TW201625777A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

Provided is a liquid crystal composition either fulfilling at least one property or having an appropriate balance of at least two properties, from among such properties as a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, a large negative dielectric anisotropy, a high specific resistance, a high stability against ultraviolet rays, and a high stability against heat. Also provided is an AM element having properties such as a short response time, a high voltage retention rate, a low threshold voltage, a high contrast ratio, and a long service life. The present invention is a liquid crystal composition which contains as a first additive a compound for contributing to high stability against heat or ultraviolet rays, which has negative dielectric anisotropy, and which has a nematic phase. The composition may contain a specific compound having a large negative dielectric anisotropy as a first component, a specific compound having a high upper limit temperature or low viscosity as a second component, and a specific compound having a polymerizable group as a second additive.

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 having a negative dielectric anisotropy, and including the composition and having in-plane switching (IPS), vertical alignment (VA), and fringe field switching. , FFS), liquid crystal display elements in a mode such as field-induced photo-reactive alignment (FPA). The present invention also relates to a polymer stable alignment type liquid crystal display element.

In the liquid crystal display device, the classification of the operating mode based on the liquid crystal molecules is: phase change (PC), twisted nematic (TN), super twisted nematic (STN), Electrically controlled birefringence (ECB), optically compensated bend (OCB), in-plane switching (IPS), vertical alignment (VA), fringe field switching (fringe field) Switching, FFS), field-induced photo-reactive alignment (FPA) and other modes. The component-based driving methods are classified into a passive matrix (PM) and an active matrix (AM). 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 is further 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. A preferred upper limit temperature of the nematic phase is about 70 ° C or higher, and a preferred lower limit temperature of the nematic phase is about -10 ° C or lower. The viscosity of 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. More preferably, the viscosity at low temperatures is small.

Table 1. Characteristics of composition and AM components

The optical anisotropy of the composition is related to the contrast ratio of the component. A large optical anisotropy or a small optical anisotropy is required depending on the mode of the element, that is, the optical anisotropy is appropriate. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The value of the appropriate product depends on the type of operation mode. In the VA mode element, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode element, the value is in the range of about 0.20 μm to about 0.30 μm. In such cases, a component having a small cell gap is preferably a composition having a large optical anisotropy. The large dielectric anisotropy in the composition contributes to low threshold voltages, low power consumption, and large contrast ratios in the components. Therefore, it is preferred that the dielectric anisotropy is large. The large specific resistance in the composition contributes to the large voltage holding ratio of the element and a large contrast ratio. Therefore, a composition having a larger specific resistance not only at room temperature but also at a high temperature in the initial stage is preferable. It is preferably a composition having a large specific resistance not only at room temperature but also at a high temperature after long-term use. The stability of the composition to ultraviolet light and heat is related to the life of the component. When the stability is high, the life of the component is long. The characteristics as described above are preferable for an AM device used in a liquid crystal projector, a liquid crystal television or the like.

In a liquid crystal display device of a polymer sustained alignment (PSA) type, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into 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 the 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. The effect of the polymer can be expected from 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 an AM element of a polymer sustained alignment (PSA) type. A compound having a negative dielectric anisotropy is disclosed in Patent Document 1 below. Prior art literature

Patent Document 1: International Publication No. 2012-053323

[Problems to be solved by the invention]

One of the objects of the present invention is a liquid crystal composition having a high upper limit temperature in a nematic phase, a low minimum temperature of a nematic phase, a small viscosity, an appropriate optical anisotropy, a large negative dielectric anisotropy, and a large specific resistance. At least one of the characteristics of high stability to ultraviolet light and high stability to heat is satisfied. Another object is a liquid crystal composition having an appropriate balance between at least two characteristics. Still another object is a liquid crystal display element containing such a composition. Still another object is an AM device having characteristics of 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 a liquid crystal composition containing at least one compound selected from the group consisting of compounds represented by formula (1) as a first additive, and having a negative liquid crystal display element, and a liquid crystal display element containing the composition Dielectric anisotropy, and has a nematic phase, In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or an alkyl group having 1 to 4 carbon atoms; and ring A and ring B are independently Is a cyclohexyl group, a cyclohexene group, a decahydronaphthalenyl group, a dihydropyranyl group, a tetrahydropyranyl group, a dioxanediyl group, a phenylene group, a naphthyldiyl group, a pyrimidinediyl group or a pyridine. a diradical, and wherein at least one hydrogen in the rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon number substituted with at least one hydrogen via fluorine or chlorine 1 to 5 alkyl substituted; Z ¹ , Z ² and Z ^{3 are} independently a single bond or a C 1 to 10 alkyl group, and in the alkyl group, at least one -CH ₂ - may be -O- , -S-, -CO-, -COO-, -OCO- or -SiH ₂ -, at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH- or -C≡C-, these groups Wherein at least one hydrogen may be substituted by fluorine or chlorine; a and b are independently 1 or 2; c is 0, 1 or 2, and when c is 0, ring A is cyclohexene, decalinyl , dihydropyranyldiyl, tetrahydropyranodiyl, dioxanediyl, naphthalenediyl, pyrimidinediyl or pyridinyl, and wherein at least one of the hydrogens may be fluorine, chlorine or carbon The alkyl group of 1 to 5, the alkoxy group having 1 to 5 carbon atoms, or the alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine is substituted. [Effects of the Invention]

An advantage of the present invention 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 large negative dielectric anisotropy, and a large specific resistance. At least one characteristic is satisfied among characteristics such as high stability of ultraviolet rays and high stability against heat. Another advantage is a liquid crystal composition having an appropriate balance between at least two characteristics. Yet another advantage is a liquid crystal display element containing such a composition. Still another advantage is an AM device having characteristics of 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 such as a nematic phase or a smectic phase, and does not have a liquid crystal phase, but adjusts the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The general term for the compounds mixed in the composition for the purpose of the properties of the class. 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. The ratio (content) of the liquid crystalline compound is represented by weight percentage (% by weight) based on the weight of the liquid crystal composition. An additive such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, or a polymerization inhibitor is added to the composition as needed. The ratio (addition amount) of the additive is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the ratio of the liquid crystal compound. Millions of parts per million (ppm) are also sometimes used. 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 of the nematic phase in the initial stage, and is not only at room temperature after long-term use. And also has a large specific resistance at a temperature close to the upper limit temperature of the nematic phase. "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 of the nematic phase in the initial stage, and is not only at room temperature after long-term use. Lower, and also has a large voltage holding ratio at a temperature close to the upper limit temperature of the nematic phase. 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 (2) is simply referred to as "compound (2)". At least one compound selected from the group consisting of the compounds represented by the formula (3) is simply referred to as "compound (3)". The "compound (3)" means a compound represented by the formula (3), a mixture of two compounds or a mixture of three or more compounds. The same is true for the compounds represented by the other formulas. The expression "at least one 'A'" means that the number of 'A' is arbitrary. The expression "at least one 'A' can be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, these The location can also be selected 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 ⁹ is used for a plurality of compounds. Among these compounds, the two groups represented by any two of R ⁹ may be the same or different. For example, there is a case where R ⁹ of the compound (2-1) is an ethyl group, and R ⁹ of the compound (2-2) is an ethyl group. Also the compound (2-1) R ⁹ is ethyl, and R of the compound (2-2) is propyl. ^9. This rule is also applied to marks of other end groups and the like. In the formula (2), when d is 2, two rings C exist. In the compound, the two rings represented by the two rings C may be the same or different. This rule also applies to any two rings C when d is greater than 2. This rule also applies to symbols such as Z ⁶ and ring F. This rule also applies to the case of two -Sp ² -P ⁵ as in the compound (4-27).

