Liquid crystal composition and liquid crystal display element

Abstract

Provided are a liquid crystal composition comprising three or more dichroic dyes selected from azo compounds represented by general formula (A) and a host liquid crystal composition, and a device using the liquid crystal composition. The liquid crystal composition of the present invention satisfies the requirements of high contrast, high solubility, and high nematic-isotropic transition temperature (T NI ), a liquid crystal composition containing a dichroic pigment with low birefringence anisotropy (Δn) that is effective for high light resistance and high heat resistance. By using the liquid crystal composition of the present invention, a liquid crystal display element or dimming element that appears to be good black and has high contrast, high display quality, and high practicality can be obtained.

Description

[0001] This application is a divisional application of the original Chinese patent application, filed on February 15, 2018, with application number 201880011699.8 and the invention name “Liquid Crystal Composition and Liquid Crystal Display Element”. Technical Field

[0002] The present invention relates to a liquid crystal composition containing an azo dichroic dye and a liquid crystal display element or a light-adjusting element using the same. Background Art

[0003] Liquid crystal materials are not only used in various display devices that display text, images, and videos, such as TVs and smartphones, but are also being put to practical use as dimming devices that adjust the transmittance of light.

[0004] Among them, when a "guest-host (GH) type liquid crystal composition" in which a dichroic dye is added to a host liquid crystal composition is used, a polarizing plate is not required, and thus a low-cost and high-transmittance light-adjusting element can be expected.

[0005] Research on GH-type liquid crystal compositions has been conducted in the past, and attempts have been made to develop liquid crystal display elements and dimming elements having useful element properties (such as a large dichroic ratio, high contrast, high solubility in liquid crystal compositions, excellent light resistance, excellent UV resistance, and excellent heat resistance) (see Patent Document 1).

[0006] However, some liquid crystal compositions containing dichroic dyes are unsuitable for use in liquid crystal displays and light-adjusting devices, depending on their compositional components, and further performance improvements are needed. For example, achieving a large dichroic ratio requires a large amount of dichroic dye in the liquid crystal composition, which can lead to solubility issues such as precipitation of the dichroic dye and the liquid crystal compound. In particular, light-adjusting devices require a nematic liquid crystal phase over a wide temperature range, but the molecular weight of the dye is greater than that of the liquid crystal compound, which poses solubility issues at low temperatures.

[0007] As a host liquid crystal composition for a dimming element, a high-reliability liquid crystal composition for TV with negative dielectric anisotropy can be used. However, in order to actually use it as a liquid crystal composition for a dimming element, it is necessary to develop a liquid crystal composition that has excellent solubility stability at low temperatures and satisfies a high nematic-isotropic transition temperature (T NI ) and a GH-type liquid crystal composition with low birefringence anisotropy (Δn) effective for high light resistance and high heat resistance.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application No. 2013-534945

[0011] Patent Document 2: International Publication No. 1997 / 17415 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] The problem to be solved by the present invention is to provide a novel material that satisfies high contrast, high solubility, and high nematic-isotropic transition temperature (T NI ), a liquid crystal composition containing a dichroic pigment with low birefringence anisotropy (Δn) that is effective for high light resistance and high heat resistance, and a liquid crystal display element or a dimming element using the same.

[0014] Methods for solving problems

[0015] The present inventors conducted intensive studies and found that the above-mentioned problems can be solved by providing a liquid crystal composition containing one or two or more compounds represented by the general formula (L) and three or four or more dichroic dyes selected from azo compounds, thereby completing the present invention.

[0016] [Chemistry 1]

[0017]

[0018] (Where R L1 and R L2 Each independently represents an alkyl group having 1 to 12 carbon atoms, and one or two or more non-adjacent -CH2- groups in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,

[0019] m L1 means 0, 1, 2 or 3,

[0020] A L1 、A L2 and A L3 Each independently expresses the freedom to choose

[0021] (a) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- groups in this group may be substituted with -O-),

[0022] (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= groups in this group may be substituted with -N=.) and

[0023] (c) 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl

[0024] In the group consisting of: the group (a), group (b) and group (c) are each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, a cyano group or a fluorine atom; A L1 、A L2 and A L3 does not represent 2,3-difluoro-1,4-phenylene, 1,7,8-trifluoronaphthalene-2,6-diyl or 3,4,5-trifluoronaphthalene-2,6-diyl,

[0025] Z L1 and Z L2 Each independently represents a single bond, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=NN=CH-, -CH=CH-, -C≡C- or -CF=CF,

[0026] m L1 A for 2 or 3 L2 and Z L2 When there are multiple L2 and Z L2 Each independently may be the same or different.)

[0027] That is, the present invention provides a liquid crystal composition containing one or two or more compounds represented by general formula (L) and three or four or more dichroic dyes selected from azo compounds, and also provides a liquid crystal display element or a light-adjusting element using the same.

[0028] Effects of the Invention

[0029] According to the present invention, it is possible to provide a material that satisfies high contrast, high solubility, and high nematic-isotropic transition temperature (T NI ), a liquid crystal composition containing a dichroic pigment with low birefringence anisotropy (Δn) that is effective for high light resistance and high heat resistance. Furthermore, by using this liquid crystal composition, a liquid crystal display element or dimming element that appears to be good black and has high contrast, high display quality, and high practicality can be provided. DETAILED DESCRIPTION

[0030] The liquid crystal composition of the present invention contains three or four or more dichroic dyes selected from azo compounds. As azo compounds, it is preferred that the composition contains three or four or more dichroic dyes selected from disazo compounds and triazo compounds. The liquid crystal composition may contain only three or four or more disazo compounds, only three or four or more triazo compounds, or both disazo and triazo compounds as dichroic dyes selected from disazo compounds and triazo compounds.

