Invention]

An advantage of the present invention is a liquid crystal composition comprising a polymerizable compound (or a polymer thereof) and a polar compound, and a vertical alignment of liquid crystal molecules can be achieved by the action of the compounds. Another advantage is a liquid crystal composition having a high upper limit temperature in the nematic phase, a low lower limit temperature of the nematic phase, a small viscosity, a suitable optical anisotropy, a negative large dielectric anisotropy, and a large At least one characteristic is satisfied among characteristics such as specific resistance, high stability against ultraviolet rays, and high stability against heat. Another advantage is a liquid crystal composition having an appropriate balance between at least two characteristics. Another advantage is a liquid crystal display element containing such a composition. Still another advantage is 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 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. The liquid crystalline compound or additive is mixed in this order. 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 not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and not only at room temperature but also after long-term use. It also has a large specific resistance at a temperature close to the upper limit temperature. "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'".

In the chemical formula of the component compound, the symbol of the terminal group R ¹ is used for a plurality of compounds. Among these compounds, the two groups represented by any two of R ¹ may be the same or different. For example, there is a case where R ¹ of the compound (2-1) is an ethyl group, and R ¹ of the compound (2-2) is an ethyl group. Also the compound ^(2-1), R ¹ is ethyl, and R of the compound (2-2) ¹ is propyl. This rule also applies to symbols such as other end groups. In the formula (2), when e is 2, two rings D exist. In the compound, the two rings represented by the two rings D may be the same or different. This rule also applies to any two rings D when e is greater than 2. This rule also applies to other tokens. This rule also applies to the case of two -Sp ² -P ² of the compound (1-11).

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. In the formula (1), the oblique line of the hexagonal cross-section indicates that any hydrogen on the ring may be substituted with a group such as -Sp ¹ -P ¹ . Subscripts such as 'b' indicate the number of substituted groups. When the subscript 'b' is 0, it means that there is no such substitution. When the subscript 'b' 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.

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 binders such as carbonyloxy (-COO- or -OCO-).

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 means that "one -CH ₂ - may be -O-substituted" and "at least two non-adjacent -CH ₂ - may be -O-substituted". 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 formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ - in the alkyl group may be substituted with -CH=CH- or the like. By this substitution, the carbon number of the alkyl group increases. At this time, the maximum carbon number is 30. This rule also applies to alkylene, cycloalkylene and the like.

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. The stereo configuration associated with 1,4-cyclohexylene is generally that the trans configuration is superior to the cis configuration. Halogen means fluorine, chlorine, bromine or iodine. Preferred halogens are fluorine or chlorine. A particularly preferred halogen is fluorine.

The present invention is as follows.

Item 1. A liquid crystal composition containing at least one polymerizable compound selected from the group consisting of compounds represented by formula (1) as a first additive, containing at least one polar compound as a second 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 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. a group, or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring B is a 1,4-cyclohexylene group, a 1,4-cyclohexene group, a 1,4-phenylene group , naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen can pass fluorine, chlorine , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; Z ¹ and Z ^{2 are} independently a single bond or a C 1-10 alkylene, which alkylene, at least one -CH ₂ - may be -O - -OCO- substituted -COO-, or, moreover, at least one -C -, - CO -, H 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 the group, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; and Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or a carbon number of 1 to 10. An alkyl group in which at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be - CH=CH- or -C≡C-substituted, wherein at least one hydrogen may be substituted by fluorine or chlorine; a is 0, 1, or 2; b, c, and d are independently 0, 1, 2 3, or 4; wherein, when ring A and ring C are phenyl groups, a is 1 or 2, and when a is 1, Sp ¹ and Sp ³ are single bonds.

The liquid crystal composition according to Item 1, wherein, in the formula (1), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of formula (P-1) to formula (P-5). Polymeric groups in the group of bases, Formula (P-1) to Formula (P-5) in, M ^1, M ^2, and M ³ are independently hydrogen, fluoro, alkyl of 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 5 carbon atoms.

The liquid crystal composition according to Item 1 or 2, wherein the first additive is at least one polymerization selected from the group consisting of compounds represented by formula (1-1) to formula (1-12) Compound, In the formulae (1-1) to (1-12), P ¹ , P ² , and P ^{3 are} independently a group selected from the group represented by the formula (P-1) to the formula (P-3). a polymerizable group, wherein 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 substituted with at least one hydrogen via fluorine or chlorine. base; 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- in the alkylene group. 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 any one of items 1 to 3, wherein the ratio of the first additive is in the range of 0.03 wt% to 10 wt% 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 ¹ and R ^{2 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 alkene having 2 to 12 carbon atoms. Oxyl; ring D and ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen substituted by fluorine or chlorine 1,4- Phenyl, or tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenyl, 2-chloro-3-fluoro-1,4-phenyl , 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-; e is 1 , 2, or 3, f is 0 or 1, and the sum of e and f 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 (2-21) is used as First ingredient, In the formulae (2-1) to (2-21), R ¹ and R ^{2 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 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, 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-;g 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, In the formulae (3-1) to (3-13), 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. 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 90% by weight based on the weight of the liquid crystal composition.

The liquid crystal composition according to any one of items 1 to 10, wherein the second additive is a polar compound containing a polar group having a hetero atom selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus.

The liquid crystal composition according to any one of items 1 to 11, comprising at least one polar compound selected from the group consisting of compounds represented by formula (4) and formula (5) as a second addition Object, In the formula (4), the MES is a liquid crystal primor having at least one ring; in the formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ - may pass through -CH in the alkyl group =CH-, -CF=CH-, -CH=CF-, -C≡C-, or a cycloalkyl group having a carbon number of 3 to 8, wherein at least one hydrogen may be substituted with fluorine or chlorine; In the formulae (4) and (5), R ⁶ is a polar group having at least one of an oxygen atom of an OH structure, a sulfur atom of an SH structure, and a nitrogen atom of a primary, secondary or tertiary amine structure; 1 or 2.

The liquid crystal composition according to any one of items 1 to 12, which contains at least one compound selected from the group consisting of compounds represented by formula (4-1) as a second additive, In the formula (4-1), the ring J and the ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or carbon. a heterocyclic ring group of 4 to 25, which may be a condensed ring, wherein at least one hydrogen may be substituted via a group T, wherein the group T is -OH, -(CH ₂ ) _j -OH , halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ⁰ ) ₂ , -C(=O)R ⁰ , -N(R ⁰ ) ₂ , -(CH ₂ ) _j -N(R ⁰ ) ₂ , an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 25 carbon atoms, and a carbon number of 1 to 25 Alkoxy group, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms, or alkoxycarbonyloxy group having 2 to 25 carbon atoms In the group, at least one hydrogen may be substituted by fluorine or chlorine, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, j is 1, 2, 3, or 4; and Z ⁶ is -O- , -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, - CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _j -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _j - , -CH=CH-, -CF=CF-, -C≡C-, -C H = CH-COO -, - OCO-CH = CH -, - C (R 0) 2, or a single bond, where, R ⁰ is hydrogen or alkyl having 1 to 12, j is 1, 2, 3, or 4; R ⁶ is an alkyl group having 1 to 25 carbon atoms, wherein at least one -CH ₂ - may be via -NR ⁰ -, -O-, -S-, -CO-, -COO- , -OCO-, -OCOO-, or a cycloalkyl group having a carbon number of 3 to 8, wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and at least one tertiary carbon (>CH-) may be Substituted by nitrogen (>N-), and at least one hydrogen may be substituted by fluorine or chlorine, wherein R ⁶ has an oxygen atom of an OH structure, a sulfur atom of an SH structure, or a nitrogen of a primary, secondary or tertiary amine structure. At least one of atoms; R ⁷ is hydrogen, halogen, alkyl having 1 to 25 carbon atoms, and at least one of -CH ₂ - may be via -NR ⁰ -, -O-, -S-, -CO -, -CO-O-, -O-CO-, -O-CO-O-, or a cycloalkyl group having a carbon number of 3 to 8, and at least one tertiary carbon (>CH-) may be nitrogen (>N-) substituted, in which at least one hydrogen may be substituted by fluorine or chlorine, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; i is 0, 1, 2, 3, 4 , or 5.

The liquid crystal composition according to any one of items 1 to 12, which contains at least one polar compound selected from the group consisting of compounds represented by formula (5-1) as a second additive, In the formula (5-1), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ - may be via -CH=CH-, -CF=CH-, -CH=CF-. , -C≡C-, or a cycloalkyl group having a carbon number of 3 to 8, wherein at least one hydrogen may be substituted by fluorine or chlorine; and R ⁶ is an alkyl group having 1 to 25 carbon atoms, the alkyl group Wherein at least one -CH ₂ - may be through -NR ⁰ -, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, or a cycloalkyl group having a carbon number of 3 to 8. Substituting, here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, at least one tertiary carbon (>CH-) may be substituted by nitrogen (>N-), and at least one hydrogen may also be fluorine or chlorine And wherein R ⁶ has at least one of an oxygen atom of an OH structure, a sulfur atom of an SH structure, or a nitrogen atom of a primary, secondary or tertiary amine structure.