The symbols A, B, and C surrounded by a hexagon correspond to a six-membered ring or a fused ring such as ring A, ring B, and ring C, respectively. In the compound (1) or the compound (4), the oblique line of the cross-cut hexagon means that any hydrogen on the ring may be substituted with a group such as -Sp ¹ -P ¹ . The subscripts such as h indicate the number of substituted groups. When the subscript is 0, this substitution does not exist. When h is 2 or more, a plurality of -Sp ¹ -P ¹ are present on the ring I. The plurality of groups represented by -Sp ¹ -P ¹ may be the same or may be different.

The alkyl group is linear or branched and does not contain a cyclic alkyl group. Linear alkyl groups are preferred over branched alkyl groups. These cases are also the same for terminal groups such as alkoxy groups and alkenyl groups. Regarding the stereo configuration associated with 1,4-cyclohexylene, in order to increase the upper limit temperature, trans is superior to cis. The 2-fluoro-1,4-phenylene group means the two 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 a bonding group such as a carbonyloxy group (-COO- and -OCO-).

The present invention is as follows.

Item 1. A liquid crystal composition containing at least one compound selected from the group consisting of compounds represented by formula (1) as a first additive, having a negative dielectric anisotropy, and having a nematic phase, In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or an alkyl group having 1 to 4 carbon atoms; and ring A and ring B are independently Is a cyclohexyl group, a cyclohexene group, a decahydronaphthalenyl group, a dihydropyranyl group, a tetrahydropyranyl group, a dioxanediyl group, a phenylene group, a naphthyldiyl group, a pyrimidinediyl group or a pyridine. a diradical, and wherein at least one hydrogen in the rings may be substituted by fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon number substituted with at least one hydrogen via fluorine or chlorine 1 to 5 alkyl substituted; Z ¹ , Z ² and Z ^{3 are} independently a single bond or a C 1 to 10 alkyl group, and in the alkyl group, at least one -CH ₂ - may be -O- , -S-, -CO-, -COO-, -OCO- or -SiH ₂ -, at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH- or -C≡C-, these groups Wherein at least one hydrogen may be substituted by fluorine or chlorine; a and b are independently 1 or 2; c is 0, 1 or 2, and when c is 0, ring A is cyclohexene, decalinyl , dihydropyranyldiyl, tetrahydropyranodiyl, dioxanediyl, naphthalenediyl, pyrimidinediyl or pyridinyl, and wherein at least one of the hydrogens may be fluorine, chlorine or carbon The alkyl group of 1 to 5, the alkoxy group having 1 to 5 carbon atoms, or the alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine is substituted.

The liquid crystal composition according to item 1, which contains at least one compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-5) as a first additive, In the formulae (1-1) to (1-5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or an alkane having 1 to 4 carbon atoms. base.

The liquid crystal composition according to Item 1 or Item 2, wherein the ratio of the first additive is in the range of 0.005 wt% to 1 wt% based on the weight of the liquid crystal composition.

The liquid crystal composition according to any one of items 1 to 3, 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 ⁹ and R ^{10 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 an oxyalkylene having 2 to 12 carbon atoms. a C 1 to 12 alkyl group substituted with at least one hydrogen substituted with fluorine or chlorine; ring C and ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1, 4-phenylene, at least one hydrogen 1,4-phenyl or tetrahydropyran-2,5-diyl substituted by fluorine or chlorine; ring D is 2,3-difluoro-1,4- Phenyl, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene- 2,6-diyl or 7,8-difluorochromane-2,6-diyl; Z ⁴ and Z ^{5 are} independently a single bond, a group, a methyleneoxy group or a carbonyloxy group; d is 1, 2 or 3, and e is 0 or 1; and the sum of d and e is 3 or less.

The liquid crystal composition according to any one of the items 1 to 4, 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 ⁹ and R ^{10 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. An alkenyloxy group having 2 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms substituted with at least one hydrogen via fluorine or chlorine.

The liquid crystal composition according to Item 4 or 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 any one of items 1 to 6, 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 ¹¹ and R ^{12 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 via fluorine or chlorine. a substituted alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms substituted with at least one hydrogen; the ring F and the ring G are independently 1,4-cyclohexylene, 1,4-stretch Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, ethyl or carbonyloxy; f is 1, 2 or 3.

The liquid crystal composition according to any one of the items 1 to 7 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 ¹¹ and R ^{12 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 carbon atoms substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms substituted with at least one hydrogen via fluorine.

The liquid crystal composition according to Item 7 or 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 any one of the items 1 to 9, comprising at least one polymerizable compound selected from the group consisting of compounds represented by formula (4) as a second additive, In the formula (4), Ring I and Ring K 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, and at least one hydrogen of the rings may be fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbon atoms Substituting, or at least one hydrogen substituted with a C 1 to 12 alkyl group substituted by fluorine or chlorine; ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene Base, 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 a di-, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl group, and wherein at least one hydrogen in the rings may be via fluorine, Chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms substituted with at least one hydrogen substituted by fluorine or chlorine; Z ⁷ and Z ^{8 are} independently a single bond or a C 1-10 alkylene group, and the alkylene, at least one -CH ₂ - may be -O -, - - COO- or -OCO-, at least one, - 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} independently a polymerizable group; and Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or a carbon number of 1 to 10. An alkyl group, wherein at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, 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; g is 0, 1 or 2; h, i and j are independently 0, 1, 2, 3 or 4 And the sum of h, i and j is 1 or more.

The liquid crystal composition according to Item 10, wherein, in the formula (4), P ¹ , P ² and P ^{3 are} independently selected from the group consisting of the formula (P-1) to the formula (P-5). Polymeric groups in the group of 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 any one of items 1 to 11, which contains at least one polymerizable group selected from the group consisting of compounds represented by formula (4-1) to formula (4-27). a compound as a second additive, In the formulae (4-1) to (4-27), P ⁴ , P ⁵ and P ^{6 are} independently selected from the group consisting of the groups represented by the formulae (P-1) to (P-3). Polymeric group; In the formulae (P-1) to (P-3), 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; in the formulae (4-1) to (4-27), Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and In the alkylene group, at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, and at least one -CH ₂ -CH ₂ - may be via -CH=CH- or -C≡ C-substituent, in which at least one hydrogen may be substituted by fluorine or chlorine.

The liquid crystal composition according to any one of items 10 to 12, wherein the ratio of the second additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition.

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

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

A liquid crystal display element according to any one of items 10 to 13, wherein the polymerizable compound in the liquid crystal composition is polymerized.

Item 17. The use of a liquid crystal composition, which is a liquid crystal composition according to any one of items 1 to 13, which is used for a liquid crystal display element.

Item 18. The use of a liquid crystal composition according to any one of items 10 to 13, which is used for a polymer-stabilized alignment type liquid crystal display element.

The invention also includes the following items. (a) the composition containing a group selected from the group consisting of an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, and a polymerization inhibitor. One compound, two compounds or more than three compounds. (b) An AM device comprising the composition. (c) A polymer stable alignment (PSA) type AM device comprising the composition further containing a polymerizable compound. (d) A polymer stabilized alignment (PSA) type AM device containing the composition, and a polymerizable compound in the composition is polymerized. (e) An element containing the composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA. (f) A transmissive element containing the composition. (g) Use of the composition as a composition having a nematic phase. (h) Use as an optically active composition by adding an optically active compound to the composition.

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 constitution of the component compounds in 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, 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. An example of the composition B is a composition containing the compound (1), the compound (2), and the compound (3) as essential components. 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 0 (zero) means that the value is zero, or close to zero.

Table 2. Characteristics of the compound 1) Compounds with negative dielectric anisotropy

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) as the first additive contributes to high stability against heat or ultraviolet rays. Since the amount of the first additive added is extremely small, the properties such as the upper limit temperature, optical anisotropy, and dielectric anisotropy are not affected. The compound (2) as the first component increases the dielectric anisotropy and lowers the minimum temperature. The compound (3) as the second component lowers the viscosity or raises the upper limit temperature. The polymerizable compound (4) as the second additive provides a polymer by polymerization, which shortens the response time of the element and improves the afterimage of the image.

