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

Abstract

Provided in the present invention are a liquid crystal composition and an AM element comprising the composition. The liquid crystal composition satisfies at least one characteristic, or has an appropriate balance with respect to at least two characteristics, among the characteristics of a high upper limit temperature, a low lower limit temperature, a low viscosity, large optical anisotropy, large negative dielectric constant anisotropy, a large elastic constant, a high specific resistance, high stability to light, and high stability to heat. The liquid crystal composition contains a specific compound having a low viscosity or a high upper limit temperature as a component A, and can also contain a specific compound having a high upper limit temperature or a low viscosity as a component B, a specific compound having large negative dielectric constant anisotropy as a component C, or a specific compound having a polymerizable group as an additive X.

Description

Liquid crystal compositions, liquid crystal display elements and their applications Technical Field

[0001] This invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, it relates to a liquid crystal composition with negative dielectric anisotropy, and a liquid crystal display element containing the composition and having modes such as IPS, VA, FFS, and FPA. This invention also relates to a polymer-stabilized alignment type liquid crystal display element. Background Technology

[0002] In liquid crystal display (LCD) elements, classification based on the operating mode of liquid crystal molecules includes 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 (FFS), and field-induced photo-reactive alignment (FPA). Classification based on the driving method of the element includes passive matrix (PM) and active matrix (AM). PM is further classified into static and multiplex types, while AM ​​is classified into thin-film transistor (TFT) and metal-insulator-metal (MIM) types. TFTs are classified into amorphous silicon and polycrystalline silicon. The latter is classified into high-temperature type and low-temperature type based on the manufacturing process. Based on the light source, it is classified into reflective type that uses natural light, transmissive type that uses backlight, and semi-transmissive type that uses both natural light and backlight.

[0003] Liquid crystal display elements contain a liquid crystal composition having a nematic phase. This composition possesses suitable properties. By improving the properties of this composition, AM elements with good properties can be obtained. The correlation among these properties is summarized in Table 1 below. The properties of the composition are further explained based on commercially available AM ​​elements. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferred upper limit temperature of the nematic phase is about 70°C or higher, and the preferred lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition is related to the response time of the element. For displaying moving images on the element, a short response time is preferred. Ideally, a response time shorter than 1 millisecond is desired. Therefore, a low viscosity of the composition is preferred. Even more preferred is a low viscosity at low temperatures.

[0004] Table 1. Properties of the composition and properties of the AM element

[0005] The optical anisotropy of the composition is related to the contrast of the element. Depending on the element mode, a large or small optical anisotropy, i.e., an appropriate optical anisotropy, is required. The product (Δn×d) of the optical anisotropy of the composition (Δn) and the element's cell gap (d) is designed to maximize the contrast. The appropriate value of the product depends on the type of operating mode. In VA mode elements, this value ranges from about 0.30 μm to about 0.40 μm, and in IPS or FFS mode elements, it ranges from about 0.20 μm to about 0.35 μm. In these cases, a composition with a large optical anisotropy is preferred for elements with a small cell gap. A large dielectric constant anisotropy of the composition contributes to a low critical voltage, low power consumption, and high contrast of the element. Therefore, a large dielectric constant anisotropy is preferred. A high resistivity of the composition contributes to a high voltage retention rate and high contrast of the element. Therefore, a composition with a high resistivity in the initial stage is preferred. Preferably, the composition retains a high specific resistivity even after prolonged use. The stability of the composition to light or heat is related to the lifespan of the component. Higher stability results in a longer component lifespan. This characteristic is particularly advantageous for AM components used in LCD monitors, LCD televisions, and the like.

[0006] In general liquid crystal display (LCD) elements, the vertical alignment of liquid crystal molecules can be achieved using a specific polyimide alignment film. In polymer sustained alignment (PSA) type LCD elements, a polymer is combined with the alignment film. First, a composition containing a small amount of a polymeric compound is injected into the element. Next, a voltage is applied between the substrates of the element, and the composition is irradiated with ultraviolet light. The polymeric compound polymerizes, forming a polymer mesh structure within the composition. In this composition, the alignment of liquid crystal molecules can be controlled by the polymer, thus shortening the element's response time and improving image retention. This effect of the polymer is expected in elements with modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

[0007] Compositions with positive dielectric anisotropy are used in AM elements with TN mode. Compositions with negative dielectric anisotropy are used in AM elements with VA mode. Compositions with positive or negative dielectric anisotropy are used in AM elements with IPS or FFS mode. Compositions with positive or negative dielectric anisotropy are used in polymer sustained alignment (PSA) type AM elements.

[0008] In order to meet the required characteristics of liquid crystal display elements as described above, various compounds have been studied and compounds with three cyclohexane rings or compounds with fluorinated alkenyl groups at the ends have been developed (Patent Document 1 and Patent Document 2, etc.).

[0009] Compounds with three cyclohexane rings can be formulated into specific compounds by selectively using bonding groups and terminal groups. When used in liquid crystal compositions, they satisfy excellent properties, but so far no research has been conducted on their use in general liquid crystal display elements.

[0010] [Existing Technical Documents]

[0011] [Patent Literature]

[0012] [Patent Document 1] Japanese Patent Application Publication No. 2018-044143

[0013] [Patent Document 2] International Publication No. 1998 / 08791 Summary of the Invention

[0014] [The technical problem that this invention aims to solve]

[0015] The technical problem of this invention is to provide a liquid crystal composition that satisfies at least one of the following characteristics: high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, high optical anisotropy, high negative dielectric constant anisotropy, high elastic constant, high resistivity, high light stability, and high thermal stability. Another technical problem is to provide a liquid crystal composition that achieves a suitable balance among at least two of these characteristics. Yet another technical problem is to provide a liquid crystal display element containing such a composition. A further objective is to provide an AM element with characteristics such as short response time, high voltage retention rate, low critical voltage, high contrast ratio, and long lifespan.

[0016] [Methods for solving technical problems]

[0017] The present invention relates to a liquid crystal composition and a liquid crystal display element containing the composition, wherein the liquid crystal composition contains at least one compound selected from the compounds represented by formula (1) as component A and has negative dielectric anisotropy.

[0018] In equation (1),

[0019] R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine;

[0020] R 2 It is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine;

[0021] Z 1 It is a single bond or a vinylidene bond;

[0022] Where R 2 When it is an alkyl group with 1 to 12 carbon atoms, Z 1 It is vinylidene, and R 1 It is an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms;

[0023] When R 2 When R is an alkenyl group with 2 to 12 carbon atoms 1 It is an alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0024] [The effects of the invention]

[0025] The advantages of this invention are that it provides a liquid crystal composition that satisfies at least one of the following characteristics: high upper limit temperature of the nematic phase, low lower limit temperature of the nematic phase, low viscosity, high optical anisotropy, high negative dielectric constant anisotropy, high elastic constant, high resistivity, high light stability, and high thermal stability. Another advantage is that it provides a liquid crystal composition that achieves a suitable balance among at least two of these characteristics. Yet another advantage is that it provides a liquid crystal display element containing this composition. A further advantage is that it provides an AM element with characteristics such as short response time, high voltage retention rate, low critical voltage, high contrast ratio, and long lifespan. Detailed Implementation

[0026] The usage of terms in this specification is as follows. Sometimes, the terms "liquid crystal composition" and "liquid crystal display element" are abbreviated as "composition" and "element," respectively. "Liquid crystal display element" is a general term for liquid crystal display panels and liquid crystal display modules. "Liquid crystal compound" is a general term for compounds having a liquid crystal phase such as a nematic or laminamatic phase, as well as compounds that, although not having a liquid crystal phase, are mixed in the composition for the purpose of adjusting the temperature range, viscosity, dielectric anisotropy, and other properties of the nematic phase. This compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecules (liquid crystal molecules) are rod-like. "Polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. Liquid crystal compounds containing alkenes are not classified as polymerizable compounds in this sense.

[0027] Liquid crystal compositions are prepared by mixing various liquid crystal compounds. Additives such as optically active compounds or polymerizable compounds are added to the liquid crystal composition as needed. Even when additives are added, the proportion of liquid crystal compounds is expressed as a mass percentage (mass %) based on the mass of the liquid crystal composition excluding additives. The proportion of additives is expressed as a mass percentage (mass %) based on the mass of the liquid crystal composition excluding additives. That is, the proportion of liquid crystal compounds or additives is calculated based on the total mass of the liquid crystal compounds. Sometimes parts per million (ppm) are used. The proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the mass of the polymerizable compounds.

[0028] Sometimes the "upper limit temperature of the nematic phase" is abbreviated as "upper limit temperature." Sometimes the "lower limit temperature of the nematic phase" is abbreviated as "lower limit temperature." The expression "increased dielectric anisotropy" means a positive increase in the dielectric constant value for compositions with positive dielectric anisotropy, and a negative increase for compositions with negative dielectric anisotropy. "High voltage retention rate" means that the device maintains a high voltage retention rate not only at room temperature but also at temperatures close to the upper limit temperature in the initial stage, and continues to maintain a high voltage retention rate not only at room temperature but also at temperatures close to the upper limit temperature after prolonged use. Sometimes, time-varying tests are used to study the characteristics of compositions or devices.

[0029] Let's take compound (1z) as an example. In formula (1z), the codes for α and β, enclosed by hexagons, correspond to ring α and ring β, respectively, and represent six-membered rings, condensed rings, etc. When the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings α can be the same or different. This rule applies to any two rings α when the subscript 'x' is greater than 2. This rule also applies to other codes such as bonding groups Z. The diagonal line that cuts across one side of ring β indicates that any hydrogen on ring β can be replaced by a substituent (-Sp-P). The subscript 'y' indicates the number of substituents. When the subscript 'y' is 0, there is no such substitution. When the subscript 'y' is 2 or more, there are multiple substituents (-Sp-P) on ring β. In this case, the rule of "can be the same or different" also applies. Furthermore, this rule also applies when the code Ra is used in multiple compounds.

[0030] In formula (1z), for example, the statement "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group consisting of alkyl, alkoxy, and alkenyl groups. That is, the group represented by Ra and the group represented by Rb may be the same or different.

[0031] Sometimes, at least one compound selected from the compounds represented by formula (1z) is abbreviated as "compound (1z)". "Compound (1z)" refers to one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1z). The same applies to compounds represented by other formulas. The statement "at least one compound selected from the compounds represented by formula (1z) and formula (2z)" means at least one compound selected from the group consisting of compound (1z) and compound (2z).