The liquid crystal composition according to any one of items 12 to 14, wherein, in the formula (4) and the formula (5) according to item 12, R ⁶ is a formula (A1) to (A4). Any of the indicated bases, From the formula (A1) to the formula (A4), Sp ⁴ , Sp ⁶ , and Sp ^{7 are} independently a single bond or a group (-Sp''-X''-), where Sp'' is a carbon number of 1 to 20 The alkyl group, at least one -CH ₂ - may be via -O-, -S-, -NH-, -N(R ⁰ )-, -CO-, -CO-O-, - O-CO, -O-CO-O-, -S-CO-, -CO-S-, -N(R ⁰ )-CO-O-, -O-CO-N(R ⁰ )-, -N (R ⁰ )-CO-N(R ⁰ )-, -CH=CH-, or -C≡C-substituted, wherein at least one hydrogen may be substituted by fluorine, chlorine, or -CN, and X '' is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R ⁰ )-, -N(R ⁰ )-CO-, -N(R ⁰ )-CO-N(R ⁰ )-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, - OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N =N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, or a single bond, this at, R ⁰ is hydrogen or alkyl having 1 to 12, Y ² and Y ³ are independently hydrogen, fluorine, chlorine, or -CN; Sp ^{5 is> CH -,> CR 11 -} ,> N-, Or >C<; X ¹ is -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N(R ¹¹ ) ₂ , -SH, -SR ¹¹ , Wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; X ² is -O-, -CO-, -NH-, -NR ¹¹ -, -S-, or a single bond; Z ⁷ is carbon An alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 or 6 carbon atoms, or a combination thereof, wherein at least one hydrogen of the groups may be via -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N(R ¹¹ ) ₂ , fluorine or chlorine substituted; R ¹¹ is an alkyl group having 1 to 15 carbon atoms, of which at least one -CH ₂ - may be via -C≡C-, - CH=CH-, -COO-, -OCO-, -CO-, or -O-, in which at least one hydrogen may be substituted by fluorine or chlorine; ring L is an aromatic group having 6 to 25 carbon atoms Or an alicyclic group having 3 to 25 carbon atoms, which may be a condensed ring, wherein one to three hydrogens may be substituted by R ^L ; R ^L is -OH, -(CH ₂ ) _j - OH, fluorine, chlorine, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ⁰ ) ₂ , -C(=O)R ⁰ , -N( R ⁰ ) ₂ , -(CH ₂ ) _j -N(R ⁰ ) ₂ , -SH, -SR ⁰ , aryl group having 6 to 20 carbon atoms, heteroaryl group having 6 to 20 carbon atoms, carbon number 1 to 25 An alkyl group, an alkoxy group having 1 to 25 carbon atoms, an alkylcarbonyl group having 2 to 25 carbon atoms, an alkoxycarbonyl group having 2 to 25 carbon atoms, an alkylcarbonyloxy group having 2 to 25 carbon atoms, or From 2 to 25, an alkoxycarbonyl group, the plurality of groups, at least one hydrogen may be replaced by fluorine or chlorine, where, R ⁰ is hydrogen or alkyl of 1 to 12 carbon atoms, j is 1, 2, 3, or 4; k is 0, 1, 2, or 3; m is 2, 3, 4, or 5.

The liquid crystal composition according to Item 13, wherein the second additive is at least one selected from the group consisting of compounds represented by formula (4-1-1) to formula (4-1-4). Compound, In the formula (4-1-1) and the formula (4-1-4), the ring J and the ring K are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4. -phenyl, 2-fluoro-1,3-phenylene, 2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoro Methyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, or 2,3,5,6-tetrafluoro-1,4-phenylene; ring L is cyclohexyl or phenyl; Z ⁶ is a single bond, an extended ethyl group, or a carbonyloxy group; Z ⁷ is a single bond, an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 or 6 carbon atoms, or a combination thereof, wherein at least one hydrogen in the group may be -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N(R ¹¹ ) ₂ , or a halogen substitution, R ¹¹ is an alkyl group having 1 to 15 carbon atoms, wherein at least one -CH ₂ - may be via -C≡ C-, -CH=CH-, -COO-, -OCO-, -CO-, -O-, or -NH-substituted; Sp ⁴ is a single bond, an extended ethyl group, a propyl group, or a methylene oxide a group, Sp ⁷ is a single bond, or an alkylene group having 1 to 5 carbon atoms, in which the -CH ₂ - may be substituted by -O- or -NH-; and R ⁷ is an alkane having 1 to 8 carbon atoms. Base or fluorine; i is 0, ¹ , 2, 3, 4, or 5; X ¹ is -OH, -COOH, -SH, -OCH ₃ , or -NH ₂ ; X ² is a single bond or -O-.

The liquid crystal composition according to Item 14, wherein the second additive is at least one selected from the group consisting of compounds represented by formula (5-1-1) to formula (5-1-29). Compound, In the formula (5-1-1) to the formula (5-1-29), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ - may be -CH=CH-, -CF=CH-, -CH=CF-, -C≡C-, or a cycloalkyl group having a carbon number of 3 to 8, in which at least one hydrogen may be substituted with fluorine or chlorine.

The liquid crystal composition according to any one of items 1 to 17, wherein the ratio of the second additive is less than 10% by weight based on the weight of the liquid crystal composition.

A liquid crystal display element comprising the liquid crystal composition according to any one of items 1 to 18.

The liquid crystal display device of claim 19, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the driving mode of the liquid crystal display element is an active matrix mode.

Item 21. A polymer-stabilized alignment type liquid crystal display device comprising the liquid crystal composition according to any one of items 1 to 18, wherein the polymerizable compound in the liquid crystal composition is polymerized.

Item 22. A liquid crystal display element which does not have an alignment film, which comprises the liquid crystal composition according to any one of items 1 to 18, wherein the polymerizable compound in the liquid crystal composition is polymerized.

The use of the liquid crystal composition according to any one of items 1 to 18, which is used in a liquid crystal display element.

The use of the liquid crystal composition according to any one of items 1 to 18, 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 18, 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 placed between two substrates, and a light is applied to the composition to irradiate light to form a polymerizable compound contained in the composition. Polymerization was carried out to produce the above liquid crystal display element. (b) The liquid crystal composition has a maximum temperature of a nematic phase of 70 ° C or higher, an optical anisotropy at a wavelength of 589 nm (measured at 25 ° C) of 0.08 or more, and dielectrics at a frequency of 1 kHz. The anisotropy (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 polymerizable compounds (1). (e) The above composition further containing a polymerizable compound different from the above polymerizable compound (1). (f) the above composition containing one, two, or at least three kinds of optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like Additives. (g) An AM device containing the above composition. (h) An element containing the above composition and having a TN, ECB, OCB, IPS, FFS, VA, or FPA mode. (i) a transmissive element containing the above composition. (j) The above composition is used as a composition having a nematic phase. (k) Use as an optically active composition by adding an optically active compound to the above 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 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 may contain additives, 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.

Table 2. Characteristics of the compound 1) The value of dielectric anisotropy is negative, and the sign indicates the magnitude of the absolute value.

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) 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. The compound (4) and the compound (5) are adsorbed on the surface of the substrate by the action of a polar group, and the alignment of the liquid crystal molecules is controlled. The polymer of the compound (1) is effective from the viewpoint of the alignment of the liquid crystal molecules. Compound (4) or Compound (5) is also effective. The combination of the compound (1) and the compound (4) or the compound (1) and the compound (5) is more effective. With this combination, the multiplication effect can be expected. This combination can expect better long-term stability than in the case of only the compound (4) or only the compound (5).

Third, the combination of the components in the composition, the preferred ratio of the components, and the basis thereof will be described. Preferred combinations of the components in the composition are the compound (1) + the compound (2) + the compound (3) + the compound (4), the compound (1) + the compound (2) + the compound (3) + the compound (5), Or compound (1) + compound (2) + compound (3) + compound (4) + compound (5). It is especially preferred to combine the compound (1) + the compound (2) + the compound (3) + the compound (4).