Third, the combination of the components in the composition, the preferred ratio of the component compounds, and the basis thereof will be described. A preferred combination of ingredients in the composition is: first additive + first component, first additive + first component + second component, first additive + first component + second additive, or first Additive + first component + second component + second additive. A particularly preferred combination is the first additive + first component + second component, or first additive + first component + second component + second additive.

In order to improve the stability against ultraviolet rays or heat, a preferred ratio of the first additive is about 0.005% by weight or more, and in order to lower the minimum temperature, a preferred ratio of the first additive is about 1% by weight or less. A more desirable ratio is in the range of from about 0.01% by weight to about 0.5% by weight. A particularly preferred ratio is in the range of from about 0.03 wt% to about 0.3 wt%.

In order to increase the dielectric anisotropy, a preferred ratio of the first component is about 10% by weight or more, and a preferred ratio of the first component is about 90% by weight or less in order to lower the minimum temperature. A more preferred ratio is in the range of from about 20% by weight to about 80% by weight. A particularly preferred ratio is in the range of from about 30% by weight to about 70% by weight.

A preferred ratio of the second component is about 10% by weight or more for increasing the maximum temperature or for lowering the viscosity, and a preferred ratio of the second component is about 90% by weight or less for increasing the dielectric anisotropy. A more preferred ratio is in the range of from about 20% by weight to about 80% by weight. A particularly preferred ratio is in the range of from about 30% by weight to about 70% by weight.

The second additive (polymerizable compound) is added to the composition for the purpose of being suitable for the element of the polymer stable alignment type. In order to align the liquid crystal molecules, a preferred ratio of the additive is about 0.03% by weight or more, and a ratio of the additive is preferably about 10% by weight or less in order to prevent display defects of the element. A more desirable ratio is in the range of from about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of from about 0.2% by weight to about 1.0% by weight.

Fourth, a preferred embodiment of the component compound will be described. In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or an alkyl group having 1 to 4 carbon atoms. Desirable R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are hydrogen or methyl. More preferably, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ or R ⁸ are a methyl group.

Ring A and Ring B are independently cyclohexyl, cyclohexenyl, decahydronaphthalenyl, dihydropyranyl, tetrahydropyranyl, dioxanediyl, phenyl, naphthalene a pyrimidinediyl or pyridyldiyl group, and at least one of the hydrogens may be fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or at least one hydrogen via fluorine Or an alkyl group substituted with 1 to 5 carbon atoms substituted by chlorine. Preferred ring A or ring B is 1,4-cyclohexylene, 1,4-cyclohexenyl, decahydronaphthalene-2,6-diyl, 3,4-dihydro-2H-pyran- 3,6-diyl, 3,4-dihydro-2H-pyran-2,5-diyl, 3,6-dihydro-2H-pyran-2,5-diyl, tetrahydropyran- 2,5-diyl, 1,3-dioxane-2,5-diyl, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 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, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and in these rings At least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. Particularly preferred ring A or ring B is 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl.

a and b are independently 1 or 2. Preferably a or b is one. When c is 0, 1 or 2, and c is 0, ring A is cyclohexene, decalin, dihydropyranyl, tetrahydropyranyl, dioxanediyl, naphthalene a diyl, pyrimidinediyl or pyridyldiyl group, and wherein at least one hydrogen in the rings may be via fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or at least one hydrogen The alkyl group having 1 to 5 carbon atoms substituted by fluorine or chlorine is substituted. Preferably c is 0 or 1.

Z ¹ , Z ² and Z ^{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 via -O-, -S-, -CO- in the alkylene group. Substituting -COO-, -OCO- or -SiH ₂ -, at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH- or -C≡C-, wherein at least one hydrogen may be fluorine-containing Or chlorine substituted. Preferably, Z ¹ , Z ² or Z ³ is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-, and at least one hydrogen may be Replaced by fluorine. A particularly good example is a single bond.

In the formulae (2) and (3), R ⁹ and R ^{10 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 2 carbon atoms. An alkenyl group of up to 12, or an alkyl group having 1 to 12 carbons substituted with at least one hydrogen via fluorine or chlorine. To enhance the stability, the preferred R ⁹ or R ¹⁰ is alkyl having 1 to 12, for increasing the dielectric anisotropy, preferred R ⁹ or R ¹⁰ is alkoxy having 1 to 12. R ¹¹ and R ^{12 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 a carbon number of 1 at least one hydrogen substituted by fluorine or chlorine. An alkyl group of 12, or an alkenyl group having 2 to 12 carbons substituted with at least one hydrogen via fluorine. To reduce the viscosity, preferred R ¹¹ or R ¹² is alkenyl having 2 to 12, to improve stability, preferred R ¹¹ or R ¹² is an alkyl group having 1 to 12 carbons.

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 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 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 reduce the viscosity and the like, in the alkenyl group such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl or 3-hexenyl Jia is a trans configuration. The alkenyl group such as 2-butenyl, 2-pentenyl or 2-hexenyl is preferably a cis configuration. Among the alkenyl groups, a linear alkenyl group is preferred to a branched alkenyl group.

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 alkenyl group in which at least one hydrogen is substituted by fluorine 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 C and Ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, at least one hydrogen substituted by fluorine or chlorine. Or tetrahydropyran-2,5-diyl. Preferred examples of "at least one 1,4-phenylene group in which hydrogen is replaced by fluorine or chlorine" are: 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-benzobenzene Or 2-chloro-3-fluoro-1,4-phenylene. In order to lower the viscosity, preferred ring C or ring E is 1,4-cyclohexylene, and in order to improve dielectric anisotropy, preferred ring C or ring E is tetrahydropyran-2,5-diyl. In order to enhance optical anisotropy, a preferred ring C or ring E is a 1,4-phenylene group. In order to increase the upper limit temperature, the stereo configuration associated with 1,4-cyclohexylene is a trans configuration superior to the cis configuration. Tetrahydropyran-2,5-diyl is or , preferably .

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

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

Z ⁴ and Z ^{5 are} independently a single bond, an ethyl group, a methylene group or a carbonyloxy group. In order to lower the viscosity, it is preferred that Z ⁴ or Z ⁵ is a single bond. In order to lower the lower limit temperature, it is preferred that Z ⁴ or Z ⁵ is an exoethyl group, and in order to improve dielectric anisotropy, Z ⁴ or Z ^{5 is} preferred. It is a methyleneoxy group. Z ⁶ is a single bond, an ethyl group or a carbonyloxy group. In order to lower the viscosity, Z ⁶ is preferably a single bond.

d is 1, 2 or 3. In order to lower the viscosity, d is preferably 1, and in order to increase the upper limit temperature, d is preferably 2 or 3. b is 0 or 1. Desirable e is 0 in order to lower the viscosity, and e is preferably 1 in order to lower the lower limit temperature. f is 1, 2 or 3. In order to lower the viscosity, it is preferable that f is 1, and in order to increase the upper limit temperature, it is preferable that f is 2 or 3.

In the formula (4), P ¹ , P ² and P ^{3 are} independently a polymerizable group. Desirable P ¹ , P ² or P ³ is a polymerizable group selected from the group consisting of the groups represented by the formulae (P-1) to (P-5). More preferably, P ¹ , P ² or P ³ is a group (P-1) or a group (P-2). A particularly preferred group (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wave line of the base (P-1) to the base (P-5) represents the portion of the bond.

In the group (P-1) to the group (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 in order to increase the reactivity. More preferably, M ¹ is a methyl group, and more preferably M ² or M ³ is hydrogen.

In the formulae (4-1) to (4-27), P ⁴ , P ⁵ and P ^{6 are} independently a group represented by the formula (P-1) to the formula (P-3). Desirable P ⁴ , P ⁵ or P ⁶ is a group (P-1) or a group (P-2). A more preferred group (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wave line of the base (P-1) to the base (P-3) represents the portion of the bond.

In the formula (4), 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 subjected to -O-, - COO-, -OCO- or -OCOO-substituted, 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.