[0032] The statement "at least one 'A'" means that the number of 'A's is arbitrary. The statement "at least one 'A' can be replaced by 'B'" means that when there is only one 'A', the position of 'A' is arbitrary; when there are two or more 'A's, their positions can also be chosen without restriction. Sometimes the statement "at least one -CH2- can be replaced by -O-" is used. In this case, -CH2CH2-CH2- can be converted to -O-CH2-O- by replacing a non-adjacent -CH2- with -O-. However, there is no case where an adjacent -CH2- is replaced by -O-. The reason is that -OO-CH2- (peroxide) is formed in this substitution.

[0033] When simply referred to as "alkyl," the alkyl group in a liquid crystal compound is either straight-chain or branched, and does not contain cycloalkyl groups. A clear distinction must be made between "alkyl" and "cycloalkyl." Straight-chain alkyl groups are preferred over branched-chain alkyl groups. The same applies to terminal groups such as alkoxy and alkenyl groups. Regarding the stereoconfiguration associated with 1,4-cyclohexylene, the trans configuration is preferred over the cis configuration to increase the upper temperature limit. Because 2-fluoro-1,4-phenylene is asymmetrical, both left-facing (L) and right-facing (R) configurations exist.

[0034] The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same also applies to bonding groups such as carbonyloxy groups (-COO- or -OCO-).

[0035] The present invention includes the following items, etc.

[0036] Item 1. A liquid crystal composition comprising at least one compound selected from the compounds represented by formula (1) as component A, and having negative dielectric anisotropy.

[0037] In equation (1),

[0038] R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine;

[0039] R 2 It is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine;

[0040] Z 1 It is a single bond or a vinylidene bond;

[0041] Where R 2 When it is an alkyl group with 1 to 12 carbon atoms, Z 1It is vinylidene, and R 1 It is an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms;

[0042] When R 2 When R is an alkenyl group with 2 to 12 carbon atoms 1 It is an alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0043] Item 2. The liquid crystal composition as described in Item 1, comprising at least one compound selected from the compounds represented by formulas (1-1) to (1-7) as component A.

[0044] In equations (1-1) to (1-6),

[0045] R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine;

[0046] R 2 It is an alkenyl group having 2 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine;

[0047] In equation (1-7),

[0048] R 17 It is an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.

[0049] Item 3. The liquid crystal composition as described in Item 1 or Item 2, wherein the proportion of component A is in the range of 1% by mass to 20% by mass.

[0050] Item 4. The liquid crystal composition as described in any one of Items 1 to 3, comprising at least one compound selected from the compounds represented by Formula (2) and Formula (3) as component B.

[0051] In equation (2),

[0052] R 3 and R 4 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine;

[0053] Ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;

[0054] Z 2It can be a single bond, ethylidene, vinylidene, methyleneoxy, or carbonyloxy;

[0055] In equation (3),

[0056] R 5 and R 6 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine;

[0057] Ring D and ring E are 1,4-cyclohexene, 1,4-cyclohexenyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene;

[0058] Z 3 It can be a single bond, ethylidene, methyleneoxy, or carbonyloxy;

[0059] a is 2 or 3;

[0060] Where a is 2 and Z 3 When it is a single bond, ring E is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.

[0061] Item 5. The liquid crystal composition of any one of Items 1 to 4, comprising at least one compound selected from the compounds represented by formulas (2-1) to (2-3) and (3-1) to (3-11) as component B.

[0062] In equations (2-1) to (2-3),

[0063] R 3 and R 4 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine;

[0064] In equations (3-1) to (3-11),

[0065] R 5 and R 6 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0066] Item 6. The liquid crystal composition as described in Item 4 or Item 5, wherein the proportion of component B is in the range of 20% by mass to 80% by mass.

[0067] Item 7. The liquid crystal composition as described in any one of Items 1 to 6, comprising at least one compound selected from the compounds represented by Formula (4) and Formula (5) as component C.

[0068] In equation (4),

[0069] R 7 and R 8 It is hydrogen, 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, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine;

[0070] The ring F and ring H are 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromoline-2,6-diyl, or chromoline-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine;

[0071] Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 1,8-difluorophenanthrene-2,7-diyl, 3,4,5-trifluoronaphthyl-2,6-diyl, 7,8-difluorochrome-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl;

[0072] Z 4 and Z 5 It can be a single bond, ethylidene, vinylidene, methyleneoxy, or carbonyloxy;

[0073] b is 0, 1, 2, or 3; c is 0 or 1; the sum of b and c is less than 3;

[0074] In equation (5),

[0075] R 9 and R 10 It is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0076] X 1 and X 2 It is oxygen or sulfur;

[0077] Y 1 and Y 2 It can be hydrogen, fluorine, or trifluoromethyl;

[0078] Ring I and ring J are 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromane-2,6-diyl, chromane-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, fluorene-2,7-diyl, or rings with at least one hydrogen substituted by fluorine or chlorine. Fluorine-2,7-diyl, dibenzofuran-3,7-diyl, dibenzofuran-3,7-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-3,7-diyl, indane-2,5-diyl, indane-2,5-diyl, thiophene-2,5-diyl, or furan-2,5-diyl are fluorine- or chlorine-substituted.

[0079] Z 6 and Z 7 It can be a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, or carbonyloxy;

[0080] d and e are 0 or 1.

[0081] Item 8. The liquid crystal composition as described in any one of Items 1 to 7, comprising at least one compound selected from the compounds represented by formulas (4-1) to (4-36) and (5-1) to (5-3) as component C.

[0082] In equations (4-1) to (4-36),

[0083] R 7 and R 8 It is hydrogen, 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, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine;

[0084] In equations (5-1) to (5-3),

[0085] R 9 and R 10 It is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0086] Y 1 and Y 2 It can be hydrogen, fluorine, or trifluoromethyl.

[0087] Item 9. The liquid crystal composition as described in Item 7 or Item 8, wherein the proportion of component C is in the range of 10% by mass to 70% by mass.

[0088] Item 10. The liquid crystal composition as described in any one of items 1 to 9, comprising at least one compound selected from the polymerizable compounds represented by formula (6) as additive X.

[0089] In equation (6),

[0090] Ring L and ring N are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridin-2-yl, wherein at least one hydrogen atom may be substituted by 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 in which at least one hydrogen atom is substituted by fluorine or chlorine; ring M is 1,4-cyclohexene, 1,4-cyclohexenyl, 1,4-phenylene, naphth-1,2-diyl, naphth-1,3-diyl, or naphth-1, 4-Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, wherein in these rings at least one hydrogen atom may be substituted by 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 whose at least one hydrogen atom is substituted by fluorine or chlorine;

[0091] Z 8 and Z 9 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- can be substituted by -O-, -CO-, -COO-, or -OCO-, and at least one -CH2CH2- can be substituted by -CH=CH-, -C(CH3)=CH-, -CH=C(CH3)-, or -C(CH3)=C(CH3)-, and wherein at least one hydrogen atom can be substituted by fluorine or chlorine;

[0092] P 1 To P 3 It is a polymerizable group; Sp 1 To Sp 3It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- can be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH2CH2- can be substituted by -CH=CH- or -C≡C-, and in these groups at least one hydrogen can be substituted by fluorine or chlorine;

[0093] h is 0, 1, or 2; i, j, and k are 0, 1, 2, 3, or 4; and the sum of i, j, and k is 1 or more.

[0094] Item 11. The liquid crystal composition as described in Item 10, wherein in formula (6), P 1 To P 3 It is a group selected from the polymerizable groups represented by formulas (P-1) to (P-5).

[0095] In equations (P-1) to (P-5), M 1 To M 3 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0096] Item 12. The liquid crystal composition as described in any one of Items 1 to 11, comprising at least one compound selected from polymerizable compounds represented by formulas (6-1) to (6-29) as additive X.

[0097] In equations (6-1) to (6-29), Sp 1 To Sp 3 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- can be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH2CH2- can be substituted by -CH=CH- or -C≡C-, and in these groups, at least one hydrogen atom can be substituted by fluorine or chlorine; P 4 To P 6 It is a polymerizable group selected from the groups represented by formulas (P-1) to (P-3);

[0098] In equations (P-1) to (P-3), M 1 To M 3 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0099] Item 13. The liquid crystal composition of any one of items 10 to 12, wherein the proportion of additive X is in the range of 0.03% by mass to 10% by mass.

[0100] Item 14. A liquid crystal display element comprising a liquid crystal composition as described in any one of items 1 to 13.

[0101] Item 15. The liquid crystal display element as described in Item 14, wherein the operating mode is IPS mode, VA mode, FFS mode, PSA mode, or FPA mode, and the driving method is active matrix mode.

[0102] Item 16. A polymer-stabilized alignment type liquid crystal display element comprising a liquid crystal composition as described in any one of Items 10 to 13, wherein the polymeric compound in the liquid crystal composition is polymerized.

[0103] Item 17. Use of a liquid crystal composition, said liquid crystal composition being any one of items 1 to 13, for use in a liquid crystal display element.

[0104] Item 18. Use of a liquid crystal composition, said liquid crystal composition being any one of items 10 to 13, for use in a polymer-stabilized alignment type liquid crystal display element.

[0105] The present invention also includes the following: (a) the composition comprising one, two, or three or more compounds selected from additives such as optically active compounds, antioxidants, UV absorbers, matting agents, pigments, defoamers, polymerizable compounds, polymerization initiators, and polymerization inhibitors. (b) an AM element comprising the composition. (c) the composition further comprising a polymerizable compound, and a polymer-stabilized alignment (PSA) type AM element comprising the composition. (d) a polymer-stabilized alignment (PSA) type AM element comprising the composition, wherein the polymerizable compound in the composition is polymerized. (e) an element comprising the composition and having a PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA pattern. (f) a transmissive element comprising the composition. (g) use of the composition as a composition having a nematic phase. (h) use of an optically active composition obtained by adding an optically active compound to the composition.

[0106] The compositions of the present invention will be described in the following order: First, the composition's structure will be described. Second, the main characteristics of the component compounds and their main effects on the composition or element will be described. Third, the combination of component compounds in the composition, their preferred proportions, and the basis thereof will be described. Fourth, the preferred forms of the component compounds will be described. Fifth, preferred component compounds will be shown. Sixth, additives that can be added to the composition will be described. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition will be described.