The compound (1) is added to the composition for the purpose of being suitable for a polymer stable alignment type element. In order to improve the long-term reliability of the element, a preferred ratio of the compound (1) is about 0.03% by weight or more, and a 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 2% by weight. A particularly preferred ratio is in the range of from about 0.2% by weight to about 1.0% 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 in order to increase the upper limit temperature or to lower the lower limit temperature, and a preferable ratio of the compound (3) is about 90% by weight or less in order to increase the dielectric anisotropy. A more desirable ratio is in the range of from about 15% by weight to about 75% by weight. A particularly preferred ratio is in the range of from about 15% by weight to about 60% by weight.

The compound (4) or the compound (5) is added to the composition for the purpose of controlling the alignment of the liquid crystal molecules. In order to align the liquid crystal molecules, a preferred ratio of the compound (4) or the compound (5) is about 0.05% by weight or more, and a ratio of the compound (4) or the compound (5) is preferably about 10 in order to prevent display defects of the element. Below weight%. 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.

Fourth, a preferred embodiment of the component compound will be described. In the formula (1), P ¹ , P ² and P ^{3 are} independently a polymerizable group. Preferably P ^1, P ^2, P ^3, or a group selected from formulas (P-1) polymerizable group to the group group of formula (P-5) is represented. More preferably, P ¹ , P ² or P ³ is a group represented by the formula (P-1), the formula (P-2), or the formula (P-3). Particularly preferred P ¹ , P ² or P ³ is a group represented by the formula (P-1) or the formula (P-2). The most preferred P ¹ , P ² , or P ³ is a group represented by the formula (P-1). A preferred group represented by the formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy line of the formula (P-1) to the formula (P-5) indicates the bonded portion.

In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. An alkyl group having 1 to 5 carbon atoms. Desirable M ¹ , M ² , or M ³ is hydrogen or methyl to increase reactivity. More preferably, M ¹ is hydrogen or methyl, and more preferably M ² or M ³ is hydrogen.

Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be -O-, -COO-, -OCO- in the alkylene group. 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 , Sp ² , or Sp ³ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH-, Or -CH=CH-CO-. Particularly preferred Sp ¹ , Sp ² or Sp ³ is a single bond. Here, when ring A and ring C are a phenyl group, Sp ¹ and Sp ³ are single bonds.

Ring A and Ring C are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidine-2-yl, or pyridin-2-yl, wherein at least one hydrogen in the ring may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen Substituted by a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms. Preferred ring A or ring C is 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, a 5-diyl group or a pyridine-2,5-diyl group, 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 carbon atoms, or at least A hydrogen is substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms. 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 -O-, -CO-, -COO-, or -OCO in the alkylene group. -Substitution, 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. 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, or 2. Preferably a is 0 or 1. b, c, and d are independently 0, 1, 2, 3, or 4, and the sum of b, c, and d is 1 or more. Preferred b, c, and d are 1 or 2. Wherein, when ring A and ring C are a phenyl group, a is 1 or 2. Therefore, a polymerizable compound having a biphenyl skeleton is excluded.

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

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 - fluoroheptyl, 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. 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. 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-benzene base. 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. 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.

Z ³ , Z ⁴ , and Z ^{5 are} independently a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. In order to 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 -. To reduce the viscosity, Z ⁵ is preferably a single bond for decreasing the minimum temperature, preferably Z ⁵ is -CH ₂ CH ₂ -, for increasing the maximum temperature, preferably Z ⁵ is -COO- or -OCO-.

e is 1, 2, or 3, f is 0 or 1, and the sum of e and f is 3 or less. In order to lower the viscosity, it is preferable that e is 1, and in order to increase the upper limit temperature, it is preferable that e is 2 or 3. Desirable f is 0 in order to lower the viscosity, and f is preferably 1 in order to lower the lower limit temperature. g is 1, 2, or 3. Desirable g is 1 for decreasing the viscosity, and 2 or 3 is preferred for increasing the maximum temperature.

In the formulae (4) and (5), R ⁶ is a polar group. The polar compound having a polar group is preferably stabilized because it is added to the composition. When a polar compound is added to the composition, it is preferred that the compound does not lower the voltage holding ratio of the element. The polar compound 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. The preferred polar compound does not have a polymerizable group such as an acryloxy group (-OCO-CH=CH ₂ ) or a methacryloxy group (-OCO-(CH ₃ )C=CH ₂ ).

The polar group has an interaction with a non-covalent bond of the surface of the glass substrate or the metal oxide film. Preferred polar groups have heteroatoms selected from the group of nitrogen, oxygen, sulfur, and phosphorus. Preferred polar groups have at least one or at least two of these heteroatoms. Particularly preferred polar groups are removed from compounds selected from the group consisting of alcohols, primary, secondary and tertiary amines, ketones, carboxylic acids, thiols, esters, ethers, thioethers, and combinations thereof. a monovalent group derived from hydrogen. The structure of the bases may also be linear, branched, cyclic, or a combination of these. A particularly preferred polar group has at least one of an oxygen atom of an OH structure or a nitrogen atom of a primary, secondary or tertiary amine structure. The most preferred polar group is a hydroxyl group (carbon-OH).

Examples of the polar group R ⁶ are groups represented by the formula (A1) to the formula (A4).

In the formulae (A1) to (A4), Sp ⁴ , Sp ⁶ , and Sp ^{7 are} independently a single bond or a group (-Sp''-X''-), and X'' is bonded to the MES group or R ⁵ . Sp'' is an alkylene group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 12 carbon atoms, and at least one of -CH ₂ - may be -O-, -S-, - NH-, -N(R ⁰ )-, -CO-, -CO-O-, -O-CO, -O-CO-O-, -S-CO-, -CO-S-, -N(R ⁰ )-CO-O-, -O-CO-N(R ⁰ )-, -N(R ⁰ )-CO-N(R ⁰ )-, -CH=CH-, or -C≡C-substituted, In these groups, at least one hydrogen may be substituted by fluorine, chlorine, or -CN, and X'' is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O- CO-O -, - CO- N (R 0) -, - N (R 0) -CO -, - N (R 0) -CO-N (R 0) -, - OCH 2 -, - CH 2 O -, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, - CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH- CO-O-, -O-CO-CH=CH-, or a single bond, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and Y ² and Y ^{3 are} independently hydrogen, fluorine, chlorine, Or -CN. Preferred X'' is -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -NR ⁰ -CO-NR ⁰ -, or a single bond. Sp ⁵ is >CH-, >CR ¹¹ -, >N-, or >C<. That is, Sp ⁵ in the formula (A2) is >CH-, >CR ¹¹ -, or >N-, and Sp ⁵ in the formula (A3) means >C<.

Preferred Sp'' is -(CH ₂ ) _p1 -, -(CH ₂ CH ₂ O) _q1 -CH ₂ CH ₂ -, -CH ₂ CH ₂ -S-CH ₂ CH ₂ -, or -CH ₂ CH ₂ -NHCH ₂ CH ₂ -, wherein p1 is an integer from 1 to 12, and q1 is an integer from 1 to 3. Preferred groups (-Sp''-X''-) are -(CH ₂ ) _p1 -, -(CH ₂ ) _p1 -O-, -(CH ₂ ) _p1 -O-CO-, -(CH ₂ ) _p1 -O-CO-O-, where p1 and q1 have the meanings indicated above. Particularly preferred bases Sp'' are exoethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, thiol, decyl, undecyl, and Dodecyl, octadecyl, ethyleneoxyethyl, methyleneoxybutyl, ethylene thioethyl, ethylene-N-methylimidoethyl, 1-methylalkyl , vinyl, propylene, and butenyl.

X ¹ is -NH ₂ , -NHR ¹¹ , -N(R ¹¹ ) ₂ , -OR ¹¹ , -OH, -COOH, -SH, -SR ¹¹ , Here, R ¹¹ is an alkyl group having 1 to 15 carbon atoms, and at least one of -CH ₂ - in the alkyl group may be -C≡C-, -CH=CH-, -COO-, -OCO-, -CO-, or -O-substituted, wherein at least one hydrogen may be substituted by fluorine or chlorine, and R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

X ² is -O-, -CO-, -NH-, -NR ¹¹ -, -S-, or a single bond, and Z ⁷ represents an alkylene group having 1 to 15 carbon atoms and an alicyclic ring having 5 to 6 carbon atoms. a group, or a combination of at least one ring and an alkyl group, wherein at least one hydrogen may be via -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N(R ¹¹ ) ₂ , fluorine Or a chlorine substitution, where R ¹¹ has the meaning indicated above. k is 0, 1, 2, or 3.