Ring I and Ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidin-2-yl or pyridin-2-yl, and at least one of the hydrogens may be via fluorine or chlorine, an alkyl group having from 1 to 12 carbons, an alkoxy group having from 1 to 12 carbon atoms, or at least one hydrogen Substituted by a fluorine or chlorine substituted alkyl group having 1 to 12 carbon atoms. Preferred ring I or ring K is phenyl. Ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl or pyridinyl-2,5-diyl, and wherein at least one hydrogen in the rings may be through fluorine or chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least One hydrogen is substituted with a C 1 to 12 alkyl group substituted by fluorine or chlorine. Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁷ and Z ^{8 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of -CH ₂ - may be via -O-, -CO-, -COO- or -OCO. Substituted, 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 )-Substituent, in which at least one hydrogen may be substituted by fluorine or chlorine. Desirable Z ⁷ or Z ⁸ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. A particularly good Z ⁷ or Z ⁸ is a single bond.

g is 0, 1, or 2. Preferably g is 0 or 1. h, i, and j are independently 0, 1, 2, 3, or 4, and the sum of h, i, and j is 1 or more. Preferably h, i or j is 1 or 2.

Fifth, a preferred component compound is shown. A preferred compound (1) is the compound (1-1) to the compound (1-5) according to item 2. Among these compounds, at least one of the first additives is preferably the compound (1-1), the compound (1-3) or the compound (1-4). It is preferred that at least two of the first additives are a combination of the compound (1-1) and the compound (1-3), or the compound (1-3) and the compound (1-4).

A preferred compound (2) is the compound (2-1) to the compound (2-21) according to item 5. Among these compounds, at least one of the first components is preferably compound (2-1), compound (2-4), compound (2-5), compound (2-7), 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), 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 8. Among these compounds, at least one of the second components is preferably compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-7) 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.

A preferred compound (4) is the compound (4-1) to the compound (4-27) according to item 12. Among these compounds, at least one of the second additives is preferably a compound (4-1), a compound (4-2), a compound (4-24), a compound (4-25), and a compound (4-26). Or compound (4-27). Preferably, at least two of the second additives are the compound (4-1) and the compound (4-2), the compound (4-1), and the compound (4-18), the compound (4-2), and the compound (4). -24), compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4) -18) and a combination of compounds (4-24). Preferred from the group (P-1) to the group (P-3), M ¹ , M ² or M ³ is hydrogen or methyl. 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-.

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, and the like. The optically active compound is added to the composition for the purpose of imparting a torsion angle to the helical structure of the liquid crystal. Examples of such a compound are the compound (5-1) to the compound (5-5). A preferred ratio of the optically active compound is about 5% by weight or less. A more desirable ratio is in the range of from about 0.01% by weight to about 2% by weight.

In order to prevent a decrease in the 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, the antioxidant is maintained. Add to the composition. A preferred example of the antioxidant is a compound (6) wherein n is an integer of from 1 to 9.

In the compound (6), preferred n is 1, 3, 5, 7 or 9. The better n is 7. Since the compound (6) having n of 7 has a small volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after using the element for a long period of time. In order to obtain the above effect, a preferred ratio of the antioxidant is about 50 ppm or more, and a preferred ratio of the antioxidant is about 600 ppm or less in order not to lower the upper limit temperature or to increase the lower limit temperature. A particularly preferred ratio is in the range of from about 100 ppm to about 300 ppm.

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

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

In order to be suitable for a polymer stable alignment (PSA) type element, a polymerizable compound is used. Compound (4) is suitable for this purpose. Compound (4) and a polymerizable compound different from compound (4) may be added to the composition together. Preferred examples of such a polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane (oxetane) )), a compound such as vinyl ketone. A preferred example is a derivative of acrylate or methacrylate. A preferred ratio of the compound (4) is about 10% by weight or more based on the total weight of the polymerizable compound. A more preferable ratio of the compound (4) is about 50% by weight or more. A particularly preferable ratio of the compound (4) is 80% by weight or more. The optimum ratio of the compound (4) is 100% by weight.

The polymerizable compound like the compound (4) 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 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 Suitable for free radical polymerization. A preferred ratio of the photopolymerization initiator is in the range of from about 0.1% by weight to about 5% by weight based on the total mass of the polymerizable compound. A more desirable ratio is in the range of from about 1% by weight to about 3% by weight.

When a polymerizable compound such as the compound (4) 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 polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, and 4-tert-butylcatechol. , 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 (2-1) is synthesized by the method described in JP-A-2000-053602. The compound (3-1) is synthesized by the method described in JP-A-59-176221. The compound (3-13) is synthesized by the method described in JP-A-2-237949. The compound (4-18) is synthesized by the method described in JP-A-7-101900. A compound of formula (6) wherein n is 1 is available from Sigma-Aldrich Corporation. The compound (6) wherein n is 7 or the like is synthesized by the method described in the specification of U.S. Patent No. 3,660,505. Compound (1-3) was synthesized by the method described below.

First step: 2,2,6,6-tetramethyl-4-piperidinol (15.00 g, 95.39 mmol) and NaH (60%, 3.80 g, 95.01 mmol) in tetrahydrofuran (THF) The mixture was heated to reflux for 2 hours. The reaction mixture was cooled to -10 ° C or lower, while maintaining the temperature, a solution of 1,1'-biphenyl-4,4'-dicarbonyldichloride (12.00 g, 43.00 mmol) in THF was gradually added dropwise. After the reaction mixture was stirred at room temperature for 1 hour, it was quenched with water and extracted with methyl tert-butyl ether (MTBE). The cerium oxide gel is added to the composite organic layer, filtered, and the solvent is distilled off to obtain bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,1'-linked. Benzene-4,4'-dicarboxylate (6 g, yield 26.7%).

¹ H-NMR (CDCl ₃ ; δ ppm): 8.12 (dd, 4H), 7.69 (dd, 4H), 5.48 (tt, 2H), 2.08 (dd, 4H), 1.57 (br, 2H), 1.36-1.31 ( m, 16H), 1.21 (s, 12H).

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

Finally, the use of the composition will be described. The composition mainly has a lower limit temperature of about -10 ° C or less, an upper limit temperature of about 70 ° C or more, and an optical anisotropy of a range of about 0.07 to about 0.20. 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 having an optical anisotropy in the range of about 0.08 to about 0.25, and further having an optical range of about 0.10 to about 0.30, can also be prepared by controlling the ratio of the component compounds or by mixing other liquid crystal compounds. Anisotropic composition. The composition can be used as a composition having a nematic phase which 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 having a mode of PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA, and the like. 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, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel or perpendicular to the glass substrate. 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. It can also be used for a nematic curvilinear aligned phase (NCAP) type element produced by microencapsulating the composition or a polymer dispersed (PD) in which a three-dimensional network polymer is formed in the composition. ) type of component. [Examples]

The invention will be further described in detail by way of examples. The invention is not limited by the embodiments. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The invention also encompasses mixtures in which at least two of the compositions of the examples are mixed. The synthesized compound is identified by a method such as nuclear magnetic resonance (NMR) analysis. The properties of the compound and the composition were measured by the methods described below.

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: The measurement was performed using a GC-14B gas chromatograph manufactured by Shimadzu Corporation. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set to 280 ° C, and the detector (flame ionization detector (FID)) was set to 300 ° C. For the separation of the component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the fixed liquid phase was dimethyl polyoxyalkylene. ; no polarity). The column was held at 200 ° C for 2 minutes and then heated to 280 ° C at a rate of 5 ° C / min. After the sample was prepared into an acetone solution (0.1% by weight), 1 μL of the sample was injected into the sample gasification chamber. The record is a C-R5A type chromatograph module (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the retention time of the peak corresponding to the component compound and the area of the peak.