[0107] First, the composition of the composition will be described. The composition contains a variety of liquid crystal compounds. The composition may also contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, etc. From the viewpoint of liquid crystal compounds, the composition is classified as composition (a) and composition (b). Composition (a) may contain liquid crystal compounds selected from compounds (1), (2), (3), (4), and (5), and may further contain other liquid crystal compounds, additives, etc. "Other liquid crystal compounds" are liquid crystal compounds that are different from compounds (1), (2), (3), (4), and (5). Such compounds are mixed into the composition for the purpose of further adjusting the properties.

[0108] Composition (b) substantially contains only liquid crystal compounds selected from compounds (1), (2), (3), (4), and (5). "Substantially" means that composition (b) may contain additives but not other liquid crystal compounds. Compared to composition (a), composition (b) has fewer components. From the viewpoint of cost reduction, composition (b) is superior to composition (a). From the viewpoint that properties can be further adjusted by mixing with other liquid crystal compounds, composition (a) is superior to composition (b).

[0109] Second, the main characteristics of the component compounds and their main effects on the composition or element are described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the codes of Table 2, L indicates large or high, M indicates moderate, and S indicates small or low. Codes L, M, and S are classifications based on qualitative comparisons between component compounds, and 0 (zero) means less than S.

[0110] Table 2. Properties of liquid crystal compounds

[0111] 1) The dielectric constant is negative and the code represents the magnitude of the absolute value.

[0112] The main effects of the component compounds are as follows. Compound (1) reduces viscosity or increases the upper limit temperature. Compound (2) or compound (3) increases the upper limit temperature or reduces viscosity. Compound (4) or compound (5) increases dielectric anisotropy or decreases the lower limit temperature. Compound (6) provides a polymer through polymerization. This polymer shortens the response time of the device and improves image retention by stabilizing the alignment of liquid crystal molecules.

[0113] Third, the combination of component compounds in the composition, the preferred proportions, and the basis for these proportions are explained. Preferred combinations of component compounds in the composition are: compound (1) + compound (4), compound (1) + compound (5), compound (1) + compound (4) + compound (5), compound (1) + compound (2) + compound (4), compound (1) + compound (2) + compound (5), compound (1) + compound (3) + compound (4), compound (1) + compound (3) + compound (5), compound (1) + compound (2) + compound (4) + compound (5), compound (1) + compound (3) + compound (4) + compound (5). Compound (1) + Compound (2) + Compound (3) + Compound (4), Compound (1) + Compound (2) + Compound (3) + Compound (5), Compound (1) + Compound (2) + Compound (4) + Compound (5) + Compound (6), Compound (1) + Compound (3) + Compound (4) + Compound (5) + Compound (6), Compound (1) + Compound (2) + Compound (3) + Compound (4) + Compound (5), or Compound (1) + Compound (2) + Compound (3) + Compound (4) + Compound (5) + Compound (6). The best combination is then Compound (1) + Compound (2) + Compound (4) or Compound (1) + Compound (2) + Compound (3) + Compound (4).

[0114] To reduce viscosity and increase the upper temperature limit, the preferred proportion of component A (compound (1)) is about 1% by mass or more, and to improve dielectric anisotropy, the preferred proportion of component A (compound (1)) is about 20% by mass or less. More preferably, the proportion is in the range of about 2% by mass to about 15% by mass. Particularly preferred, the proportion is in the range of about 2% by mass to about 10% by mass.

[0115] To increase the upper temperature limit or to reduce viscosity, the preferred proportion of component B (compounds (2) and (3)) is about 20% by mass or more. To increase dielectric anisotropy, the preferred proportion of component B (compounds (2) and (3)) is about 80% by mass or less. More preferably, the proportion is in the range of about 25% by mass to about 70% by mass. Particularly preferred, the proportion is in the range of about 30% by mass to about 70% by mass.

[0116] The preferred proportion of compound (2) is in the range of about 20% by mass to about 60% by mass.

[0117] To improve dielectric anisotropy, the preferred proportion of component C (compounds (4) and (5)) is about 10% by mass or more. To reduce viscosity or to lower the lower limit temperature, the preferred proportion of component C (compounds (4) and (5)) is about 70% by mass or less. More preferably, the proportion is in the range of about 20% by mass to about 60% by mass. Particularly preferred, the proportion is in the range of about 30% by mass to about 60% by mass.

[0118] Compound (6) is added to the composition for the purpose of suitable polymer-stabilized alignment of the element. To align the liquid crystal molecules, the preferred proportion of compound (6) is about 0.03% by mass or more; to prevent display defects of the element, the preferred proportion of compound (6) is about 10% by mass or less. More preferably, the proportion ranges from about 0.1% by mass to about 2% by mass. Particularly preferred, the proportion ranges from about 0.2% by mass to about 1.0% by mass.

[0119] Fourth, the preferred forms of the component compounds are described. In formulas (1), (2), (3), (4), and (5), R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine. For improved stability, R is preferred. 1 For alkyl groups having 1 to 12 carbon atoms, R is preferred to reduce viscosity. 1 Alkenyl groups with 2 to 12 carbon atoms. Excellent R 1 It is an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, with propyl being the most preferred. R 2 It is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine. Preferred R 2 It is an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine. The best R 2 It is an alkenyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms in which at least one hydrogen atom is substituted by fluorine. R is preferred.1 It is an alkyl group having 1 to 12 carbon atoms and R 2 A combination of alkenyl groups having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine, or R 1 It is an alkenyl group with 2 to 12 carbon atoms and R 2 A combination of alkyl groups having 1 to 12 carbon atoms. R 3 and R 4 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine. For improved stability, R is preferred. 3 or R 4 For alkyl groups having 1 to 12 carbon atoms, R is preferred to reduce viscosity. 3 or R 4 It is an alkenyl group with 2 to 12 carbon atoms. R 5 and R 6 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine. For improved stability, R is preferred. 5 or R 6 For alkyl groups having 1 to 12 carbon atoms, R is preferred to reduce viscosity. 5 or R 6 It is an alkenyl group with 2 to 12 carbon atoms. R 7 and R 8 It is hydrogen, 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, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine. For improved stability, R is preferred. 7 or R 8 For alkyl groups having 1 to 12 carbon atoms, R is preferred to reduce viscosity. 7 or R 8 For alkenyl groups with 2 to 12 carbon atoms, to improve dielectric anisotropy, a preferred R... 7 or R 8 It is an alkoxy group having 1 to 12 carbon atoms. R 9 and R 10 It is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, 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 in which at least one hydrogen atom is substituted by fluorine or chlorine. For improved stability, R is preferred. 9 and R 10 For alkyl groups with 1 to 12 carbon atoms, in order to improve the anisotropy of the dielectric constant, the preferred R is... 9 and R10 It is an alkoxy group with 1 to 12 carbon atoms.

[0120] Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. Further preferred alkyl groups are methyl, ethyl, propyl, butyl, or pentyl to reduce viscosity.

[0121] Preferred cycloalkyl groups are cyclopropyl, cyclobutyl, or cyclopentyl.

[0122] Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, or heptoxy. Furthermore, to reduce viscosity, methoxy or ethoxy groups are preferred.

[0123] Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. To reduce viscosity, further preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred stereoconfiguration of the -CH=CH- group in these alkenyl groups depends on the position of the double bond. For the purpose of reducing viscosity, etc., the trans configuration is preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl. The cis configuration is preferred among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

[0124] Preferred olefin groups are ethoxy, propenoxy, 3-butenoxy, 3-pentenoxy, or 4-pentenoxy. To reduce viscosity, propenoxy or 3-butenoxy are even more preferred.

[0125] Preferred examples of alkyl groups in which at least one hydrogen atom is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7-fluoroheptyl, or 8-fluorooctyl. Further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl to improve dielectric anisotropy.

[0126] Preferred examples of an alkenyl group in which at least one hydrogen atom is substituted by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. For reducing viscosity, 2,2-difluorovinyl or 4,4-difluoro-3-butenyl are even more preferred examples.

[0127] Rings B, C, D, and E are 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. For reducing viscosity, rings B, C, D, or E are preferably 1,4-cyclohexylene; for improving optical anisotropy, rings B, C, D, or E are preferably 1,4-phenylene.

[0128] Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 1,8-difluorophenanthrene-2,7-diyl, 3,4,5-trifluoronaphthyl-2,6-diyl, 7,8-difluorochrome-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4).

[0129] To reduce viscosity, the preferred ring G is 2,3-difluoro-1,4-phenylene, and to improve dielectric anisotropy, the preferred ring G is 1,8-difluorophenanthrene-2,7-diyl or 4,6-difluorodibenzothiophene-3,7-diyl.

[0130] The ring F and ring H are 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromoline-2,6-diyl, or chromoline-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine. Preferred examples of "1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, or 2-chloro-3-fluoro-1,4-phenylene.

[0131] The tetrahydropyran-2,5-diyl group in ring F and ring H is:

[0132] or

[0133] The preferred option is:

[0134] To reduce viscosity or to increase the upper limit temperature, the preferred ring F or ring H is 1,4-cyclohexylene, and to reduce the lower limit temperature, the preferred ring F or ring H is 1,4-phenylene.

[0135] Ring I and ring J are 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromane-2,6-diyl, chromane-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, fluorene-2,7-diyl, or rings with at least one hydrogen substituted by fluorine or chlorine. Fluorine-2,7-diyl, dibenzofuran-3,7-diyl, dibenzofuran-3,7-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-3,7-diyl, indane-2,5-diyl, indane-2,5-diyl, thiophene-2,5-diyl, or furan-2,5-diyl are all fluorine- or chlorine-substituted. Preferred ring I or ring J is 1,4-cyclohexylene or 1,4-phenylene.

[0136] Z 1 It is a single bond or a vinylidene bond. Z 2 It can be a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. For reducing viscosity, Z is preferred. 2 It is a single bond. Z 3 It can be a single bond, ethylidene, methyleneoxy, or carbonyloxy. For reducing viscosity, Z is preferred. 3 It is a single bond. Z 4 and Z 5 It can be a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. For reducing viscosity, Z is preferred. 4 or Z 5 For single bonds, to improve the elastic constant, the optimal Z... 4 or Z 5 For ethylene, to improve dielectric anisotropy, the preferred Z is... 4 or Z 5 It is a methylene oxide. Z 6 and Z 7 It can be a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, or carbonyloxy. For reducing viscosity, Z is preferred. 6 、or Z 7 For single bonds, to improve dielectric anisotropy, a better Z-axis is preferred. 6 、or Z 7 It is a methylene oxide.

[0137] Divalent groups such as methyleneoxy groups are asymmetrical. Among methyleneoxy groups, -CH2O- is preferred over -OCH2-. Among carbonyloxy groups, -COO- is preferred over -OCO-.