Particularly preferred nitrogen-containing groups R ⁶ are -NH ₂ , -NH-(CH ₂ ) _n3 H, -(CH ₂ ) _n -NH ₂ , -(CH ₂ ) _n -NH-(CH ₂ ) _n3 H, - NH-(CH ₂ ) _n -NH ₂ , -NH-(CH ₂ ) _n -NH-(CH ₂ ) _n3 H, -(CH ₂ ) _n1 -NH-(CH ₂ ) _n2 -NH ₂ , -(CH ₂ ) _n1 -NH-(CH ₂ ) _n2 -NH-(CH ₂ ) _n3 H, -O-(CH ₂ ) _n -NH ₂ , -(CH ₂ ) _n1 -O-(CH ₂ ) _n -NH ₂ , -(CH ₂ ) _n1 -NH-(CH ₂ ) _n2 -OH, -O-(CH ₂ ) _n1 -NH-(CH ₂ ) _n2 -NH ₂ , -O-(CH ₂ ) _n1 -NH-( CH ₂ ) _{n 2} —OH, or —(CH ₂ ) _{n 1} —NH—(CH ₂ ) _{n 2} —NH—(CH ₂ ) _{n 3} H, where n, n 1 , n 2 , and n 3 are independently 1 to 12 An integer, preferably 1, 2, 3, or 4.

Particularly preferred non-nitrogen-containing groups R ⁶ are -OH, -(CH ₂ ) _n -OH, -O-(CH ₂ ) _n -OH, -[O-(CH ₂ ) _n1 -] _n2 -OH, -COOH , -(CH ₂ ) _n -COOH, -O-(CH ₂ ) _n -COOH, or -[O-(CH ₂ ) _n1 -] _n2 -COOH, where n, n1, and n2 are independently 1 An integer of up to 12, preferably 1, 2, 3, or 4.

From the viewpoint of high solubility in the liquid crystal composition, R ^{6 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.

In the formula (4), the MES is a liquid crystal priming unit having at least one ring. Liquid crystal primaries are well known to those skilled in the art. The liquid crystal primordium refers to a portion which contributes to the formation of a liquid crystal phase when the compound has a liquid crystal phase (intermediate phase). A preferred example of the compound (4) is the compound (4-1).

In the formula (4-1), the ring J and the ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or carbon. a heterocyclic ring group of 4 to 25, which may be a condensed ring, wherein at least one hydrogen may be substituted by a group T, and among these groups, preferably having a carbon number of 4 to 25, these groups It may be a condensed ring in which at least one hydrogen may be substituted via a group T. The meaning of the base T is described at the end of the paragraph. Preferred ring J or ring K is 1,4-phenylene, naphthalene-1,4-diyl, or naphthalene-2,6-diyl (of the three bases, at least one tertiary carbon (> CH-) may be substituted by nitrogen (>N-), 1,4-cyclohexyl (in this group, at least one -CH ₂ - may be substituted by -O- or -S-), 3,3'-bicyclic Butylene, 1,4-cyclohexenylene, bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro ring [3.3] Heptane-2,6-diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, Indole-2,5-diyl, octahydro-4,7-methyleneindan-2,5-diyl, or perhydrocyclopenta[a]phenanthrene-3,17-diyl (especially Is a decane-3,17-diyl), wherein at least one hydrogen may be substituted via a group T, wherein the group T is -OH-, -(CH ₂ ) _j -OH, halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ⁰ ) ₂ , -C(=O)R ⁰ , -N(R ⁰ ) ₂ , -(CH _{2 j} -N(R ⁰ ) ₂ , an aryl or heteroaryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 25 carbon atoms, an alkoxy group, an alkylcarbonyl group having 2 to 25 carbon atoms, an alkoxycarbonyl group An alkylcarbonyloxy group or an alkoxycarbonyloxy group, wherein at least one of the hydrogen groups is Or chlorine, where, R ⁰ is hydrogen or alkyl of 1 to 12 carbon atoms, j is 2, 3, or 4.

Z ⁶ is a single bond, -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _j -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _j -, -CH=CH-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or -C(R ⁰ ) ₂ -. R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, j is 2, 3, or 4. Preferred Z ⁶ is a single bond.

R ⁶ is an alkyl group having 1 to 25 carbon atoms, and at least one of -CH ₂ - may be via -NR ⁰ -, -O-, -S-, -CO-, -COO-, -OCO- , -OCOO-, or a cycloalkyl group having a carbon number of 3 to 8, wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and at least one tertiary carbon (>CH-) may be nitrogen (> N-) is substituted, and at least one hydrogen may be substituted by fluorine or chlorine, wherein R ⁶ has at least one of an oxygen atom of an OH structure, a sulfur atom of an SH structure, and a nitrogen atom of a primary, secondary or tertiary amine structure. One. Preferably R ⁶ has at least one of >NH, -OH, or -SH. R ⁷ is hydrogen, halogen, alkyl having 1 to 25 carbon atoms, and at least one of -CH ₂ - may be via -NR ⁰ -, -O-, -S-, -CO-, -CO- O-, -O-CO-, -O-CO-O-, or a cycloalkyl group having a carbon number of 3 to 8, and at least one tertiary carbon (>CH-) may be nitrogen (>N-) Alternatively, in the group, at least one hydrogen may be substituted by fluorine or chlorine, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms. Preferred R ⁷ is an alkyl group.

The aromatic group means an aryl group or a substituted aryl group. Heteroaromatic group means a heteroaryl group or a substituted heteroaryl group. Heteroaryl refers to an aromatic group having at least one hetero atom. The aryl and heteroaryl groups may be either monocyclic or polycyclic. That is, the groups have at least one ring which can be condensed (for example, naphthyl), the two rings can be linked by a covalent bond (for example, a biphenyl group), or can have a combination of a condensed ring and a linked ring. . Preferred heteroaryl groups have at least one hetero atom selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus.

Preferred aryl or heteroaryl groups have a carbon number of from 6 to 25 and may also be a five membered ring, a six membered ring, or a seven membered ring. Preferred aryl or heteroaryl groups may be monocyclic or bicyclic or tricyclic. These groups may be condensed rings or substituted.

Preferred aryl groups are derived from benzene, biphenyl, terphenyl, [1,1':3',1''] terphenyl, naphthalene, anthracene, binaphthyl, phenanthrene, anthracene, indoline, A monovalent group derived by removing one hydrogen from hydrazine, hydrazine, fused tetraphenyl, pentacene, benzopyrene, hydrazine, hydrazine, hydrazine, and hydrazine.

Preferred heteroaryl groups are derived from pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, metabolite Oxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4- a five-membered ring compound such as oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, or Pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1, A monovalent group derived by removing one hydrogen from a six-membered ring compound such as 2,3,4-tetrazine or 1,2,3,5-tetrazine.

Preferred heteroaryl groups are also derived from oxime, isoindole, pyridazine, oxazole, benzimidazole, benzotriazole, indole, naphthimidazole, phenamimidazole, pyridoimidazole, pyrazine Imidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthraquinone, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran , quinoline, isoquinoline, acridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzisoquinoline, acridine, Phthathiazine, phenoloxazine, benzoxazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzoporphyrin, phenanthridine, phenanthroline, thieno[2,3b] A monovalent group derived by removing one hydrogen from a condensed ring compound such as thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene or benzothiadiazolethiophene. Preferred heteroaryl groups are also monovalent groups derived by removing one hydrogen from a ring formed by combining two groups selected from the five-membered ring, the six-membered ring, and the condensed ring. The heteroaryl groups can be substituted with alkyl, alkoxy, thioalkyl, fluoro, fluoroalkyl, aryl, or heteroaryl groups.

The alicyclic and heteroalicyclic groups may be saturated or unsaturated. That is, the groups may have only a single bond, or may have a combination of a single bond and a multiple bond. A saturated ring is preferred over an unsaturated ring. Preferred heteroalicyclic groups have at least one hetero atom selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus.

The alicyclic group and the heteroalicyclic group may be one ring or a plurality of rings. Preferred examples of the groups are monocyclic, bicyclic or tricyclic rings having a carbon number of 3 to 25, and these groups may be a condensed ring or may be substituted. Preferred examples of such groups are a five-membered ring, a six-membered ring, a seven-membered ring, or an eight-membered ring, wherein at least one carbon may be substituted by deuterium, and at least one >CH- may be substituted by >N-, Moreover, at least one -CH ₂ - may be substituted with -O- or -S-.

Preferred alicyclic and heteroalicyclic groups are by a five-membered ring such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran or pyrrolidine, cyclohexane, cyclohexene, tetrahydropyran, tetra a six-membered ring such as hydrogen thiopyran, 1,3-dioxane, 1,3-dithiane or piperidine, a seven-membered ring such as cycloheptane, tetrahydronaphthalene, decahydronaphthalene, indane, and bicyclo [ 1.1.1] a divalent group derived by removing two hydrogens in a condensed ring such as pentane, bicyclo[2.2.2]octane, spiro[3.3]heptane or octahydro-4,7-methylene indan .

i is 0, 1, 2, 3, 4, or 5.