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

The ratio of the liquid crystalline compound contained in the composition can be calculated by the method described below. A mixture of liquid crystal compounds was detected by a gas chromatograph (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio (weight ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of various liquid crystal compounds can be regarded as 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 characteristics of the composition or element are measured, the composition is 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 extrapolation 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 or described in the JEITA standard (JEITA ED-2521B) which was developed by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA). Methods. 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 changes from the nematic phase to the isotropic liquid is 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 (T _C ; ° 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 in the nematic phase at -20 ° C and changes to crystal or smectic phase at -30 ° C, T _{C is} described as < -20 ° C. The lower limit temperature of the nematic phase is sometimes simply referred to as "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa·s): According to M. Imai et al., "Molecular Crystals and Liquid Crystals" No. 259 The method described in 37 (1995) was carried out. A sample was placed in 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 no voltage for 0.2 seconds, it was applied repeatedly by applying only one rectangular wave (rectangular pulse; 0.2 second) and no voltage application (2 seconds). The peak current and the peak time of the transient current generated by the application were measured. The values of the rotational viscosity were obtained from the measured values and the calculation formula (8) on page 40 of M. Imai et al.'s paper. The dielectric anisotropy required for this calculation was measured in accordance with the measurement (6) described below.

(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 was 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 element having a distance (cell gap) of 2 glass substrates of 4 μm, and the element was sealed by an adhesive which was cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and after 2 seconds, the dielectric constant (ε∥) of the liquid crystal molecule in the long axis direction was measured. 2) Measurement of dielectric constant (ε⊥): A polyimide solution was coated on a sufficiently washed glass substrate. After the glass substrate was fired, the obtained alignment film was subjected to a rubbing treatment. A sample was placed in a TN device in which the distance (cell gap) of two glass substrates 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 device in which the interval (cell gap) of two glass substrates 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 is prepared. The threshold voltage is expressed by the voltage at which the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-9; 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 sample was added, the element was sealed with an adhesive which was cured by ultraviolet rays. A pulse voltage (1 V, 60 microseconds) was applied to the TN device to charge. The attenuated voltage was measured between 166.7 msec by a high-speed voltmeter, and the area A between the voltage curve in the unit period and the horizontal axis was obtained. Area B is the area when it 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-10; measured at 60 ° C; %): The voltage holding ratio was measured in the same procedure as described above except that the measurement was carried out at 60 ° C instead of 25 ° C. The obtained value is represented by VHR-10.

(10) Voltage holding ratio (VHR-11; measured at 60 ° C; %): After irradiating ultraviolet rays, the voltage holding ratio was measured to evaluate the stability against ultraviolet rays. The TN element used for the measurement had a polyimide film with a cell gap of 5 μm. A sample was injected into the device, and ultraviolet rays of 5 mW/cm ² were irradiated for 167 minutes. The light source is black light manufactured by Eyegraphics Co., Ltd., F40T10/BL (peak wavelength 369 nm), and the distance between the components and the light source is 5 mm. In the measurement of VHR-11, the attenuated voltage was measured between 166.7 msec. The composition having a large VHR-11 has great stability to ultraviolet rays.

(11) Voltage holding ratio (VHR-12; measured at 60 ° C; %): The TN element in which the sample was injected was heated in a thermostat at 120 ° C for 20 hours, and then the voltage holding ratio was measured to evaluate the heat. stability. In the measurement of VHR-12, the attenuated voltage was measured between 166.7 msec. The composition having a large VHR-12 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 normally black mode VA device in which the interval (cell gap) of two glass substrates was 4 μm and the rubbing direction was anti-parallel. The element is sealed using an adhesive that hardens with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 second) 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, the transmittance is regarded as 100%, and when the amount of light is the smallest, the transmittance is regarded as 0%. The response time is represented by the time (fall time; fall time; milliseconds) required for the transmittance to change from 90% to 10%.

(13) Specific resistance (ρ; measured at 25 ° C; Ω cm): 1.0 mL of a sample was injected into 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 was calculated from the following formula. (specific resistance) = {(voltage) × (capacitance of the container)} / {(direct current) × (dielectric constant of vacuum)}.

The compounds in the examples are represented by symbols based on the definitions of Table 3 below. In Table 3, the stereo configuration associated with 1,4-cyclohexylene is in the trans configuration. The number in parentheses after the mark corresponds to the number of the compound. 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.

[Example 1] 2-H1OB(2F,3F)-O2 (2-4) 3% 3-H1OB(2F,3F)-O2 (2-4) 10% 1V2-BB(2F,3F)-O2 ( 2-5) 10% V-HHB(2F,3F)-O1 (2-7) 12% V-HHB(2F,3F)-O2 (2-7) 12% 3-HH1OB(2F,3F)-O2 (2-10) 6% 2-BB(2F,3F)B-3 (2-11) 6% 3-HH-V (3-1) 25% 3-HH-V1 (3-1) 6% 4 -HH-V1 (3-1) 3% V-HHB-1 (3-5) 3% V2-HHB-1 (3-5) 4% Preparation of the composition having negative dielectric anisotropy, measurement characteristic. NI=80.1°C; Tc<-20°C;Δn=0.103;Δε=-3.9; Vth=2.09 V; η=20.7 mPa·s; VHR-11=36.3%. In the composition, 0.05% by weight Compound (1-1) was added in a ratio, and VHR-11 was measured. VHR-11=67.1%.

[Example 2] 3-H1OB(2F,3F)-O2 (2-4) 8% V2-BB(2F,3F)-O1 (2-5) 4% V2-BB(2F,3F)-O2 ( 2-5) 9% 1V2-BB(2F,3F)-O4 (2-5) 6% V-HHB(2F,3F)-O2 (2-7) 10% V-HHB(2F,3F)-O4 (2-7) 3% 1V2-HHB(2F,3F)-O2 (2-7) 4% 3-HH1OB(2F,3F)-O2 (2-10) 12% 3-HH-V (3-1 26% 1-HH-2V1 (3-1) 3% 3-HH-2V1 (3-1) 3% 5-HB-O2 (3-2) 3% 3-HHB-O1 (3-5) 5 % V-HHB-1 (3-5) 4% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=77.0°C; Tc<-20°C;Δn=0.099;Δε=-3.4; Vth=2.22 V; η=18.6 mPa·s; VHR-11=34.7%. In the composition, 0.1% by weight Compound (1-3) was added in a ratio, and VHR-11 was measured. VHR-11=64.5%.

[Example 3] 3-H1OB(2F,3F)-O2 (2-4) 8% 3-BB(2F,3F)-O2 (2-5) 8% 2O-BB(2F,3F)-O2 ( 2-5) 5% 2-HH1OB(2F,3F)-O2 (2-10) 8% 3-HH1OB(2F,3F)-O2 (2-10) 7% 2-BB(2F,3F)B- 3 (2-11) 8% 3-HDhB(2F,3F)-O2 (2-13) 10% 3-HH-V (3-1) 24% 3-HH-V1 (3-1) 10% V2 -HHB-1 (3-5) 9% 1O1-HBBH-4 (-) 3% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=83.7°C; Tc<-20°C;Δn=0.107;Δε=-3.7; Vth=2.21 V; η=22.9 mPa·s; VHR-11=37.9%. In the composition, 0.05% by weight Compound (1-2) was added in proportion to measure VHR-11. VHR-11=69.5%.

[Example 4] 3-H2B(2F,3F)-O2 (2-3) 15% 5-H2B(2F,3F)-O2 (2-3) 12% 3-HHB(2F,3F)-O2 ( 2-7) 8% 5-HHB(2F,3F)-O2 (2-7) 6% 2-HHB(2F,3F)-1 (2-7) 5% 3-HBB(2F,3F)-O2 (2-15) 10% 4-HBB(2F,3F)-O2 (2-15) 6% 1V2-HBB(2F,3F)-O2 (2-15) 4% 2-HH-3 (3-1 20% 3-HH-4 (3-1) 10% V2-BB(F)B-1 (3-8) 4% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=80.0°C; Tc<-20°C;Δn=0.096;Δε=-3.4; Vth=2.19 V; η=19.0 mPa·s. In the composition, the compound (1-3) was added in a ratio of 0.1% by weight. ), measure VHR-11. VHR-11=90.4%.