[0138] a is 2 or 3. To reduce viscosity, a is preferably 2; to improve optical anisotropy or to increase the upper temperature limit, a is preferably 3. b is 0, 1, or 2; c is 0 or 1, and the sum of b and c is 3 or less. To reduce viscosity, b is preferably 0; to increase the upper temperature limit, b is preferably 1. To reduce viscosity, c is preferably 0; to increase the upper temperature limit, c is preferably 1. d and e are 0 or 1. To reduce viscosity, d or e is preferably 0; to increase the upper temperature limit, d or e is preferably 1.

[0139] In equation (1), R 2 When it is an alkyl group with 1 to 12 carbon atoms, Z 1 It is vinylidene, and R 1 It is an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.

[0140] In equation (1), R 2 When R is an alkenyl group with 1 to 12 carbon atoms 1 It is an alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

[0141] In equation (3), a is 2 and Z 3 When it is a single bond, ring E is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.

[0142] In formula (6), ring L and ring N are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridin-2-yl, wherein at least one hydrogen atom may be substituted by 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 by fluorine or chlorine. Preferably, ring L or ring N is phenyl. Ring M is 1,4-cyclohexene, 1,4-cyclohexenyl, 1,4-phenylene, 1,2-diyl, 1,3-diyl, 1,4-diyl, 1,5-diyl, 1,6-diyl, 1,7-diyl, 1,8-diyl, 2,3-diyl, 2,6-diyl, 2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidin-2,5-diyl, or pyridine-2,5-diyl, wherein at least one hydrogen atom may be substituted by 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 in which at least one hydrogen atom is substituted by fluorine or chlorine. Preferred ring M is 1,4-phenylene or 2-fluoro-1,4-phenylene.

[0143] Z 8 and Z 9It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- group can be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -CH2CH2- group can be substituted with -CH=CH-, -C(CH3)=CH-, -CH=C(CH3)-, or -C(CH3)=C(CH3)-, and in these groups, at least one hydrogen atom can be substituted with fluorine or chlorine. Preferred Z 8 or Z 9 It can be a single bond, -CH2CH2-, -CH2O-, -OCH2-, -COO-, or -OCO-. Therefore, the best Z... 8 or Z 9 It is a single key.

[0144] Sp 1 To Sp 3 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- group can be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH2CH2- group can be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen atom can be substituted with fluorine or chlorine. Preferred Sp 1 To Sp 3 These are single bonds, -CH2CH2-, -CH2O-, -OCH2-, -COO-, -OCO-, -CO-CH=CH-, or -CH=CH-CO-. Furthermore, the best Sp... 1 To Sp 3 It is a single key.

[0145] h is 0, 1, or 2. Preferably, h is 0 or 1. i, j, and k are 0, 1, 2, 3, or 4, and the sum of i, j, and k is 1 or more. Preferably, i, j, or k is 1 or 2.

[0146] P 1 To P 3 It is a polymerizable group. Preferred P 1 To P 3 The polymerizable group is selected from the groups represented by formulas (P-1) to (P-5). Furthermore, P is preferred. 1 To P 3 The group represented by formula (P-1), formula (P-2), or formula (P-3). Preferred P 1 To P 3 The group represented by formula (P-1) or formula (P-2). The optimal P 1 To P 3 The group represented by formula (P-1). The preferred group represented by formula (P-1) is -OCO-CH=CH2 or -OCO-C(CH3)=CH2. The wavy lines in formulas (P-1) to (P-5) indicate the bonding sites.

[0147] In equations (P-1) to (P-5), M 1 To M 3 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine. For improved reactivity, M is preferred. 1 To M 3 It is hydrogen or methyl. Therefore, the preferred M... 1 It is hydrogen or methyl, and thus preferably M 2 Or M 3 It is hydrogen.

[0148] In equations (6-1) to (6-29), P 4 To P 6 The group represented by formulas (P-1) to (P-3). Preferred P 4 To P 6 The group represented by formula (P-1) or formula (P-2). Preferably, the group represented by formula (P-1) is -OCO-CH=CH2 or -OCO-C(CH3)=CH2. The wavy lines in formulas (P-1) to (P-3) indicate the bonding sites.

[0149] Fifth, preferred component compounds are shown. Preferred compound (1) is compounds (1-1) to (1-7) as described in item 2. Particularly preferred compound (1) is compound (1-3) or compound (1-7).

[0150] The preferred compound (2) is compound (2-1) to compound (2-3) as described in item 5. Among these compounds, at least one of component B is preferably compound (2-1) or compound (2-3). More preferably, at least one of component B is compound (2-1). The proportion of compound (2-1) is preferably 15% by mass or more, and more preferably 20% by mass or more.

[0151] Preferred compound (3) is compounds (3-1) to (3-11) as described in item 5. Among these compounds, at least one of component C is preferably compound (3-2), compound (3-3), or compound (3-5). Particularly preferred compound (3) is compound (3-2) or compound (3-3).

[0152] The preferred compound (4) is compound (4-1) to compound (4-36) as described in item 8. Among these compounds, at least one of component C is preferably compound (4-1), compound (4-3), compound (4-6), compound (4-8), compound (4-9), compound (4-10), compound (4-14), or compound (4-36). Preferably, component C is a combination of at least two compounds (4-8) and (4-9), compound (4-8) and (4-10), compound (4-8) and (4-14), compound (4-8) and (4-36), compound (4-9) and (4-10), compound (4-9) and (4-14), compound (4-9) and (4-36), compound (4-10) and (4-14), compound (4-10) and (4-36), or compound (4-14) and (4-36).

[0153] The preferred compound (5) is compound (5-1) to compound (5-3) as described in item 8.

[0154] Preferred compound (6) is compound (6-1) to compound (6-29) as described in item 12. Among these compounds, at least one of additive X is preferably compound (6-1), compound (6-2), compound (6-24), compound (6-25), compound (6-26), or compound (6-27). Preferred at least two of additive X are combinations of compound (6-1) and compound (6-2), compound (6-1) and compound (6-18), compound (6-2) and compound (6-24), compound (6-2) and compound (6-25), compound (6-2) and compound (6-26), compound (6-25) and compound (6-26), or compound (6-18) and compound (6-24).

[0155] Sixth, additives that can be added to the composition are described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, etc. Optically active compounds are added to the composition to impart a torsion angle by inducing a helical structure in the liquid crystal molecules. Examples of such compounds are compounds (7-1) to (7-5). A preferred proportion of the optically active compound is about 5% by mass or less. A more preferred proportion is in the range of about 0.01% by mass to about 2% by mass.

[0156] To prevent the decrease in resistivity caused by heating in the atmosphere, or to maintain a high voltage retention rate not only at room temperature but also at temperatures close to the upper limit after prolonged use of the component, antioxidants such as compounds (8-1) to (8-3) may be added to the composition.

[0157] Compound (8-2) is effective in maintaining a high voltage retention rate not only at room temperature but also at temperatures close to the upper limit temperature after prolonged use of the component. To achieve this effect, the preferred proportion of the antioxidant is about 50 ppm or more, and to avoid lowering the upper limit temperature or raising the lower limit temperature, the preferred proportion of the antioxidant is about 600 ppm or less. More preferably, the proportion is in the range of about 100 ppm to about 300 ppm.

[0158] Preferred examples of ultraviolet absorbers include benzophenone derivatives, benzoic acid ester derivatives, triazole derivatives, etc. Additionally, light stabilizers such as sterically hindered amines are also preferred. Preferred examples of light stabilizers are compounds (9-1) to (9-16), etc. To obtain the aforementioned effect, the preferred proportion of these absorbers or stabilizers is about 50 ppm or more, and to avoid lowering the upper limit temperature or raising the lower limit temperature, the preferred proportion of these absorbers or stabilizers is about 10,000 ppm or less. More preferably, the proportion is in the range of about 100 ppm to about 10,000 ppm.

[0159] A matting agent is a compound that prevents the decomposition of a liquid crystal compound by accepting the light energy absorbed by the liquid crystal compound and converting it into heat energy. Preferred examples of matting agents are compounds (10⁻¹) to (10⁻⁷). To achieve the aforementioned effect, the preferred proportion of these matting agents is about 50 ppm or more, and to avoid raising the lower limit temperature, the preferred proportion of these matting agents is about 20,000 ppm or less. More preferably, the proportion is in the range of about 100 ppm to about 10,000 ppm.

[0160] To suit components in a guest-host (GH) mode, dichroic dyes such as azo dyes and anthraquinone dyes are added to the composition. The preferred proportion of the dye is in the range of about 0.01% by mass to about 10% by mass. To prevent foaming, defoamers such as dimethyl silicone oil and methylphenyl silicone oil are added to the composition. To achieve the desired effect, the preferred proportion of the defoamer is about 1 ppm or more; to prevent poor display, the preferred proportion of the defoamer is about 1000 ppm or less. More preferably, the proportion is in the range of about 1 ppm to about 500 ppm.

[0161] Polymerizable compounds are used to suit polymerically stable alignment (PSA) type components. Compound (6) is suitable for this purpose. Polymerizable compounds different from compound (6) may also be added to the composition together with compound (6). Preferred examples of such polymerizable compounds are acrylates, methacrylates, vinyl compounds, ethylene oxy compounds, propylene ethers, epoxy compounds (oxetane, oxetane), vinyl ketones, etc. More preferred examples are acrylates or derivatives of methacrylates. Based on the total mass of the polymerizable compounds, the preferred proportion of compound (6) is 10% by mass or more. More preferably, the proportion is 50% by mass or more. Particularly preferred, the proportion is 80% by mass or more. The most desirable proportion is 100% by mass.

[0162] Polymerizable compounds such as compound (6) are polymerized by ultraviolet irradiation. Polymerization can also be carried out in the presence of suitable initiators such as photopolymerization initiators. Suitable conditions for 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) are suitable for free radical polymerization as photopolymerization initiators. Based on the total mass of the polymerizable compound, a preferred proportion of the photopolymerization initiator is in the range of about 0.1% by mass to about 5% by mass. A more preferred proportion is in the range of about 1% by mass to about 3% by mass.

[0163] When storing polymerizable compounds such as compound (6), polymerization inhibitors may be added to prevent polymerization. Polymerizable compounds are usually added to the composition with the polymerization inhibitors removed. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methyl hydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, etc.