In the formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ - in the alkyl group may be -CH=CH-, -CF=CH-, -CH=CF-, -C≡C-, or a cycloalkyl group having a carbon number of 3 to 8, and at least one hydrogen may be substituted by fluorine or chlorine. h is 1 or 2, preferably 1.

Desirable R ⁵ is an alkyl group having 4 to 20 carbon atoms. More preferably, R ⁵ is an alkyl group having 6 to 18 carbon atoms. At least one -CH ₂ - may be substituted with -CH=CH-, -CF=CH-, -CH=CF-, -C≡C-, or -O-, and at least one hydrogen may be substituted with fluorine or chlorine.

Particularly preferred compound (4-1) is selected from the following compounds.

In the formula (4-1-1-1) to the formula (4-1-4-4), R ⁷ is an alkyl group having 1 to 8 carbon atoms or fluorine.

Particularly preferred compound (5-1) is selected from the following compounds (5-1-1-1) to (5-1-29-1).

Fifth, a preferred component compound is shown. Desirable compound (1) is the compound (1-1) to the compound (1-12) according to item 3. Among these compounds, at least one of the first additives is preferably the compound (1-7), the compound (1-8), the compound (1-9), or the compound (1-10). It is preferred that at least two of the first additives are a combination of the compound (1-8) and the compound (1-9), or the compound (1-2) and the compound (1-7).

Desirable compound (2) is the compound (2-1) to the compound (2-21) according to item 6. Among these compounds, at least one of the first components is preferably a compound (2-1), a compound (2-4), a compound (2-5), a compound (2-7), and a compound (2-10). Or compound (2-15). Preferably, at least two of the first components are the compound (2-1) and the compound (2-7), the compound (2-1) and the compound (2-15), the compound (2-4), and the compound (2- 7), a combination of the compound (2-4) and the compound (2-15), or the compound (2-5) and the compound (2-10).

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), and compound (3-7). Or compound (3-8). Preferably, at least two of the second components are the compound (3-1) and the compound (3-3), the compound (3-1) and the compound (3-5), or the compound (3-1) and the compound (3). -6) combination.

Desirable compound (4) is the compound (4-1) according to item 13. Particularly preferred compound (4) is the compound (4-1-1) to the compound (4-1-4) according to item 16. Desirable compound (5) is the compound (5-1) according to item 14. Particularly preferred compound (5) is the compound (5-1-1) to the compound (5-1-29) according to item 17. In general, the compound (4) is superior to the compound (5).

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 imparting a helical structure of the liquid crystal molecules to impart a torsion angle. Examples of such a compound are the compound (6-1) to the compound (6-5). 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 (7) wherein n is an integer of 1 to 9.

In the compound (7), preferred n is 1, 3, 5, 7, or 9. The better n is 7. Since the compound (7) 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 effects, 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 minimum 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 above effects, a preferred ratio of the absorbents or stabilizers is about 50 ppm or more, and in order not to lower the upper limit temperature or to increase the minimum temperature, a preferred ratio of the absorbents or stabilizers is about 10,000 ppm. the following. 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 effects, 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) is suitable for this purpose. The compound (1) and another polymerizable compound different from the compound (1) may be added to the composition. Preferred examples of the other polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone, etc. Compound. A preferred example is acrylate or methacrylate. A preferred ratio of the compound (1) 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 of the polymerizable compound or the pretilt angle of the liquid crystal molecules can be adjusted by changing the kind of the compound (1) or by combining the other polymerizable compound with the compound (1) at an appropriate ratio. 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 such as the compound (1) 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) as a photoinitiator is suitable for 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 a polymerizable compound such as the compound (1) 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.

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 compound (1-2) is synthesized by the method described in JP-A-7-101900. 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 (4-1) was synthesized by the method described in International Publication No. 2012-038026. A part of the compound (5) is commercially available. A compound of formula (7) wherein n is 1 is available from Sigma-Aldrich Corporation. The compound (7) 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 above manner 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 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 polymerization in which a three-dimensional network polymer is formed in the composition. Component of polymer dispersed (PD) type.

An example of a method of producing a conventional polymer stable alignment type element is as follows. An element including two substrates, which are referred to as an array substrate and a color filter substrate, is assembled. 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.

An example of a method of producing an element having no alignment film is as follows. An element including two substrates, which are referred to as an array substrate and a color filter substrate, is prepared. The substrate does not have 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 and a polar compound are 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. By this polymerization, a layer containing a composition of a polymer and a polar compound is formed on a substrate.

In this sequence, the polar compound 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 a voltage is applied, the alignment of the liquid crystal molecules is further promoted, and the polymerizable compound is also aligned according to the alignment. 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 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 invention comprises a mixture of composition M1 and 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 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), which are reviewed by the Japan Electronics and Information Technology Industries Association (JEITA), or modified. 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): A sample having a nematic phase is placed in a glass bottle at 0 ° C, -10 ° C, -20 ° C, -30 ° C, and -40 ° C. After storage in a freezer for 10 days, 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, TC 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 device in which the interval (cell gap) of two glass substrates was 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 applying a voltage for 0.2 seconds, the voltage was repeatedly applied with a condition of applying 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 octadecyltriethoxydecane (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 device having a gap (cell gap) of 2 glass substrates of 4 μm, and the device was sealed with 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 长 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 by 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 device 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, and the cell gap was 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 two glass substrates was 3.5 μm and the alignment film was not provided. The element is sealed using an adhesive that hardens with 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: spray elastic constant, K33: bend elastic constant; measured at 25 ° C; pN): EC-manufactured by Toyo Corporation (TOYO Corporation) Co., Ltd. Type 1 elastic constant tester. A sample was injected into a vertical alignment element having a spacing (cell gap) of 20 glass substrates 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) × (electric capacity of the container)} / {(direct current) × (dielectric constant of vacuum)}.

(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. Bryant, and JJ Hilfiker, 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.

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. Finally, the characteristic values of the composition are summarized.

EXAMPLES OF ELEMENTS 1. Raw materials An element having no alignment film was produced to investigate the vertical alignment of liquid crystal molecules, the conversion ratio of a polymerizable compound, and the response time. First, the raw materials will be explained. The raw materials are a liquid crystal composition (M1) to a liquid crystal composition (M15), a polymerizable compound (RM-1) to a polymerizable compound (RM-8), a polar compound (PC-1) to a polar compound (PC-33), And according to the sequence.

[Composition M1] 3-HB(2F,3F)-O2 (2-1) 10% 5-HB(2F,3F)-O2 (2-1) 7% 2-BB(2F,3F)-O2 ( 2-5) 7% 3-BB(2F,3F)-O2 (2-5) 7% 3-B(2F,3F)B(2F,3F)-O2 (2-6) 3% 2-HHB( 2F,3F)-O2 (2-7) 5% 3-HHB(2F,3F)-O2 (2-7) 10% 2-HBB(2F,3F)-O2 (2-15) 8% 3-HBB (2F,3F)-O2 (2-15) 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; Δε=-4.0; Vth=2.18 V; η=22.6 mPa·s.

[Composition M2] 3-HB(2F,3F)-O4 (2-1) 6% 3-H2B(2F,3F)-O2 (2-3) 8% 3-H1OB(2F,3F)-O2 ( 2-4) 4% 3-BB(2F,3F)-O2 (2-5) 7% 2-HHB(2F,3F)-O2 (2-7) 7% 3-HHB(2F,3F)-O2 (2-7) 7% 3-HH2B(2F,3F)-O2 (2-9) 7% 5-HH2B(2F,3F)-O2 (2-9) 4% 2-HBB(2F,3F)- O2 (2-15) 5% 3-HBB(2F,3F)-O2 (2-15) 5% 4-HBB(2F,3F)-O2 (2-15) 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 ( 2-5) 8% 3-HHB(2F,3F)-O2 (2-7) 5% 5-HHB(2F,3F)-O2 (2-7) 4% 3-HH1OB(2F,3F)-O2 (2-10) 4% 2-BB(2F,3F)B-3 (2-11) 5% 2-HBB(2F,3F)-O2 (2-15) 3% 3-HBB(2F,3F) -O2 (2-15) 8% 4-HBB(2F,3F)-O2 (2-15) 5% 5-HBB(2F,3F)-O2 (2-15) 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; Δ ε = -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 ( 2-3) 8% 5-H2B(2F,3F)-O2 (2-3) 8% 3-HDhB(2F,3F)-O2 (2-13) 5% 2-HBB(2F,3F)-O2 (2-15) 6% 3-HBB(2F,3F)-O2 (2-15) 8% 4-HBB(2F,3F)-O2 (2-15) 7% 5-HBB(2F,3F)- O2 (2-15) 7% 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 ( 2-3) 8% 3-BB(2F,3F)-O2 (2-5) 10% 2-HHB(2F,3F)-O2 (2-7) 4% 3-HHB(2F,3F)-O2 (2-7) 7% 3-HHB(2F,3F)-1 (2-7) 6% 3-HDhB(2F,3F)-O2 (2-13) 5% 2-HBB(2F,3F)- O2 (2-15) 6% 3-HBB(2F,3F)-O2 (2-15) 6% 4-HBB(2F,3F)-O2 (2-15) 5% 5-HBB(2F,3F) -O2 (2-15) 4% 3-HEB(2F,3F)B(2F,3F)-O2 (2-17) 3% 3-H1OCro(7F,8F)-5 (2-20) 3% 3 -HH-O1 (3-1) 5% 1-BB-5 (3-3) 4% V-HHB-1 (3-5) 4% 5-HBBH-3 (3-11) 5% NI=81.5°C; Tc<-30°C; Δn=0.119; Δε=-4.5; Vth=1.70 V ;η=31.8 mPa·s.