[Example 5] V2-BB(2F,3F)-O2 (2-5) 12% 1V2-BB(2F,3F)-O2 (2-5) 5% 1V2-BB(2F,3F)-O4 ( 2-5) 3% V-HHB(2F,3F)-O1 (2-7) 5% V-HHB(2F,3F)-O2 (2-7) 12% V-HHB(2F,3F)-O4 (2-7) 5% 3-HDhB(2F,3F)-O2 (2-13) 5% 3-dhBB(2F,3F)-O2 (2-16) 4% 3-HH-V (3-1 32% 1-BB-3 (3-3) 5% 3-HHEH-3 (3-4) 3% V-HHB-1 (3-5) 3% 1-BB(F)B-2V (3 -8) 3% 3-HHEBH-4 (3-9) The composition having a negative dielectric anisotropy was prepared at 3%, and the properties were measured. NI=78.6°C; Tc<-20°C;Δn=0.107;Δε=-2.7; Vth=2.36 V; η=18.8 mPa·s. In the composition, the compound was added in a ratio of 0.05% by weight. ), measure VHR-11. VHR-11=89.6%.

[Example 6] V2-BB(2F,3F)-O2 (2-5) 12% 1V2-BB(2F,3F)-O2 (2-5) 6% 1V2-BB(2F,3F)-O4 ( 2-5) 3% V-HHB(2F,3F)-O1 (2-7) 6% V-HHB(2F,3F)-O2 (2-7) 7% V-HHB(2F,3F)-O4 (2-7) 5% 1V2-HHB(2F,3F)-O4 (2-7) 5% 3-DhH1OB(2F,3F)-O2 (2-14) 5% 3-dhBB(2F,3F)- O2 (2-16) 5% 3-HH-V (3-1) 26% 3-HH-VFF (3-1) 3% V2-HB-1 (3-2) 6% V-HHB-1 ( 3-5) 5% 2-BB(F)B-5 (3-8) 3% 5-HBB(F)B-3 (3-13) 3% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=79.0°C; Tc<-20°C;Δn=0.112;Δε=-2.9; Vth=2.35 V; η=19.8 mPa·s. In the composition, the compound (1-5) was added in a ratio of 0.05% by weight. ), measure VHR-11. VHR-11=79.7%.

[Example 7] 3-H1OB(2F,3F)-O2 (2-4) 10% 1V2-BB(2F,3F)-O2 (2-5) 10% V-HHB(2F,3F)-O1 ( 2-7) 11% V-HHB(2F,3F)-O2 (2-7) 12% 3-HH1OB(2F,3F)-O2 (2-10) 9% 2-BB(2F,3F)B- 3 (2-11) 7% 3-HH-V (3-1) 26% 3-HH-V1 (3-1) 6% 1-HH-2V1 (3-1) 3% 3-HHB-3 ( 3-5) 3% V-HHB-1 (3-5) 3% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=81.6°C; Tc<-20°C;Δn=0.103;Δε=-3.7; Vth=2.15 V; η=20.9 mPa·s. In the composition, the compound (1-4) was added in a ratio of 0.06% by weight. ), measure VHR-11. VHR-11=66.8%.

[Example 8] 3-HB(2F,3F)-O2 (2-1) 8% 3-H1OB(2F,3F)-O2 (2-4) 8% 3-BB(2F,3F)-O2 ( 2-5) 5% 2-HH1OB(2F,3F)-O2 (2-10) 8% 3-HH1OB(2F,3F)-O2 (2-10) 7% 3-HDhB(2F,3F)-O2 (2-13) 10% 3-HH-V (3-1) 25% 3-HH-V1 (3-1) 10% V2-HHB-1 (3-5) 11% 2-BB(F)B -3 (3-8) 8% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=79.4°C; Tc<-20°C;Δn=0.100;Δε=-3.5; Vth=2.20 V; η=19.5 mPa·s. In the composition, the compound was added in a ratio of 0.1% by weight. ), measure VHR-11. VHR-11=68.9%.

[Example 9] V2-HB(2F,3F)-O2 (2-1) 5% 3-H2B(2F,3F)-O2 (2-3) 9% 3-HHB(2F,3F)-O2 ( 2-7) 12% 2-HH1OB(2F,3F)-O2 (2-10) 7% 3-HH1OB(2F,3F)-O2 (2-10) 12% 3-HDhB(2F,3F)-O2 (2-13) 3% 2-HH-3 (3-1) 27% 1-BB-3 (3-3) 13% 3-HHB-1 (3-5) 3% 3-B(F)BB -2 (3-7) 3% 3-HB(F)HH-5 (3-10) 3% 3-HB(F)BH-3 (3-12) 3% Preparation of dielectric anisotropy is negative The composition was measured for characteristics. NI=78.9°C; Tc<-20°C;Δn=0.098;Δε=-2.9; Vth=2.34 V; η=18.2 mPa·s. In the composition, the compound (1-1) was added in a ratio of 0.05% by weight. ), measure VHR-11. VHR-11=81.3%.

[Example 10] 5-H2B(2F,3F)-O2 (2-3) 9% 5-BB(2F,3F)-O4 (2-5) 5% 5-HHB(2F,3F)-O2 ( 2-7) 3% V-HHB(2F,3F)-O2 (2-7) 6% 3-HH2B(2F,3F)-O2 (2-9) 3% 3-HH1OB(2F,3F)-O2 (2-10) 13% 2-BB(2F,3F)B-3 (2-11) 3% 2-HHB(2F,3CL)-O2 (2-18) 3% 4-HHB(2F,3CL) -O2 (2-18) 3% 2-HH-3 (3-1) 22% 3-HH-V (3-1) 5% V2-BB-1 (3-3) 3% 1-BB-3 (3-3) 13% 3-HB(F)HH-5 (3-10) 3% 5-HBBH-3 (3-11) 3% 3-HB (F) BH-3 (3-12) 3% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=78.9°C; Tc<-20°C;Δn=0.103;Δε=-2.6; Vth=2.49 V; η=17.6 mPa·s. In the composition, the compound (1-3) was added in a ratio of 0.1% by weight. ), measure VHR-11. VHR-11=80.0%.

[Example 11] 3-H2B(2F,3F)-O2 (2-3) 20% 5-H2B(2F,3F)-O2 (2-3) 12% 3-HHB(2F,3F)-O2 ( 2-7) 8% 5-HHB(2F,3F)-O2 (2-7) 6% 3-HDhB(2F,3F)-O2 (2-13) 5% 3-HBB(2F,3F)-O2 (2-15) 10% 4-HBB(2F,3F)-O2 (2-15) 6% 2-HH-3 (3-1) 16% 3-HH-4 (3-1) 13% 1V- HBB-2 (3-6) 4% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=76.2°C; Tc<-20°C;Δn=0.089;Δε=-3.6; Vth=2.12 V; η=19.8 mPa·s. In the composition, the compound (1-3) was added in a ratio of 0.05% by weight. ), measure VHR-11. VHR-11=87.1%.

[Example 12] 3-HB(2F,3F)-O2 (2-1) 5% V-HB(2F,3F)-O4 (2-1) 4% 5-BB(2F,3F)-O2 ( 2-5) 6% 3-B(2F,3F)B(2F,3F)-O2 (2-6) 3% V-HHB(2F,3F)-O2 (2-7) 10% 3-HH1OB( 2F,3F)-O2 (2-10) 10% 2-BB(2F,3F)B-3 (2-11) 5% 4-HBB(2F,3F)-O2 (2-15) 5% V- HBB(2F,3F)-O2 (2-15) 7% 3-HBB(2F,3CL)-O2 (2-19) 3% 3-HH-O1 (3-1) 3% 3-HH-V ( 3-1) 26% 3-HB-O2 (3-2) 3% V-HHB-1 (3-5) 7% 3-BB(F)B-5 (3-8) 3% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=80.6°C; Tc<-20°C;Δn=0.114;Δε=-3.2; Vth=2.27 V; η=24.0 mPa·s. In the composition, the compound (1-4) was added in a ratio of 0.06% by weight. ), measure VHR-11. VHR-11=82.9%.