[0164] Seventh, the synthesis methods of the component compounds are described. These compounds can be synthesized by known methods. Examples of synthesis methods are given. Similar compounds to compound (1) are synthesized using the method described in German Patent Application Publication No. 4414647. Compound (2-1) is synthesized using the method described in Japanese Patent Application Publication No. 9-77692. Compound (4-1) is synthesized using the method described in Japanese Patent Application Publication No. 2-503441. Compound (4-3) is synthesized using the method described in Japanese Patent Application Publication No. 2-503568. Compound (4-16) is synthesized using the method described in "Molecular Crystals and Liquid Crystals", 2011, Vol. 542, No. 1, pp. 16-27. Compound (6-18) is synthesized using the method described in Japanese Patent Application Publication No. 7-101900. Antioxidants are commercially available. Compound (8-1) is available from Sigma-Aldrich Corporation. Compounds (8-2), etc., are synthesized using the method described in U.S. Patent No. 3,660,505.

[0165] Compounds for which no synthetic method is described can be synthesized using methods described in publications such as *Organic Syntheses* (John Wiley & Sons, Inc.), *Organic Reactions* (John Wiley & Sons, Inc.), *Comprehensive Organic Synthesis* (Pergamon Press), and *New Lectures in Experimental Chemistry* (Maruzen). The composition is prepared from compounds obtained in the described manner using known methods. For example, the component compounds are mixed and then dissolved together by heating.

[0166] Finally, the uses of the composition are described. The composition primarily exhibits a lower limit temperature below about -10°C, an upper limit temperature above about 70°C, and an optical anisotropy in the range of about 0.07 to about 0.20. Compositions with an optical anisotropy in the range of about 0.08 to about 0.25 can be prepared by controlling the proportions of the component compounds or by mixing with other liquid crystal compounds. Compositions with an optical anisotropy in the range of about 0.10 to about 0.30 can also be prepared by trial and error. Devices containing this composition exhibit a high voltage retention rate. This composition is suitable for AM devices. This composition is particularly suitable for transmissive AM devices. This composition can be used as a nematic composition and can be used as an optically active composition by adding optically active compounds.

[0167] This composition can be used in AM devices, and further in PM devices. It can be used in AM and PM devices with modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. It is particularly suitable for AM devices with TN, OCB, IPS, or FFS modes. In AM devices with IPS or FFS modes, the liquid crystal molecules can be aligned parallel or perpendicularly relative to the glass substrate when no voltage is applied. These devices can be reflective, transmissive, or semi-transmissive. Transmissive devices are preferred. It can also be used in amorphous silicon-TFT or polycrystalline silicon-TFT devices. This composition can also be used in nematic curvilinear aligned phase (NCAP) devices fabricated through microencapsulation or in polymer dispersed (PD) devices where a three-dimensional network of polymers is formed in the composition.

[0168] [Example]

[0169] The present invention will be further described in detail with reference to the embodiments. The present invention is not limited to these embodiments. The present invention includes mixtures of the composition of Example 1 and the composition of Example 2. The present invention also includes mixtures formed by mixing at least two of the compositions of the examples. The synthesized compounds are identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of the compounds, compositions, and components are determined by the methods described below.

[0170] NMR analysis: A Bruker BioSpin DRX-500 was used for the determination. 1In the H-NMR determination, the sample was dissolved in a deuterated solvent such as CDCl3, and the determination was performed at room temperature at 500 MHz with a cumulative count of 16. Tetramethylsilane was used as an internal standard. 19 In F-NMR measurements, CFC13 was used as an internal standard, and the measurements were performed with a cumulative count of 24. In the description of nuclear magnetic resonance spectra, s refers to a singlet, d to a doublet, t to a triplet, q to a quartet, quintet, sextet, m to multiplet, and br to broad.

[0171] Gas chromatography analysis: A Shimadzu GC-14B gas chromatograph was used for the determination. Helium was used as the carrier gas (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 component compounds, an Agilent Technologies DB-1 capillary column (30 m in length, 0.32 mm in inner diameter, 0.25 μm in film thickness; dimethylpolysiloxane as the stationary phase; non-polar) was used. The column was held at 200°C for 2 minutes, then heated to 280°C at a rate of 5°C / min. The sample was prepared as an acetone solution (0.1% by mass), and 1 μL of this solution was injected into the sample vaporization chamber. The recorder was a Shimadzu C-R5A chromatography kit (Chromatopac) or equivalent. The obtained gas chromatography chromatograms show the retention time and area of ​​the peaks corresponding to the component compounds.

[0172] The solvent used to dilute the sample can be chloroform, hexane, etc. To separate the component compounds, the following capillary columns can be used: HP-1 (30m length, 0.32mm inner diameter, 0.25μm film thickness) manufactured by Agilent Technologies Inc., Rtx-1 (30m length, 0.32mm inner diameter, 0.25μm film thickness) manufactured by Restek Corporation, and BP-1 (30m length, 0.32mm inner diameter, 0.25μm film thickness) manufactured by SGE International Pty. Ltd., Australia. To prevent overlap of compound peaks, the Shimadzu CBP1-M50-025 capillary column (50m length, 0.25mm inner diameter, 0.25μm film thickness) can be used.

[0173] The proportion of liquid crystal compounds in the composition can be calculated using the method described below. The mixture of liquid crystal compounds is analyzed using gas chromatography (FID). The area ratio of the peaks in the gas chromatography pattern corresponds to the proportion of the liquid crystal compounds. When using the capillary column described above, the correction factor for each liquid crystal compound can be considered as 1. Therefore, the proportion of the liquid crystal compounds (mass%) can be calculated based on the area ratio of the peaks.

[0174] Test Sample: When determining the properties of a composition or component, the composition is used directly as a test sample. When determining the properties of a compound, a test sample is prepared by mixing the compound (15% by mass) with a master liquid crystal (85% by mass). The property values ​​of the compound are calculated using an extrapolation method based on the measured values. (Extrapolation value) = {(Test value of the sample) - 0.85 × (Test value of the master liquid crystal)} / 0.15. When the lamellae phase (or crystals) precipitates at 25°C at this ratio, the ratio of compound to master liquid crystal is varied in the order of 10% by mass: 90% by mass, 5% by mass: 95% by mass, and 1% by mass: 99% by mass. The values ​​of the upper limit temperature, optical anisotropy, viscosity, and dielectric constant anisotropy related to the compound are determined using this extrapolation method.

[0175] The following master liquid crystal is used. The proportions of the component compounds are expressed as mass %

[0176] Measurement Methods: The characteristics were measured using the methods described below. These methods are mostly those described in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (JEITA), or modified versions thereof. No thin-film transistors (TFTs) were installed in the TN element used for measurement.

[0177] (1) Upper limit temperature of nematic phase (NI; °C): The sample is placed on the heating 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 portion of the sample changes from a nematic phase to an isotropic liquid is measured. Sometimes the upper limit temperature of the nematic phase is abbreviated as "upper limit temperature".

[0178] (2) Upper limit temperature of the nematic phase (Tsn; °C): The sample is placed on the heating plate of a melting point measuring device equipped with a polarizing microscope and cooled at a rate of -1 °C / min. The temperature at which a portion of the sample changes from the nematic phase to the nematic phase is measured. Sometimes the upper limit temperature of the nematic phase, i.e. the lower limit temperature of the nematic phase, is abbreviated as "lower limit temperature".

[0179] (3) Viscosity (volume viscosity; η; measured at 20°C; mPa·s): The E-type rotational viscometer manufactured by Tokyo Keiki Co., Ltd. was used for the measurement.

[0180] (4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): The rotational viscosity measurement system LCM-2 from Toyo Technica Corporation was used for the measurement. The sample was injected into a VA element with a spacing (unit gap) of 10 μm between two glass substrates. A rectangular wave (55 V, 1 ms) was applied to the element. The peak current and peak time of the transient current generated by the application were measured. The rotational viscosity was obtained using these measured values ​​and the dielectric anisotropy. The dielectric anisotropy was measured using the method described in (6).

[0181] (5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25°C): Measurements were performed using light with a wavelength of 589 nm, employing an Abbe refractometer with a polarizing plate mounted on the eyepiece. The sample was dropped onto the main prism after rubbing its surface in one direction. The refractive index n∥ was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index n⊥ was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated using the formula Δn = n∥ - n⊥.

[0182] (6) Dielectric constant anisotropy (Δε; measured at 25°C): The value of dielectric constant anisotropy is calculated according to the formula Δε=ε∥-ε⊥. The dielectric constant (ε∥ and ε⊥) is measured in the following manner.

[0183] 1) Determination of dielectric constant (ε∥): A solution of 0.16 mL of octadecyltriethoxysilane in 20 mL of ethanol was coated onto a thoroughly cleaned glass substrate. After rotating the glass substrate using a rotator, it was heated at 150 °C for 1 hour. The sample was placed in a VA element with a 4 μm gap (cell gap) between the two glass substrates, and the element was sealed using an adhesive that hardens by ultraviolet light. A sine wave (0.5 V, 1 kHz) was applied to the element, and the dielectric constant (ε∥) along the long axis of the liquid crystal molecules was measured after 2 seconds.

[0184] 2) Determination of dielectric constant (ε⊥): A polyimide solution was coated onto a thoroughly cleaned glass substrate. After calcining the glass substrate, the resulting alignment film was subjected to a rubbing treatment. The sample was placed in a TN element with a spacing (cell gap) of 9 μm between the two glass substrates and a twist angle of 80 degrees. A sine wave (0.5V, 1kHz) was applied to the element, and the dielectric constant (ε⊥) of the liquid crystal molecules in the short axis direction was measured after 2 seconds.

[0185] (7) Critical Voltage (Vth; measured at 25°C; V): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. A halogen lamp was used as the light source. The sample was placed in a VA element with a spacing (unit gap) of 4 μm between two glass substrates and an antiparallel rubbing direction in a normally black mode. The element was sealed using an adhesive that hardens by ultraviolet light. The voltage (60 Hz, rectangular wave) applied to the element was increased stepwise from 0 V to 20 V in 0.02 V increments. At this time, light was irradiated onto the element from a vertical direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was prepared with the transmittance at the maximum of 100% and the transmittance at the minimum of 0%. The critical voltage is expressed as the voltage at which the transmittance becomes 10%.

[0186] (8) Voltage Retention Rate (VHR-1; measured at 25°C; %): The TN element used for the measurement has a polyimide alignment film, and the spacing (unit gap) between the two glass substrates is 5 μm. The element is sealed with an adhesive that hardens by ultraviolet light after the sample is placed in it. The TN element is charged by applying a pulsed voltage (5V, 60 μs). The decaying voltage is measured over a period of 16.7 milliseconds using a high-speed voltmeter, and the area A between the voltage curve per unit period and the horizontal axis is calculated. Area B is the area before decay. The voltage retention rate is expressed as a percentage of area A relative to area B.