[Composition M6] 3-HB(2F,3F)-O4 (2-1) 15% 3-chB(2F,3F)-O2 (2-2) 7% 2-HchB(2F,3F)-O2 ( 2-8) 8% 3-HBB(2F,3F)-O2 (2-15) 8% 4-HBB(2F,3F)-O2 (2-15) 5% 5-HBB(2F,3F)-O2 (2-15) 7% 3-dhBB(2F,3F)-O2 (2-16) 5% 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; Δε=-3.2; Vth=2.47 V; η=23.9 mPa·s.

[Composition M7] 3-H2B(2F,3F)-O2 (2-3) 18% 5-H2B(2F,3F)-O2 (2-3) 17% 3-DhHB(2F,3F)-O2 ( 2-12) 5% 3-HHB(2F,3CL)-O2 (2-18) 5% 3-HBB(2F,3CL)-O2 (2-19) 8% 5-HBB(2F,3CL)-O2 (2-19) 7% 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-HHEBH-3 (3-9) 4% 3-HB(F)HH-2 (3-10) 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 (2-3) 10% 3-BB(2F,3F)-O2 ( 2-5) 10% 2O-BB(2F,3F)-O2 (2-5) 3% 2-HHB(2F,3F)-O2 (2-7) 4% 3-HHB(2F,3F)-O2 (2-7) 7% 2-HHB(2F,3F)-1 (2-7) 5% 2-BB(2F,3F)B-3 (2-11) 6% 2-BB(2F,3F) B-4 (2-11) 6% 3-HDhB(2F,3F)-O2 (2-13) 6% 2-HBB(2F,3F)-O2 (2-15) 4% 3-HBB(2F, 3F)-O2 (2-15) 7% 3-dhBB(2F,3F)-O2 (2-16) 4% 3-HH1OCro(7F,8F)-5 (2-21) 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 (2-4) 3% 3-BB(2F,3F)-O2 ( 2-5) 10% 2-HHB(2F,3F)-O2 (2-7) 7% 3-HHB(2F,3F)-O2 (2-7) 7% 3-HH1OB(2F,3F)-O2 (2-10) 6% 2-HBB(2F,3F)-O2 (2-15) 4% 3-HBB(2F,3F)-O2 (2-15) 6% 4-HBB(2F,3F)- O2 (2-15) 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; Δε=-4.0; Vth=2.27 V; η=29.6 mPa·s.

[Composition M10] 3-HB(2F,3F)-O4 (2-1) 6% 3-H2B(2F,3F)-O2 (2-3) 8% 3-H1OB(2F,3F)-O2 ( 2-4) 5% 3-BB(2F,3F)-O2 (2-5) 10% 2-HHB(2F,3F)-O2 (2-7) 7% 3-HHB(2F,3F)-O2 (2-7) 7% 5-HHB(2F,3F)-O2 (2-7) 7% 2-HBB(2F,3F)-O2 (2-15) 4% 3-HBB(2F,3F)- O2 (2-15) 7% 5-HBB(2F,3F)-O2 (2-15) 6% 3-HH-V (3-1) 11% 1-BB-3 (3-3) 6% 3 -HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 4% 3-B(F)BB-2 (3-7) 4% NI = 87.6 ℃; Tc <-30 ℃; Δn = 0.126; Δε = -4.5; Vth = 2.21 V; η = 25.3 mPa · s.

[Composition M11] 3-HB(2F,3F)-O4 (2-1) 6% 3-H2B(2F,3F)-O2 (2-3) 8% 3-H1OB(2F,3F)-O2 ( 2-4) 4% 3-BB(2F,3F)-O2 (2-5) 7% 2-HHB(2F,3F)-O2 (2-7) 6% 3-HHB(2F,3F)-O2 (2-7) 10% 5-HHB(2F,3F)-O2 (2-7) 8% 2-HBB(2F,3F)-O2 (2-15) 5% 3-HBB(2F,3F)- O2 (2-15) 7% 5-HBB(2F,3F)-O2 (2-15) 5% 2-HH-3 (3-1) 12% 1-BB-3 (3-3) 6% 3 -HHB-1 (3-5) 3% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 6% 3-B(F)BB-2 (3-7) 3% NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.124; Δε = -4.5; Vth = 2.22 V; η = 25.0 mPa · s.

[Composition M12] 3-HB(2F,3F)-O2 (2-1) 7% 5-HB(2F,3F)-O2 (2-1) 7% 3-BB(2F,3F)-O2 ( 2-5) 8% 3-HHB(2F,3F)-O2 (2-7) 4% 5-HHB(2F,3F)-O2 (2-7) 5% 3-HH1OB(2F,3F)-O2 (2-10) 5% 2-BB(2F,3F)B-3 (2-11) 4% 2-HBB(2F,3F)-O2 (2-15) 3% 3-HBB(2F,3F) -O2 (2-15) 8% 4-HBB(2F,3F)-O2 (2-15) 5% 5-HBB(2F,3F)-O2 (2-15) 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 (2-4) 6% 3-H1OB(2F,3F)-O2 (2-4) 4% 3-BB(2F,3F)-O2 ( 2-5) 3% 2-HH1OB(2F,3F)-O2 (2-10) 14% 2-HBB(2F,3F)-O2 (2-15) 7% 3-HBB(2F,3F)-O2 (2-15) 11% 5-HBB(2F,3F)-O2 (2-15) 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; Δε =-3.2; Vth = 2.17 V; η = 17.7 mPa·s.

[Composition M14] 3-HB(2F,3F)-O2 (2-1) 5% 5-HB(2F,3F)-O2 (2-1) 7% 3-BB(2F,3F)-O2 ( 2-5) 8% 3-HHB(2F,3F)-O2 (2-7) 5% 5-HHB(2F,3F)-O2 (2-7) 4% 3-HH1OB(2F,3F)-O2 (2-10) 5% 2-BB(2F,3F)B-3 (2-11) 4% 2-HBB(2F,3F)-O2 (2-15) 3% 3-HBB(2F,3F) -O2 (2-15) 9% 4-HBB(2F,3F)-O2 (2-15) 4% 5-HBB(2F,3F)-O2 (2-15) 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 (2-3) 7% 3-HHB(2F,3F)-O2 (2-7) 8% 2-HchB(2F,3F)-O2 ( 2-8) 8% 3-HH1OB(2F,3F)-O2 (2-10) 5% 2-BB(2F,3F)B-3 (2-11) 7% 2-BB(2F,3F)B -4 (2-11) 7% 3-HDhB(2F,3F)-O2 (2-13) 3% 3-DhH1OB(2F,3F)-O2 (2-14) 4% 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=88.3°C; Tc<-30°C; Δn=0.115; Δε=-2.0; Vth=2.80 V; η=17.8 mPa・s.

The following polymerizable compound (RM-1) to polymerizable compound (RM-8) was used as the first additive.

The following polar compound (PC-1) to polar compound (PC-33) was used as the second additive.

2. Vertical alignment of liquid crystal molecules Test No. 1 The polymerizable compound (RM-1) was added to the composition (M1) at a ratio of 0.5% by weight and a polar compound (PC-1) 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 polymerizable compound 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 in parallel, and the element was irradiated with light from below to observe the presence or absence of light leakage. When the liquid crystal molecules are sufficiently aligned and the light does not pass through the element, the vertical alignment is judged to be "good". When the light transmitted through the element is observed, it is expressed as "poor".

Test No. 2 to Test No. 33 An element having no alignment film was produced by using a mixture of a composition, a polymerizable compound, and a polar compound. The presence or absence of light leakage was observed in the same manner as in Test No. 1. The results are summarized in Table 4.