[Example 13] 3-chB(2F,3F)-O2 (2-2) 6% 3-BB(2F,3F)-O4 (2-5) 6% V2-BB(2F,3F)-O2 ( 2-5) 6% 3-HHB(2F,3F)-O2 (2-7) 5% V-HHB(2F,3F)-O1 (2-7) 6% V-HHB(2F,3F)-O2 (2-7) 9% 2-HchB(2F,3F)-O2 (2-8) 3% 3-DhHB(2F,3F)-O2 (2-12) 5% 3-HEB(2F,3F)B (2F,3F)-O2 (2-17) 3% 3-H1OCro(7F,8F)-5 (2-20) 3% 3-HH1OCro(7F,8F)-5 (2-21) 3% 3- HH-V (3-1) 23% 4-HH-V (3-1) 3% 5-HH-V (3-1) 6% 7-HB-1 (3-2) 3% V-HHB-1 (3-5) 4% V-HBB-2 (3-6) 3% 2-BB(F)B-3 (3-8) 3% Preparation of Dielectric The composition having an anisotropy was negative, and the characteristics were measured. NI=70.9°C; Tc<-20°C;Δn=0.092;Δε=-3.2; Vth=2.16 V; η=22.9 mPa·s. In the composition, the compound (1-5) was added in a ratio of 0.05% by weight. ), measure VHR-11. VHR-11=84.3%.

[Example 14] 5-H2B(2F,3F)-O2 (2-3) 9% 5-BB(2F,3F)-O4 (2-5) 5% 5-HHB(2F,3F)-O2 ( 2-7) 3% V-HHB(2F,3F)-O2 (2-7) 6% 3-HH2B(2F,3F)-O2 (2-9) 3% 3-HH1OB(2F,3F)-O2 (2-10) 13% 2-BB(2F,3F)B-3 (2-11) 3% 2-HHB(2F,3CL)-O2 (2-18) 3% 4-HHB(2F,3CL) -O2 (2-18) 3% 2-HH-3 (3-1) 22% 3-HH-V (3-1) 5% V2-BB-1 (3-3) 3% 1-BB-5 (3-3) 13% 3-HBB-2 (3-6) 3% 3-HB(F)HH-5 (3-10) 3% 3-HB(F)BH-3 (3-12) 3% Preparation of the composition having negative dielectric anisotropy, measurement characteristics . NI=76.1°C; Tc<-20°C;Δn=0.103;Δε=-2.6; Vth=2.47 V; η=16.8 mPa·s. In the composition, the compound (1-1) was added in a ratio of 0.05% by weight. ), measure VHR-11. VHR-11=82.3%.

[Example 15] 3-BB(2F,3F)-O4 (2-5) 6% V2-BB(2F,3F)-O2 (2-5) 12% 3-HHB(2F,3F)-O2 ( 2-7) 5% V-HHB(2F,3F)-O1 (2-7) 6% V2-HHB(2F,3F)-O2 (2-7) 12% 3-DhHB(2F,3F)-O2 (2-12) 5% 3-HEB(2F,3F)B(2F,3F)-O2 (2-17) 3% 3-H1OCro(7F,8F)-5 (2-20) 3% 3-HH1OCro (7F,8F)-5 (2-21) 3% 3-HH-V (3-1) 23% 4-HH-V (3-1) 3% 5-HH-V (3-1) 6% 7-HB-1 (3-2) 3% V-HHB-1 (3-5) 4% V-HBB-2 (3-6) 3% 2-BB (F) B-3 (3-8) 3% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=76.1°C; Tc<-20°C;Δn=0.099;Δε=-3.0; Vth=2.25 V; η=22.7 mPa·s. In the composition, the compound (1-4) was added in a ratio of 0.03 wt%. ), measure VHR-11. VHR-11=81.4%.

[Example 16] 3-H2B(2F,3F)-O2 (2-3) 20% 5-H2B(2F,3F)-O2 (2-3) 12% 3-HHB(2F,3F)-O2 ( 2-7) 8% 5-HHB(2F,3F)-O2 (2-7) 6% 3-HDhB(2F,3F)-O2 (2-13) 5% 3-HBB(2F,3F)-O2 (2-15) 10% 4-HBB(2F,3F)-O2 (2-15) 6% 2-HH-3 (3-1) 16% 3-HH-4 (3-1) 13% 1V- HBB-2 (3-6) 4% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=76.2°C; Tc<-20°C;Δn=0.089;Δε=-3.6; Vth=2.12 V; η=19.8 mPa·s. In the composition, the compound (1-2) was added in a ratio of 0.03% by weight. ), measure VHR-11. VHR-11=86.2%.

[Example 17] 3-BB(2F,3F)-O4 (2-5) 6% V2-BB(2F,3F)-O2 (2-5) 12% 3-HHB(2F,3F)-O2 ( 2-7) 8% V-HHB(2F,3F)-O1 (2-7) 6% V2-HHB(2F,3F)-O2 (2-7) 12% 3-DhHB(2F,3F)-O2 (2-12) 5% 3-HEB(2F,3F)B(2F,3F)-O2 (2-17) 3% 3-H1OCro(7F,8F)-5 (2-20) 3% 3-HH -V (3-1) 23% 4-HH-V (3-1) 3% 5-HH-V (3-1) 6% 7-HB-1 (3-2) 3% V-HHB-1 (3-5) 4% V-HBB-2 (3-6) 3% 2-BB(F)B-3 (3-8) 3% The composition having a negative dielectric anisotropy was prepared, and the properties were measured. NI=77.1°C; Tc<-20°C;Δn=0.100;Δε=-2.9; Vth=2.30 V; η=21.2 mPa·s. In the composition, the compound (1-5) was added in a ratio of 0.03 wt%. ), measure VHR-11. VHR-11=82.5%.

[Example 18] 3-HB(2F,3F)-O2 (2-1) 6% 3-BB(2F,3F)-O4 (2-5) 6% V2-BB(2F,3F)-O2 ( 2-5) 12% 3-HHB(2F,3F)-O2 (2-7) 8% V-HHB(2F,3F)-O1 (2-7) 6% V2-HHB(2F,3F)-O2 (2-7) 12% 3-HDhB(2F,3F)-O2 (2-13) 5% 3-HH-V (3-1) 23% 4-HH-V (3-1) 3% 5- HH-V (3-1) 6% 7-HB-1 (3-2) 3% V-HHB-1 (3-5) 4% V-HBB-2 (3-6) 3% 2-BB ( F) B-3 (3-8) The composition having a negative dielectric anisotropy was prepared at 3%, and the properties were measured. NI=72.3°C; Tc<-20°C;Δn=0.098;Δε=-2.8; Vth=2.28 V; η=17.8 mPa·s. In the composition, the compound (1-3) was added in a ratio of 0.1% by weight. ), measure VHR-11. VHR-11=85.8%.

The effects of adding the first additive in Examples 1 to 3 were compared. The voltage holding ratio was measured according to the method described in the measuring method (10). First, a composition to which the first additive is not added is injected into the TN element. After the element was irradiated with ultraviolet rays of 5 mW/cm ² for 167 minutes, the voltage holding ratio was measured. Then, the composition to which the first additive was added was injected into the TN device, and after the ultraviolet ray was irradiated in the same manner, the voltage holding ratio was measured. The effect of the first additive was evaluated by comparing the measured values. The results are summarized in Table 4. The voltage holding ratio (VHR-11) of the composition in which the first additive was not added in Examples 1 to 3 was about 36%. VHR-11 can be controlled to be about 67% by adding a first additive to the composition. The VHR-11 in Examples 4 to 18 was in the range of 66.8% to 90.4%, and a high voltage holding ratio was maintained. Therefore, the conclusion that the liquid crystal composition of the present invention has excellent characteristics can be obtained.