[0187] (9) Voltage retention rate (VHR-2; measured at 80°C; %): The voltage retention rate was measured at 80°C instead of 25°C, following the same procedure as described above. The obtained value is expressed as VHR-2.

[0188] (10) Voltage Retention Rate (VHR-3; measured at 25°C; %): The voltage retention rate was measured after irradiation with ultraviolet light to evaluate the stability against ultraviolet light. The TN element used for the measurement had a polyimide alignment film and a unit spacing of 5 μm. The sample was injected into the element and irradiated for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Electric), and the distance between the element and the light source was 20 cm. In the VHR-3 measurement, the decaying voltage was measured over a period of 16.7 milliseconds. Compositions with a large VHR-3 exhibit high stability against ultraviolet light. The VHR-3 is preferably 90% or higher, and more preferably 95% or higher.

[0189] (11) Voltage Retention Rate (VHR-4; determined at 25°C; %): The thermal stability was evaluated by measuring the voltage retention rate after heating the TN element containing the sample in a thermostat at 80°C for 500 hours. In the VHR-4 determination, the decaying voltage was measured over a period of 16.7 milliseconds. Compositions with a large VHR-4 exhibit high thermal stability.

[0190] (12) Response time (τ; measured at 25°C; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set to 5 kHz. The sample was placed in a VA element with a spacing (cell gap) of 4 μm between the two glass substrates and an antiparallel rubbing direction in a normally black mode. The element was sealed using an adhesive that hardens by ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 s) was applied to the element. At this time, light was irradiated onto the element from a vertical direction, and the amount of light transmitted through the element was measured. When the amount of light reaches its maximum, the transmittance is considered to be 100%, and when the amount of light reaches its minimum, the transmittance is considered to be 0%. The response time is expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

[0191] (13) Specific resistance (ρ; measured at 25°C; Ωcm): 1.0 mL of the sample is injected into a container equipped with electrodes. A DC voltage (10V) is applied to the container, and the DC current is measured after 10 seconds. The specific resistance is calculated by the following formula: (Specific resistance) = {(voltage) × (capacitance of the container)} / {(DC current) × (dielectric constant of vacuum)}.

[0192] (14) Line Image Sticking Parameter (LISP; %): Line image sticking is generated by applying electrical stress to the liquid crystal display element. The brightness of the area where line image sticking exists is measured and compared with the brightness of the remaining area. The percentage reduction in brightness due to line image sticking is calculated, and this percentage represents the size of the line image sticking.

[0193] 14a) Brightness Measurement: Images of the component were captured using an imaging color luminance meter (Radiant Zemax, PM-1433F-0). The brightness of each area of ​​the component was calculated by analyzing the image using software (Prometric 9.1, Radiant Imaging). An average luminance of 3500 cd / m² was used as the light source. 2 LED backlight.

[0194] 14b) Setting the stress voltage: A sample was placed in an FFS element (16 elements, 4 vertical elements × 4 horizontal elements) with a matrix structure and a unit spacing of 3.5 μm. The element was then sealed using an adhesive that hardens with ultraviolet light. Polarizing plates were placed on the upper and lower surfaces of the element, orthogonal to the polarizing axis. The element was irradiated with light and a voltage (rectangular wave, 60 Hz) was applied. The voltage was increased in 0.1 V increments from 0 V to 7.5 V, and the transmittance was measured at each voltage. The voltage at which the transmittance reached maximum was abbreviated as V255. The voltage at which the transmittance reached 21.6% of V255 (i.e., 127 gray levels) was abbreviated as V127.

[0195] 14c) Stress conditions: V255 (rectangular wave, 30Hz) and 0.5V (rectangular wave, 30Hz) were applied to the element at 60°C for 23 hours, and a checkerboard pattern was displayed. Next, V127 (rectangular wave, 0.25Hz) was applied, and the brightness was measured at an exposure time of 4000 ms.

[0196] 14d) Calculation of Line Afterimage: The calculation uses the central 4 units (2 vertical units × 2 horizontal units) of the 16-unit matrix. These 4 units are divided into 25 regions (5 vertical units × 5 horizontal units). The average brightness of the four corner regions (2 vertical units × 2 horizontal units) is denoted as Brightness A. The regions obtained by removing the corner regions from the 25 regions form a cross shape. The minimum brightness value among the four regions obtained by removing the central intersection region from this cross shape is denoted as Brightness B. The line afterimage is calculated using the following formula: (Line Afterimage) = (Brightness A - Brightness B) / Brightness A × 100.

[0197] (15) Expandability: The expandability of the additive is qualitatively evaluated by applying voltage to the element and measuring the brightness. The brightness measurement is performed in the same manner as described in item 14a. The voltage (V127) setting is performed in the same manner as described in item 14b. A VA element is used instead of an FFS element. The brightness is measured as follows: First, a DC voltage (2V) is applied to the element for 2 minutes. Next, V127 (square wave, 0.05Hz) is applied, and the brightness is measured at an exposure time of 4000 milliseconds. The expandability is evaluated based on this result.

[0198] (16) Response time (τ-2; measured at -20°C; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. A halogen lamp was used as the light source. The low-pass filter was set to 5 kHz. The sample was placed in a VA element with a spacing (cell gap) of 4 μm between the two glass substrates and an antiparallel rubbing direction in a normally black mode. The element was sealed using an adhesive that hardens by ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 s) was applied to the element. At this time, light was irradiated onto the element from a vertical direction, and the amount of light transmitted through the element was measured. When the amount of light reaches its maximum, the transmittance is considered to be 100%, and when the amount of light reaches its minimum, the transmittance is considered to be 0%. The response time is expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

[0199] (17) Response time (τ-3; measured at -30°C; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. A halogen lamp was used as the light source. The low-pass filter was set to 5 kHz. The sample was placed in a VA element with a spacing (cell gap) of 4 μm between the two glass substrates and an antiparallel rubbing direction in a normally black mode. The element was sealed with an adhesive that was cured by ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 s) was applied to the element. At this time, light was irradiated onto the element from a vertical direction, and the amount of light transmitted through the element was measured. When the amount of light reached its maximum, the transmittance was considered to be 100%, and when the amount of light reached its minimum, the transmittance was considered to be 0%. The response time is expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

[0200] (18) Elastic constants (K11: splay elastic constant, K33: bending elastic constant; measured at 25°C; pN): An EC-1 type elastic constant measuring instrument manufactured by Toyo Technica Co., Ltd. was used for the measurement. The sample was placed in a vertical alignment unit with a spacing (unit gap) of 20 μm between two glass substrates. A charge of 20 volts to 0 volts was applied to the unit, and the electrostatic capacitance and the applied voltage were measured. Using Equations (2.98) and (2.101) on page 75 of the "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), the measured electrostatic capacitance (C) was fitted to the applied voltage (V), and the value of the elastic constant was obtained by Equation (2.100).

[0201] Compound (1-3-1) was synthesized using the following route.

[0202] First step: Synthesis of compound (b)

[0203] Compound (a) (200 g, 1.39 mol) was dissolved in tetrahydrofuran (THF) (3 L), and NaH (66.6 g, 1.39 mol) was added at room temperature. The mixture was heated and stirred at 50 °C for 3 hours. After cooling to 10 °C, triisopropylchlorosilane (267 g, 1.39 mol) was added dropwise, and the mixture was stirred overnight. After cooling to 10 °C, ice water (500 mL) was slowly added dropwise into an aqueous solution of NH4Cl (1 L), and ethyl acetate (500 mL) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solid was then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene:ethyl acetate = 9:1 by volume), and the crude product was removed by vacuum distillation to obtain compound (b) (302 g, 1.00 mol, yield 72.4%).

[0204] Step 2: Synthesis of compound (c)

[0205] Compound (b) (102 g, 0.34 mol) was dissolved in CH2Cl2 (1 L), and Dess-Martin periodinane (173 g, 0.41 mol) was slowly added at a temperature below 20 °C, with stirring for 4 hours. The reaction solution was removed by vacuum distillation, purified by short column chromatography (toluene:ethyl acetate = 9:1 by volume), and then purified by vacuum distillation. The crude product was purified by column chromatography (toluene), and then purified by vacuum distillation to obtain compound (c) (74.8 g, 0.25 mol, yield 73.8%).

[0206] Third step: Synthesis of compound (d)

[0207] CBr2F2 (82.6 g, 0.39 mol) was dissolved in THF (700 mL). A THF solution of P(NEt2)3 (194 g, 0.79 mol) in 100 mL was added dropwise at a temperature below 30 °C, and the mixture was stirred for 1 hour. A THF solution of compound (c) (106 g, 0.36 mol) in 100 mL was added dropwise at a temperature below 50 °C, and the mixture was stirred overnight. The solution was then added to an NH4Cl aqueous solution (800 mL), and heptane (500 mL) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (with heptane), and compound (d) (84.2 g, 0.25 mol, yield 71.3%) was obtained by vacuum distillation.

[0208] Step 4: Synthesis of compound (e)

[0209] Compound (d) (84.2 g, 0.25 mol) was dissolved in THF (250 mL), cooled to 0 °C, and tetrabutylammonium fluoride (approximately 1 mol / L THF solution, 380 mL, 0.38 mol) was added dropwise, and the mixture was stirred overnight. The reaction solution was removed by vacuum distillation and purified by column chromatography (toluene:ethyl acetate = 9:1 by volume ratio). Compound (e) (39.9 g, 0.23 mol, 89.5% yield) was obtained by vacuum distillation.

[0210] Step 5: Synthesis of compound (f)

[0211] Compound (e) (39.9 g, 0.23 mol) was dissolved in CH₂Cl₂ (150 mL), and Dess-Martin periodinane (95.4 g, 0.22 mol) was slowly added, followed by stirring for 2 hours. The reaction solution was removed by vacuum distillation, purified by short-column chromatography (CH₂Cl₂), and then separated into an organic layer in 100 mL of NH₄Cl aqueous solution, with magnesium sulfate added as a drying agent. The solids were then separated by filtration, and the filtrate was concentrated under reduced pressure. Compound (f) (20.0 g, 0.11 mol, yield 50.8%) was obtained by vacuum distillation.