Table 4. Vertical alignment of liquid crystal molecules

3. Conversion Ratio of Polymerizable Compound A polar compound is added to the composition together with the polymerizable compound. The polymerizable compound is consumed by polymerization to form a polymer. The conversion rate of the reaction is preferably large. This is because the residual amount of the polymerizable compound (the amount of the unreacted polymerizable compound) is preferably small from the viewpoint of the image afterimage. In the case of producing a polymer-stabilized alignment type element, ultraviolet rays are usually irradiated in two stages for the purpose of optimizing the pretilt angle of liquid crystal molecules. In the next test, after the ultraviolet rays of the first stage were irradiated, the residual amount of the polymerizable compound was measured, and the conversion ratio was calculated. For comparison, the following polymerizable compound (RM-9) was selected. This compound is excluded from the compound (1) by the definition of the symbol.

The polymerization was carried out in the following manner. An element having no alignment film was produced by the method described in the paragraph "Vertical alignment of liquid crystal molecules". While applying a voltage of 30 V to the device, ultraviolet rays of 78 mW/cm ² (405 nm) were irradiated for 359 seconds (28 J). A multi-metal lamp M04-L41 for ultraviolet curing manufactured by EYE GRAPHICS Co., Ltd. was used for the irradiation of ultraviolet rays. Then, the residual amount of the polymerizable compound was measured by HPLC, and the conversion rate was calculated. The results are summarized in Table 5. The conversion of Test No. 1 to Test No. 8 was in the range of 34% to 44%. In Comparative Example 1, the polymerizable compound (RM-1) used in Test No. 1 was replaced with a polymerizable compound (RM-9) to carry out polymerization. In this case, the conversion rate was 16%. From this comparison, it can be concluded that the composition of the present invention is excellent in terms of conversion.

Table 5. Conversion of polymerizable compounds

4. Response time As described in Table 6, a mixture prepared by combining various compositions, a polymerizable compound, and a polar compound was injected into an element having no alignment film. According to the above item (12), the polymerizable compound was polymerized by irradiation of ultraviolet rays, and the response time of the element was measured. For comparison, an element was produced from the composition (M5) or the composition (M9) in a state in which the polymerizable compound and the polar compound were not added, and the response time was measured in the same manner. As is known from Table 6, in Test No. 1 to Test No. 33, the response time was in the range of 5.2 msec to 10.4 msec. On the other hand, the response times of Comparison 1 and Comparison 2 are 21.8 milliseconds and 21.7 milliseconds, respectively. That is, when the polymerizable compound and the polar compound were not added, the response time was about 2 times. Therefore, it can be concluded that the combination of the polymer derived from the polymerizable compound (1) and the polar compound (4) or the polar compound (5) is effective in shortening the response time.

Table 6. Response time

In the liquid crystal display element, the response time is preferably short. The response time of the embodiment shown in Table 6 is in the range of 5.2 milliseconds to 10.4 milliseconds, which is shorter than the comparative example. As a result, since a liquid crystal composition containing a polymerizable compound and a polar compound was used, an element having no alignment film achieved a short response time regardless of the type of each component. This is because even if there is no alignment film, the liquid crystal molecules are stably aligned, which is a feature of the present invention which should be specifically described. [Industrial availability]

The liquid crystal composition of the present invention can control the alignment of liquid crystal molecules in an element having no alignment film. The composition has a high upper limit temperature, a low lower limit temperature, a small viscosity, a suitable optical anisotropy, a negative large dielectric anisotropy, a large specific resistance, a high stability against ultraviolet rays, and a heat. Among the characteristics such as high stability, at least one characteristic is satisfied, or an appropriate balance is satisfied with respect to at least two characteristics. The liquid crystal display element containing the composition has characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life, and thus can be used for a liquid crystal projector, a liquid crystal television, or the like.

no

Claims (25)