Table 4. Effect of adding the first additive [Industrial availability]

The liquid crystal composition of the present invention has high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, and high stability against heat. The at least one characteristic is satisfied or has an appropriate balance with respect to at least two characteristics. The liquid crystal display device including the composition can be used for a liquid crystal projector, a liquid crystal television, or the like because of its short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life.

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Claims (18)

A liquid crystal composition containing at least one compound selected from the group consisting of compounds represented by formula (1) as a first additive, having a negative dielectric anisotropy, and having a nematic phase, In the formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or an alkyl group having 1 to 4 carbon atoms; and ring A and ring B are independently Is a cyclohexyl group, a cyclohexene group, a decahydronaphthalenyl group, a dihydropyranyl group, a tetrahydropyranyl group, a dioxanediyl group, a phenylene group, a naphthyldiyl group, a pyrimidinediyl group or a pyridine. a diradical, and wherein at least one hydrogen in the ring may be substituted by fluorine, chlorine, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a carbon number substituted with at least one hydrogen by fluorine or chlorine a substituted alkyl group of 1 to 5; Z ^1, Z ² and Z ^{3 are} independently a single bond or a C 1-10 alkylene group, and the alkylene, at least one -CH ₂ - may be -O -, -S-, -CO-, -COO-, -OCO- or -SiH ₂ -, at least one -CH ₂ -CH ₂ - may be substituted by -CH=CH- or -C≡C-, In the group, at least one hydrogen may be substituted by fluorine or chlorine; a and b are independently 1 or 2; c is 0, 1 or 2, and when c is 0, ring A is cyclohexene, decalin a base, a dihydropyranodiyl group, a tetrahydropyranodiyl group, a dioxanediyl group, a naphthalenediyl group, a pyrimidinediyl group or a pyridyldiyl group, and wherein at least one hydrogen in the ring may be via fluorine, chlorine, carbon The alkyl group having 1 to 5 carbon atoms, the alkoxy group having 1 to 5 carbon atoms, or the alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine is substituted. The liquid crystal composition according to claim 1, which contains at least one compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-5) as a first additive, In the formulae (1-1) to (1-5), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen or an alkane having 1 to 4 carbon atoms. base. The liquid crystal composition according to claim 1 or 2, wherein the ratio of the first additive is in the range of 0.005 wt% to 1 wt% based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of the items 1 to 3, 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 ⁹ and R ^{10 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 an oxyalkylene having 2 to 12 carbon atoms. a C 1 to 12 alkyl group substituted with at least one hydrogen substituted with fluorine or chlorine; ring C and ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenyl, 1, 4-phenylene, at least one hydrogen substituted by fluorine or chlorine, 1,4-phenylene or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4- Phenyl, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene- 2,6-diyl or 7,8-difluorochroman-2,6-diyl; Z ⁴ and Z ^{5 are} independently a single bond, an extended ethyl group, a methyleneoxy group or a carbonyloxy group; 1, 2 or 3, e is 0 or 1; and the sum of d and e is 3 or less. The liquid crystal composition according to any one of the items 1 to 4, which contains at least one selected from the group consisting of compounds represented by formula (2-1) to formula (2-21). Compound as the first component, In the formulae (2-1) to (2-21), R ⁹ and R ^{10 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms. An alkenyloxy group having 2 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms substituted with at least one hydrogen via fluorine or chlorine. The liquid crystal composition according to Item 4 or 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 any one of claims 1 to 6, 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 ¹¹ and R ^{12 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 via fluorine or chlorine. a substituted alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms substituted with at least one hydrogen; the ring F and the ring G are independently 1,4-cyclohexylene, 1,4-stretch Phenyl, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁶ is a single bond, ethyl or carbonyloxy; f is 1, 2 or 3. The liquid crystal composition according to any one of claims 1 to 7, which contains at least one selected from the group consisting of compounds represented by formula (3-1) to formula (3-13). a compound as a second component, In the formulae (3-1) to (3-13), R ¹¹ and R ^{12 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 carbon atoms substituted by fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms substituted with at least one hydrogen via fluorine. The liquid crystal composition according to Item 7 or Item 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 any one of claims 1 to 9, which contains at least one polymerizable compound selected from the group consisting of compounds represented by formula (4) as a second additive, In the formula (4), Ring I and Ring K are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxin Alkan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and wherein at least one hydrogen in the ring may be through fluorine, chlorine, an alkyl group having 1 to 12 carbons, or an alkoxy group having 1 to 12 carbon atoms Substituting, or at least one hydrogen substituted with a C 1 to 12 alkyl group substituted by fluorine or chlorine; ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene Base, 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 a di-, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl group, and at least one hydrogen in the ring may be via fluorine, Chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms substituted with at least one hydrogen substituted by fluorine or chlorine; Z ⁷ and Z ^{8 are} independently a single bond or a C 1-10 alkylene group, and the alkylene, at least one -CH ₂ - may be -O -, - - COO- or -OCO-, at least, - CO A -CH ₂ -CH ₂ - may be -CH = CH -, - C ( CH 3) = CH -, - CH = C (CH 3) - or _{-C (CH 3) = C (} CH 3) - substituted , the group at least one hydrogen may be substituted by fluorine or chlorine; P ^1, P ² and P ³ are independently a polymerizable group; Sp ^1, Sp ² and Sp ³ independently a single bond or a C 1-10 And an alkylene group, wherein at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ -CH ₂ - may be - CH=CH- or -C≡C-substitution, wherein at least one hydrogen may be substituted by fluorine or chlorine; g is 0, 1 or 2; h, i and j are independently 0, 1, 2, 3 Or 4; and the sum of h, i and j is 1 or more. The liquid crystal composition according to claim 10, wherein, in the formula (4), P ¹ , P ² and P ^{3 are} independently selected from the group consisting of the formula (P-1) to the formula (P-5). Polymeric groups in the group of groups, In the formulae (P-1) to (P-5), M ¹ , M ² and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms or a carbon substituted with at least one hydrogen via fluorine or chlorine. A number of 1 to 5 alkyl groups. The liquid crystal composition according to any one of claims 1 to 11, which contains at least one selected from the group consisting of compounds represented by formula (4-1) to formula (4-27). a polymerizable compound as a second additive, In the formulae (4-1) to (4-27), P ⁴ , P ⁵ and P ^{6 are} independently selected from the group consisting of the groups represented by the formulae (P-1) to (P-3). Polymeric group; In the formulae (P-1) to (P-3), 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; in the formulae (4-1) to (4-27), Sp ¹ , Sp ² and Sp ^{3 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and In the alkyl group, at least one -CH ₂ - may be substituted by -O-, -COO-, -OCO- or -OCOO-, and at least one -CH ₂ -CH ₂ - may be via -CH=CH- or -C ≡C-substituted, wherein at least one hydrogen in the group may be substituted with fluorine or chlorine. The liquid crystal composition according to any one of claims 10 to 12, wherein the ratio of the second additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 13. The liquid crystal display device of claim 14, wherein the operation mode of the liquid crystal display device is a coplanar switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced photoreaction alignment mode, and the driving mode of the liquid crystal display element is Active matrix approach. A polymer-stabilized alignment type liquid crystal display device comprising the liquid crystal composition according to any one of claims 10 to 13, wherein the polymerizable compound in the liquid crystal composition is polymerized. A liquid crystal composition which is used for a liquid crystal display element, which is a liquid crystal composition according to any one of claims 1 to 13. A liquid crystal composition which is used for a polymer-stabilized alignment type liquid crystal display element, which is a liquid crystal composition according to any one of claims 10 to 13.