[0212] Step 6: Synthesis of compound (h)

[0213] Compound (g) (144 g, 0.48 mol), 5-mercapto-1-phenyl-1H-tetrazole (103 g, 0.58 mol), and tetrabutylammonium hydrogen sulfate (10.9 g, 32.1 mol) were dissolved in toluene (800 mL). KOH (42.2 g, 0.75 mol) dissolved in water (300 mL) was added dropwise at a temperature below 40 °C, and the mixture was stirred at 90 °C for 2 hours. The organic layer was separated by adding water (500 mL), and magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation to obtain compound (h) (195 g, 0.48 mol, quantitative yield).

[0214] Step 7: Synthesis of compound (i)

[0215] Compound (h) (185 g, 0.46 mol) was dissolved in chloroform (2 L), and 3-chloroperbenzoic acid (240 g, 1.39 mol) was slowly added at a temperature below 20 °C, with stirring overnight. The reaction mixture was filtered, and the filtered solids were washed with chloroform, followed by washing the filtrate with aqueous solutions of NaHCO3 (1 L) and NaHSO3 (1 L). Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene) and recrystallization (heptane / ethyl acetate), and dried to obtain compound (i) (192 g, 0.45 mol, yield 96.1%).

[0216] Step 8: Synthesis of compound (1-3-1)

[0217] Compound (f) (20.0 g, 0.11 mol) and compound (i) (54.1 g, 0.13 mol) were dissolved in 1,2-dimethoxyethane (700 mL) and cooled to -30 °C. A THF solution of potassium bis(trimethylsilyl)amidide (1 M, 140 mL, 0.14 mol) was added dropwise, and the mixture was slowly heated to room temperature and then stirred at 80 °C for 2 hours. The solution was then injected into a 1 N HCl (500 mL) aqueous solution, and toluene (500 mL) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (heptane) and recrystallization (ethanol / ethyl acetate), and dried to obtain compound (1-3-1) (10.7 g, 0.028 mol, yield 24.6%).

[0218] 1 H-NMR(CDCl3)δ5.33-5.25(m,2H),4.00(ddd,J=26Hz,9.5Hz,3.0Hz,1H),2.11-2.03(m,1H),1.85- 1.76(m,14H),1.30(sext,J=7.5Hz,2H),1.16-1.07(m,7H),1.05-0.91(m,8H),0.88-0.80(m,5H).

[0219] Upper limit temperature (NI) = 240.1℃; dielectric anisotropy (Δε) = 0.83; optical anisotropy (Δn) = 0.0864; viscosity (η) = 23.8 mPa·s.

[0220] Compound (1-7-1) was synthesized using the following route.

[0221] First step: Synthesis of compound (b)

[0222] Compound (a) (477 g, 2.00 mol) and triethyl phosphonoacetate (471 g, 2.10 mol) were dissolved in toluene (2 L). A solution of sodium ethoxide (143 g, 2.10 mol) in ethanol (465 mL) was added dropwise at a temperature below 10 °C, and the mixture was stirred for 1 hour. The solution was then added to water (2 L), and toluene (2 L) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene), and the residue was removed by vacuum distillation to obtain compound (b) (460 g, 1.49 mol, yield 74.5%).

[0223] Step 2: Synthesis of compound (c)

[0224] Compound (b) (259 g, 0.84 mol) was dissolved in a mixed solvent of toluene (1.3 L) and 2-propanol (1.3 L), and Pd / C (13 g) was added. The mixture was stirred for 8 hours under hydrogen atmosphere. Pd / C was separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene), and the crude product was removed by vacuum distillation to obtain compound (c) (260 g, 0.84 mol, quantitative yield).

[0225] Third step: Synthesis of compound (d)

[0226] Lithium aluminum hydride (19.1 g, 0.50 mol) was suspended in THF (1.5 L). A THF (1 L) solution of compound (c) (260 g, 0.84 mol) was added dropwise at a temperature below 10 °C, and the mixture was stirred for 3 hours. Ethyl acetate (500 mL) and NH4Cl aqueous solution (500 mL) were added dropwise at a temperature below 10 °C, and the mixture was stirred for 30 minutes. The organic layer was separated, and magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by recrystallization (heptane / toluene) to obtain compound (d) (135 g, 0.50 mol, yield 60.0%).

[0227] Step 4: Synthesis of compound (e)

[0228] Compound (d) (135 g, 0.50 mol), triphenylphosphine (172 g, 0.65 mol), and 1H-imidazole (42.8 g, 0.63 mol) were dissolved in toluene (1.4 L), cooled to 0 °C, and iodine (166 g, 0.65 mol) was slowly added while stirring for 2 hours. Heptane (1 L) was added, and the solids were separated by filtration. The filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (heptane:toluene = 2:1 by volume), and the crude product was removed by vacuum distillation. Further purification by recrystallization (in heptane) yielded compound (e) (131 g, 0.35 mol, yield 68.8%).

[0229] Step 5: Synthesis of compound (f)

[0230] Compound (e) (131 g, 0.35 mol) was dissolved in dimethylformamide (DMF) (600 mL), cooled to 0 °C, and potassium tert-butoxide (46.6 g, 0.42 mol) was slowly added while stirring for 2 hours. The solution was then added to water (1 L), and toluene (1 L) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene), and the residue was removed by vacuum distillation to obtain compound (f) (70.7 g, 0.28 mol, yield 81.5%).

[0231] Step 6: Synthesis of compound (g)

[0232] Compound (f) (70.7 g, 0.28 mol) and tetrabutylammonium bromide (27.3 g, 0.085 mol) were dissolved in toluene (300 mL), and formic acid (150 mL) was added. The mixture was stirred for 2 hours. The organic layer was separated by adding water (500 mL) and magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene:ethyl acetate = 10:1 by volume), and the crude product was removed by vacuum distillation to obtain compound (g) (56.2 g, 0.27 mol, yield 96.5%).

[0233] Step 7: Synthesis of compound (h)

[0234] (Methoxymethyl)triphenylphosphonium chloride (117 g, 0.34 mol) was suspended in THF (500 mL), cooled to -30 °C, and potassium tert-butoxide (36.7 g, 0.33 mol) was slowly added while stirring for 1 hour. A THF (200 mL) solution of compound (g) (56.2 g, 0.27 mol) was added dropwise while stirring for 2 hours. The solution was then added to water (500 mL), and toluene (700 mL) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (heptane:ethyl acetate = 8:1 by volume ratio), and the residue was removed by vacuum distillation to obtain compound (h) (58.2 g, 0.25 mol, yield 91.2%).

[0235] Step 8: Synthesis of compound (i)

[0236] Compound (h) (58.2 g, 0.25 mol) and p-toluenesulfonic acid monohydrate (14.2 g, 0.074 mol) were dissolved in methanol (600 mL) and stirred under reflux for 10 hours. The solution was added to water (500 mL), and toluene (1 L) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene), and the residue was removed by vacuum distillation to obtain compound (i) (39.6 g, 0.15 mol, yield 59.8%).

[0237] Step 9: Synthesis of compound (j)

[0238] Compound (i) (39.6 g, 0.15 mol) and tetrabutylammonium bromide (14.4 g, 0.045 mol) were dissolved in toluene (400 mL), and formic acid (80 mL) was added. The mixture was stirred for 2 hours. The organic layer was separated by adding water (300 mL), and magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation to obtain compound (j) (24.4 g, 0.11 mol, yield 74.5%).

[0239] Step 10: Synthesis of compound (l)

[0240] Compound (k) (140 g, 0.64 mol), 5-mercapto-1-phenyl-1H-tetrazole (103 g, 0.58 mol), and tetrabutylammonium hydrogen sulfate (9.8 g, 0.029 mol) were dissolved in toluene (300 mL). KOH (35.8 g, 0.64 mol) dissolved in water (150 mL) was added dropwise at a temperature below 40 °C, and the mixture was stirred at 70 °C for 2 hours. The organic layer was separated by adding water (500 mL), and magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene), and the residue was removed by vacuum distillation to obtain compound (l) (172 g, 0.54 mol, yield 85.1%).

[0241] Step 11: Synthesis of compound (m)

[0242] Compound (l) (172 g, 0.54 mol) was dissolved in chloroform (2 L), and 3-chloroperbenzoic acid (281 g, 1.63 mol) was slowly added at a temperature below 20 °C, with stirring overnight. The reaction mixture was filtered, and the filtered solids were washed with chloroform. The filtrate was washed with aqueous solutions of NaHCO3 (1 L) and NaHSO3 (1 L), and magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (toluene:ethyl acetate = 5:1 by volume) and recrystallization (ethanol), and dried to obtain compound (m) (182 g, 0.52 mol, yield 96.1%).

[0243] Step 12: Synthesis of compound (1-7-1)

[0244] Compound (j) (24.4 g, 0.11 mol) and compound (m) (50.2 g, 0.14 mol) were dissolved in 1,2-dimethoxyethane (700 mL) and cooled to -30 °C. A THF solution of potassium bis(trimethylsilyl)amidide (1 M, 166 mL, 0.17 mol) was added dropwise, and the mixture was slowly heated to room temperature and then stirred at 80 °C for 2 hours. The solution was then injected into a 1 N HCl (500 mL) aqueous solution, and toluene (500 mL) was added to separate the organic layer. Magnesium sulfate was added as a drying agent. The solids were then separated by filtration, and the filtrate was removed by vacuum distillation. The crude product was purified by column chromatography (heptane) and recrystallization (heptane / ethanol), and dried to obtain compound (1-7-1) (9.9 g, 0.029 mol, yield 26.1%).

[0245] 1 H-NMR(CDCl3)δ5.77(ddd,J=17.0Hz,10.5Hz,6.5Hz,1H),5.33-5.25(m,2H),4.95(d,J=17.5Hz,1H),4.86(d,J=10. 5Hz,1H),1.91-1.65(m,15H),1.29(sext,J=7.0Hz,2H),1.20-1.11(m,3H),1.10-0.95(m,12H),0.93-0.84(m,5H).

[0246] Upper limit temperature (NI) = 246.1℃; dielectric anisotropy (Δε) = -0.5; optical anisotropy (Δn) = 0.086; viscosity (η) = 21.2 mPa·s.

[0247] Examples of the compositions are shown below. The component compounds are represented by codes based on the definitions in Table 3 below. In Table 3, the stereoconfiguration associated with 1,4-cyclohexylene is the trans configuration. The numbers in parentheses following the codes correspond to the compound numbers. Codes with parentheses (-) indicate other liquid crystal compounds. The proportions (percentages) of the liquid crystal compounds are mass percentages (mass %) based on the mass of the liquid crystal composition. Finally, the characteristic values ​​of the compositions are summarized.