A liquid crystal composition containing at least one polymerizable compound selected from the group consisting of compounds represented by formula (1) as a first additive, containing at least one polar compound as a second 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 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. a group, or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; ring B is a 1,4-cyclohexylene group, a 1,4-cyclohexene group, a 1,4-phenylene group , naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in which at least one hydrogen can pass fluorine, chlorine , an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or at least one hydrogen substituted with a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms; Z ¹ and Z ^{2 are} independently a single bond or a C 1-10 alkylene group, said alkylene, at least one -CH ₂ - may be -O - -OCO- substituted -COO-, or, moreover, at least a -, - CO -, -CH ₂ -CH ₂ - may be -CH = CH -, - C ( CH 3) = CH -, - CH = C (CH 3) -, or _{-C (CH 3) = C (} CH 3) - substituted In the group, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; and Sp ¹ , Sp ² , and Sp ^{3 are} independently a single bond or a carbon number of 1 to 10 The alkylene group, wherein at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - Substituted by -CH=CH- or -C≡C-, at least one of the hydrogens may be substituted by fluorine or chlorine; a is 0, 1, or 2; b, c, and d are independently 0, 1 2, 3, or 4; wherein, when ring A and ring C are phenyl groups, a is 1 or 2, and when a is 1, Sp ¹ and Sp ³ are single bonds. The liquid crystal composition according to claim 1, wherein, in the formula (1), P ¹ , P ² and P ^{3 are} independently selected from the group consisting of the formula (P-1) to the formula (P-5). The polymerizable group in the group of the indicated groups, In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen substituted by fluorine or chlorine. An alkyl group having 1 to 5 carbon atoms. The liquid crystal composition according to claim 1, wherein the first additive is at least one polymerizable compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-12). , In the formulae (1-1) to (1-12), P ¹ , P ² , and P ^{3 are} independently a group selected from the group represented by the formula (P-1) to the formula (P-3). a polymerizable group, wherein 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 substituted with at least one hydrogen via fluorine or chlorine. base; 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 in the alkylene group. -, 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 1, wherein the ratio of the first additive is in the range of 0.03 wt% to 10 wt% 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 ¹ and R ^{2 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 alkene having 2 to 12 carbon atoms. Oxyl; ring D and ring F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen substituted by fluorine or chlorine 1,4- Phenyl, or tetrahydropyran-2,5-diyl; ring E is 2,3-difluoro-1,4-phenyl, 2-chloro-3-fluoro-1,4-phenyl , 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-; e is 1, 2 Or 3, f is 0 or 1, and the sum of e and f 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 (2-21) as a first component, In the formulae (2-1) to (2-21), R ¹ and R ^{2 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 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, 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-;g 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, In the formulae (3-1) to (3-13), 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. 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 8, wherein the ratio of the second 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, wherein the second additive is a polar compound containing a polar group having a hetero atom selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus. The liquid crystal composition according to claim 11, which contains at least one polar compound selected from the group consisting of compounds represented by formula (4) and formula (5) as a second additive, In the formula (4), the MES is a liquid crystal primor having at least one ring; in the formula (5), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ - through the alkyl group may be - CH=CH-, -CF=CH-, -CH=CF-, -C≡C-, or a cycloalkyl group having a carbon number of 3 to 8, in which at least one hydrogen may be substituted by fluorine or chlorine In the formulae (4) and (5), R ⁶ is a polar group having at least one of an oxygen atom having an OH structure, a sulfur atom of an SH structure, and a nitrogen atom of a primary, secondary or tertiary amine structure; It is 1 or 2. The liquid crystal composition according to claim 12, which contains at least one compound selected from the group consisting of compounds represented by formula (4-1) as a second additive, In the formula (4-1), the ring J and the ring K are independently an aromatic group having 6 to 25 carbon atoms, a heteroaromatic group having 5 to 25 carbon atoms, an alicyclic group having 3 to 25 carbon atoms, or carbon. a heterocyclic ring group of 4 to 25, which may be a condensed ring, wherein at least one hydrogen may be substituted via a group T, wherein the group T is -OH, -(CH ₂ ) _j -OH , halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ⁰ ) ₂ , -C(=O)R ⁰ , -N(R ⁰ ) ₂ , -(CH ₂ ) _j -N(R ⁰ ) ₂ , an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms, an alkyl group having 1 to 25 carbon atoms, and a carbon number of 1 to 25 Alkoxy group, alkylcarbonyl group having 2 to 25 carbon atoms, alkoxycarbonyl group having 2 to 25 carbon atoms, alkylcarbonyloxy group having 2 to 25 carbon atoms, or alkoxycarbonyloxy group having 2 to 25 carbon atoms In the group, at least one hydrogen may be substituted by fluorine or chlorine, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, j is 1, 2, 3, or 4; and Z ⁶ is -O- , -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, - CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -(CH ₂ ) _j -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -(CF ₂ ) _j - , -CH=CH-, -CF=CF-, -C≡C-, -C H=CH-COO-, -OCO-CH=CH-, -C(R ⁰ ) ₂ , or a single bond, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and j is 1, 2 3 or 4; R ⁶ is an alkyl group having 1 to 25 carbon atoms, and at least one of -CH ₂ - may be via -NR ⁰ -, -O-, -S-, -CO-, -COO -, -OCO-, -OCOO-, or a cycloalkyl group having a carbon number of 3 to 8, wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, and at least one tertiary carbon (>CH-) It may be substituted by nitrogen (>N-), and at least one hydrogen may be substituted by fluorine or chlorine, wherein R ⁶ has an oxygen atom of an OH structure, a sulfur atom of an SH structure, or a primary, secondary or tertiary amine structure. At least one of nitrogen atoms; R ⁷ is hydrogen, halogen, alkyl having 1 to 25 carbon atoms, and at least one of -CH ₂ - may be via -NR ⁰ -, -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, or a cycloalkyl group having a carbon number of 3 to 8, and at least one tertiary carbon (>CH-) Substituted by nitrogen (>N-), at least one of the hydrogens may be substituted by fluorine or chlorine, where R ⁰ is hydrogen or an alkyl group having 1 to 12 carbons; i is 0, 1, 2, 3 , 4, or 5. The liquid crystal composition according to claim 12, which contains at least one polar compound selected from the group consisting of compounds represented by formula (5-1) as a second additive, In the formula (5-1), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and at least one of -CH ₂ - in the alkyl group may be -CH=CH-, -CF=CH-, -CH=CF -, -C≡C-, or a cycloalkyl group having a carbon number of 3 to 8, wherein at least one hydrogen may be substituted by fluorine or chlorine; and R ⁶ is an alkyl group having 1 to 25 carbons, In the alkyl group, at least one -CH ₂ - may be through -NR ⁰ -, -O-, -S-, -CO-, -COO-, -OCO-, -OCOO-, or a carbon number of 3 to 8 Alkyl substituted, wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, at least one tertiary carbon (>CH-) may be substituted by nitrogen (>N-), and at least one hydrogen may also be fluorine Or a chlorine substitution, wherein R ⁶ has at least one of an oxygen atom of an OH structure, a sulfur atom of an SH structure, or a nitrogen atom of a primary, secondary or tertiary amine structure. The liquid crystal composition according to claim 12, wherein, in the formulas (4) and (5) described in claim 12, R ⁶ is a formula (A1) to (A4). Any of the indicated bases, In the formulae (A1) to (A4), Sp ⁴ , Sp ⁶ , and Sp ^{7 are} independently a single bond or a group (-Sp''-X''-), where Sp'' is a carbon number of 1 to An alkylene group of 20, wherein at least one -CH ₂ - may be via -O-, -S-, -NH-, -N(R ⁰ )-, -CO-, -CO-O- , -O-CO, -O-CO-O-, -S-CO-, -CO-S-, -N(R ⁰ )-CO-O-, -O-CO-N(R ⁰ )-, -N(R ⁰ )-CO-N(R ⁰ )-, -CH=CH-, or -C≡C-substituted, wherein at least one hydrogen may be substituted by fluorine, chlorine, or -CN, and , X'' is -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O-, -CO-N(R ⁰ )-, -N( R ⁰ )-CO-, -N(R ⁰ )-CO-N(R ⁰ )-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O- , -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=N-, -N=CH-, -N=N-, -CH=CR ⁰ -, -CY ² =CY ³ -, -C≡C-, -CH=CH-CO-O-, -O-CO-CH=CH-, or single bond Here, R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms, Y ² and Y ^{3 are} independently hydrogen, fluorine, chlorine, or -CN; and Sp ⁵ is >CH-, >CR ¹¹ -, >N -, or >C<; X ¹ is -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -N(R ¹¹ ) ₂ , -SH, -SR ¹¹ , Wherein R ⁰ is hydrogen or an alkyl group having 1 to 12 carbon atoms; X ² is -O-, -CO-, -NH-, -NR ¹¹ -, -S-, or a single bond; Z ⁷ is carbon An alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 or 6 carbon atoms, or a combination thereof, wherein at least one hydrogen of the groups may be via -OH, -OR ¹¹ , -COOH, -NH ₂ , ^{-NHR 11, -N (R 11)} 2, fluorine, or chlorine; R ¹¹ is an alkyl group having 1 to 15 carbons, in the alkyl group, at least one -CH ₂ - may be -C≡C-, -CH=CH-, -COO-, -OCO-, -CO-, or -O-, in which at least one hydrogen may be substituted by fluorine or chlorine; ring L is an aromatic having 6 to 25 carbons Or an alicyclic group having 3 to 25 carbon atoms, which may be a condensed ring, wherein one to three hydrogens may be substituted by R ^L ; R ^L is -OH, -(CH ₂ ) _j -OH, fluorine, chlorine, -CN, -NO ₂ , -NCO, -NCS, -OCN, -SCN, -C(=O)N(R ⁰ ) ₂ , -C(=O)R ⁰ , -N (R ⁰ ) ₂ , —(CH ₂ ) _j —N (R ⁰ ) ₂ , —SH, —SR ⁰ , an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms, and a carbon number of 1 to 25 alkyl, carbon 1 to 25 alkoxy, carbon 2 to 25 alkylcarbonyl, carbon 2 to 25 alkoxycarbonyl, carbon 2 to 25 alkylcarbonyloxy, Carbon atoms, an alkoxycarbonyl group having 2 to 25, the plurality of groups, at least one hydrogen may be replaced by fluorine or chlorine, where, R ⁰ is hydrogen or alkyl of 1 to 12 carbon atoms, j is 1, 2 , 3, or 4; k is 0, 1, 2, or 3; m is 2, 3, 4, or 5. The liquid crystal composition according to claim 13, wherein the second additive is at least one selected from the group consisting of compounds represented by formula (4-1-1) to formula (4-1-4). a compound, In the formula (4-1-1) and the formula (4-1-4), the ring J and the ring K are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4. -phenyl, 2-fluoro-1,3-phenylene, 2-ethyl-1,4-phenylene, 2,6-diethyl-1,4-phenylene, 2-trifluoro Methyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1, 4-phenylene, or 2,3,5,6-tetrafluoro-1,4-phenylene; ring L is cyclohexyl or phenyl; Z ⁶ is a single bond, an extended ethyl group, or a carbonyloxy group; Z ⁷ is a single bond, an alkylene group having 1 to 15 carbon atoms, an alicyclic group having 5 or 6 carbon atoms, or a combination thereof, wherein at least one hydrogen in the group may be -OH, -OR ¹¹ , -COOH, -NH ₂ , -NHR ¹¹ , -NR ¹¹ ₂ , or halogen substitution, R ¹¹ is an alkyl group having 1 to 15 carbon atoms or a halogenated alkyl group, of which at least one -CH ₂ - Substituted by -C≡C-, -CH=CH-, -COO-, -OCO-, -CO-, -O-, or -NH-; Sp ⁴ is a single bond, an extended ethyl group, a propyl group, or a methylene group, Sp ⁷ is a single bond, or alkylene group having a carbon number of 1 to 5, in the alkylene, -CH ₂ - may be substituted by -O- or -NH-; R ⁷ is a C 1 to 8 alkyl or fluorine; i is 0, ¹ , 2, 3, 4, or 5; X ¹ is -OH, -COOH, -SH, -OCH ₃ , or -NH ₂ ; X ² is a single bond or -O-. The liquid crystal composition according to claim 14, wherein the second additive is at least one selected from the group consisting of compounds represented by formula (5-1-1) to formula (5-1-29). a compound, In the formula (5-1-1) to the formula (5-1-29), R ⁵ is an alkyl group having 4 to 20 carbon atoms, and among the alkyl groups, at least one -CH ₂ - may be subjected to -CH=CH- And -CF=CH-, -CH=CF-, -C≡C-, or a cycloalkyl group having a carbon number of 3 to 8, in which at least one hydrogen may be substituted with fluorine or chlorine. The liquid crystal composition according to claim 11, wherein the ratio of the second additive is less than 10% by weight based on the weight of the liquid crystal composition. A liquid crystal display element comprising the liquid crystal composition as described in claim 1 of the patent application. The liquid crystal display element according to claim 19, wherein the operation mode of the liquid crystal display element is a coplanar switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced photoreaction alignment mode, and the liquid crystal display element The driving method is active matrix mode. A polymer-stabilized alignment type liquid crystal display device comprising the liquid crystal composition according to claim 1, wherein the polymerizable compound 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 as described in claim 1, wherein the polymerizable compound in the liquid crystal composition is 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. A liquid crystal composition which is a liquid crystal composition as described in claim 1, which is used in a polymer-stabilized alignment type liquid crystal display element. 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.