[0248] Table 3. Representation of compounds using codes

[0249] [Example 1]

[0250] NI=119.2℃; Tsn=-34.2℃; Δn=0.1004; Δε=-2.94; γ1=178mPa·s.

[0251] [Example 2]

[0252] NI=120.1℃; Tsn=-33.2℃; Δn=0.1009; Δε=-2.86; γ1=179mPa·s.

[0253] [Comparative Example 1]

[0254] A composition was prepared by replacing component A, i.e. compound (1), in the compositions of Examples 1 and 2 with a similar compound.

[0255] NI=120.4℃; Tsn=-29.9℃; Δn=0.1003; Δε=-2.94; γ1=180mPa·s.

[0256] The compositions of Comparative Example 1 have γ1 and Tsn values ​​of 180 mPa·s and -29.9 °C, respectively. On the other hand, the compositions of Example 1 have γ1 and Tsn values ​​of 178 mPa·s and -34.2 °C, respectively, and the compositions of Example 2 have γ1 and Tsn values ​​of 179 mPa·s and -33.2 °C, respectively. Thus, compared to the compositions of the comparative examples, the compositions of the comparative examples, with their substitution of component compounds, exhibit lower rotational viscosity and lower lower limit temperature of the nematic phase (lower upper limit temperature of the lamellae phase). Therefore, it can be concluded that the liquid crystal compositions of the present invention possess excellent properties.

[0257] [Example 3]

[0258] Add 0.15% by weight of the following compound to the composition.

[0259] NI=120.6℃;Tsn=-41.4℃;Δn=0.0900;Δε=-2.45;γ1=123mPa·s.

[0260] [example4]

[0261] NI=120.7℃;Tsn=-40.8℃;Δn=0.0902;Δε=-2.44;γ1=124mPa·s.

[0262] [example5]

[0263] NI=119.8℃;Tsn=-40.2℃;Δn=0.0912;Δε=-2.40;γ1=130mPa·s.

[0264] [ example 6 ]

[0265] NI=120.6℃;Tsn=-40.3℃;Δn=0.0906;Δε=-2.45;γ1=123mPa·s.

[0266] [example7]

[0267] NI=112.5℃;Tsn=-39.2℃;Δn=0.0925;Δε=-2.49;γ1=121mPa·s.

[0268] [example8]

[0269] NI=112.4℃;Tsn=-38.2℃;Δn=0.0923;Δε=-2.49;γ1=122mPa·s.

[0270] [example9]

[0271] NI=110.1℃;Tsn=-35.2℃;Δn=0.0999;Δε=-3.94;γ1=137mPa·s.

[0272] [example10]

[0273] NI=82.5℃;Δn=0.0900;Δε=-2.72;γ1=76mPa·s.;Tsn=-32.2℃

[0274] [Example 11]

[0275] NI=80.6℃; Tsn=-31.4℃; Δn=0.1102; Δε=-3.35; γ1=89mPa·s. Industrial applicability

[0276] The liquid crystal composition of the present invention can be used in liquid crystal monitors, liquid crystal televisions, etc.

Claims

1. A liquid crystal composition comprising at least one compound selected from the compounds represented by formula (1) as component A, and having negative dielectric anisotropy, In equation (1), R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine; R 2 It is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine; Z 1 It is a single bond or a vinylidene bond; in, When R 2 When it is an alkyl group with 1 to 12 carbon atoms, Z 1 It is vinylidene, and R 1 It is an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms; When R 2 When R is an alkenyl group with 2 to 12 carbon atoms 1 It is an alkenyl group with 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

2. The liquid crystal composition of claim 1, wherein at least one compound selected from the compounds represented by formulas (1-1) to (1-7) is component A. In equations (1-1) to (1-6), R 1 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine; R 2 It is an alkenyl group having 2 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine; In equation (1-7), R 17 It is an alkoxy group having 1 to 12 carbon atoms or an alkenyl group having 2 to 12 carbon atoms.

3. The liquid crystal composition of claim 1 or 2, wherein the proportion of component A is in the range of 1% by mass to 20% by mass.

4. The liquid crystal composition according to claim 1 or 2, wherein it contains at least one compound selected from the compounds represented by formula (2) and formula (3) as component B. In equation (2), R 3 and R 4 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine; Ring B and ring C are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z 2 It can be a single bond, ethylidene, vinylidene, methyleneoxy, or carbonyloxy; In equation (3), R 5 and R 6 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine; Ring D and ring E are 1,4-cyclohexene, 1,4-cyclohexenyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z 3 It can be a single bond, ethylidene, methyleneoxy, or carbonyloxy; a is 2 or 3; in, When a is 2 and Z 3 When it is a single bond, ring E is 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene.

5. The liquid crystal composition according to claim 1 or 2, comprising at least one compound selected from the compounds represented by formulas (2-1) to (2-3) and (3-1) to (3-11) as component B. In equations (2-1) to (2-3), R 3 and R 4 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is substituted by fluorine or chlorine; In equations (3-1) to (3-11), R 5 and R 6 It is an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

6. The liquid crystal composition of claim 4, wherein the proportion of component B is in the range of 20% by mass to 80% by mass.

7. The liquid crystal composition according to claim 1 or 2, wherein it contains at least one compound selected from the compounds represented by formula (4) and formula (5) as component C. In equation (4), R 7 and R 8 It is hydrogen, 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, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine; The ring F and ring H are 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromoline-2,6-diyl, or chromoline-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine; Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 1,8-difluorophenanthrene-2,7-diyl, 3,4,5-trifluoronaphthyl-2,6-diyl, 7,8-difluorochrome-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl, or 1,1,6,7-tetrafluoroindane-2,5-diyl; Z 4 and Z 5 It can be a single bond, ethylidene, vinylidene, methyleneoxy, or carbonyloxy; b is 0, 1, 2, or 3; c is 0 or 1; the sum of b and c is less than 3; In equation (5), R 9 and R 10 It is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine. X 1 and X 2 It is oxygen or sulfur; Y 1 and Y 2 It can be hydrogen, fluorine, or trifluoromethyl; Ring I and ring J are 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine, naphth-2,6-diyl, naphth-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, chromane-2,6-diyl, chromane-2,6-diyl with at least one hydrogen substituted by fluorine or chlorine, fluorene-2,7-diyl, or rings with at least one hydrogen substituted by fluorine or chlorine. Fluorine-2,7-diyl, dibenzofuran-3,7-diyl, dibenzofuran-3,7-diyl, dibenzothiophene-3,7-diyl, dibenzothiophene-3,7-diyl, indane-2,5-diyl, indane-2,5-diyl, thiophene-2,5-diyl, or furan-2,5-diyl are fluorine- or chlorine-substituted. Z 6 and Z 7 It can be a single bond, ethylidene, vinylidene, ethynylidene, methyleneoxy, or carbonyloxy; d and e are 0 or 1.

8. The liquid crystal composition according to claim 1 or 2, comprising at least one compound selected from the compounds represented by formulas (4-1) to (4-36) and (5-1) to (5-3) as component C. In equations (4-1) to (4-36), R 7 and R 8 It is hydrogen, 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, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine; In equations (5-1) to (5-3), R 9 and R 10 It is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenoxy group having 2 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine. Y 1 and Y 2 It can be hydrogen, fluorine, or trifluoromethyl.

9. The liquid crystal composition of claim 7, wherein the proportion of component C is in the range of 10% by mass to 70% by mass.

10. The liquid crystal composition of claim 1 or 2, wherein at least one compound selected from the polymerizable compounds represented by formula (6) is added as additive X. In equation (6), Ring L and ring N are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidin-2-yl, or pyridin-2-yl, wherein at least one hydrogen atom may be substituted by 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 in which at least one hydrogen atom is substituted by fluorine or chlorine; ring M is 1,4-cyclohexene, 1,4-cyclohexenyl, 1,4-phenylene, naphth-1,2-diyl, naphth-1,3-diyl, or naphth-1, 4-Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, wherein in these rings at least one hydrogen atom may be substituted by 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 whose at least one hydrogen atom is substituted by fluorine or chlorine; Z 8 and Z 9 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- can be substituted by -O-, -CO-, -COO-, or -OCO-, and at least one -CH2CH2- can be substituted by -CH=CH-, -C(CH3)=CH-, -CH=C(CH3)-, or -C(CH3)=C(CH3)-, and wherein at least one hydrogen atom can be substituted by fluorine or chlorine; P 1 To P 3 It is a polymerizable group; Sp 1 To Sp 3 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- can be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH2CH2- can be substituted by -CH=CH- or -C≡C-, and in these groups at least one hydrogen can be substituted by fluorine or chlorine; h is 0, 1, or 2; i, j, and k are 0, 1, 2, 3, or 4; and the sum of i, j, and k is 1 or more.

11. The liquid crystal composition of claim 10, wherein in formula (6), P 1 To P 3 The group is selected from the polymerizable groups represented by formulas (P-1) to (P-5). In equations (P-1) to (P-5), M 1 To M 3 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

12. The liquid crystal composition of claim 1 or 2, wherein it contains at least one compound selected from polymerizable compounds represented by formulas (6-1) to (6-29) as additive X. In equations (6-1) to (6-29), Sp 1 To Sp 3 It is a single bond or an alkylene group having 1 to 10 carbon atoms, wherein at least one -CH2- can be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH2CH2- can be substituted with -CH=CH- or -C≡C-, and in these groups, at least one hydrogen atom can be substituted with fluorine or chlorine; P 4 To P 6 It is a polymerizable group selected from the groups represented by formulas (P-1) to (P-3); In equations (P-1) to (P-3), M 1 To M 3 It is hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom is replaced by fluorine or chlorine.

13. The liquid crystal composition of claim 10, wherein the proportion of additive X is in the range of 0.03% by mass to 10% by mass.

14. A liquid crystal display element comprising the liquid crystal composition as described in claim 1 or 2.

15. The liquid crystal display element as claimed in claim 14, wherein the operating mode is IPS mode, VA mode, FFS mode, PSA mode, or FPA mode, and the driving method is active matrix mode.

16. A polymer-stabilized alignment liquid crystal display element comprising the liquid crystal composition as described in claim 10, wherein the polymeric compound in the liquid crystal composition is polymerized.

17. Use of a liquid crystal composition, said liquid crystal composition being the liquid crystal composition as described in claim 1 or 2, for use in a liquid crystal display element.

18. Use of a liquid crystal composition, said liquid crystal composition being the liquid crystal composition of claim 10, for use in a polymer-stabilized alignment type liquid crystal display element.

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