[0031] As the disazo compound or trisazo compound, for example, it is preferable to contain a compound selected from the compounds represented by the following general formula (A).

[0032] [Chemistry 2]

[0033]

[0034] (Where R A1 and R A2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or a dialkylamino group to which an alkyl group having 1 to 12 carbon atoms is bonded, and one or two or more non-adjacent -CH2- groups in the alkyl group and the dialkylamino group are each independently substituted with -O-, -CO-, -COO-, or -OCO-. Furthermore, the hydrogen atoms in the alkyl group and the dialkylamino group may be substituted with fluorine atoms.

[0035] X 1 and X 2 Each independently represents a single bond, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=NN=CH-, -CH=CH-, -C≡C- or -CF=CF,

[0036] Ar 1 and Ar 3 Each independently represents a member selected from

[0037] [Chemistry 3]

[0038]

[0039] (R A3 and R A4 Each independently represents an alkyl group having 1 to 12 carbon atoms.)

[0040] These groups may be independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, a cyano group or a fluorine atom,

[0041] Ar 2Indicates selected from

[0042] [Chemistry 4]

[0043]

[0044] These groups may be independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, a cyano group or a fluorine atom,

[0045] p represents 0, 1 or 2, p is 2 and Ar 1 and X 1 When there are multiple 1 and X 1 Each independently may be the same or different,

[0046] q represents 2 or 3, Ar 2 Each independently may be the same or different.)

[0047] The alkyl group in the general formula (A) may be linear or branched.

[0048] As the azo compound, it is preferred to use at least one dichroic dye selected from a dichroic dye having a maximum absorption wavelength of 390 nm to 440 nm (hereinafter referred to as "Compound A"), a dichroic dye having a maximum absorption wavelength of 490 nm to 540 nm (hereinafter referred to as "Compound B"), and a dichroic dye having a maximum absorption wavelength of 550 nm to 650 nm (hereinafter referred to as "Compound C"), and it is more preferred to contain at least one compound A, at least one compound B, and at least one compound C. By separately containing Compound A, Compound B, and Compound C, even if the total amount of dichroic dye added is increased, solubility and low-temperature stability in the liquid crystal composition can be maintained.

[0049] The mixing ratio of Compound A, Compound B, and Compound C is preferably 10-60% by weight: 10-60% by weight: 10-60% by weight relative to the total amount of the dichroic pigment in the liquid crystal composition. The mixing ratio of Compound A, Compound B, and Compound C is appropriately adjusted depending on the target chromaticity. Furthermore, the total amount of Compound A, Compound B, and Compound C added relative to the total amount of the dichroic pigment in the liquid crystal composition is preferably 50% by weight or more, preferably 60% by weight or more, preferably 70% by weight or more, preferably 80% by weight or more, preferably 90% by weight or more, preferably 95% by weight or more, and preferably 100% by weight.

[0050] The liquid crystal composition of the present invention is preferably adjusted so that the chromaticity x and y are 0.310 to 0.370, respectively, under standard illuminant D65. This is to achieve a liquid crystal composition with a black color and an excellent contrast ratio. Chromaticity is expressed using the CIE 1931 xy coordinate system. Chromaticity is preferably measured with the liquid crystal composition injected into a cell having a cell thickness of 10 μm, and more preferably, an antiparallel cell.

[0051] The liquid crystal composition of the present invention preferably contains 0.5 to 5 parts by weight of a dichroic dye per 100 parts by weight of the liquid crystal composition. More specifically, the liquid crystal composition preferably contains 1 part by weight or more of a dichroic dye, preferably 1.3 parts by weight or more, preferably 1.5 parts by weight or more, preferably 2.0 parts by weight or more, preferably 2.5 parts by weight or more, preferably 4 parts by weight or less, preferably 3.5 parts by weight or less, and preferably 3 parts by weight or less.

[0052] The liquid crystal composition of the present invention may also contain dichroic dyes other than disazo compounds and triazo compounds. The dichroic dyes contained in the liquid crystal composition of the present invention are preferably all azo-based dichroic dyes. When all dichroic dyes are azo-based dichroic dyes, the dichroic ratio, solubility, and low-temperature stability of the liquid crystal composition are further improved.

[0053] The liquid crystal composition of the present invention contains one or more compounds represented by the general formula (L). The compounds represented by the general formula (L) can be used alone or in combination. There is no particular limitation on the types of compounds that can be combined, and they can be used in appropriate combinations based on desired properties such as solubility at low temperatures, transition temperature, and birefringence. Regarding the types of compounds used, for example, as one embodiment of the present invention, there is one type. Alternatively, in other embodiments of the present invention, there are two, three, four, five, six, seven, eight, nine, or ten or more types.

[0054] In the composition of the present invention, the content of the compound represented by the general formula (L) must be appropriately adjusted depending on the required performance such as solubility at low temperatures, transition temperature, and birefringence.

[0055] The preferred lower limit of the content of the compound represented by formula (L) relative to the total amount of the composition of the present invention is 1%, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%. Furthermore, since excessive content may cause problems such as precipitation, the preferred upper limit of the content is 85%, 75%, 65%, 55%, 45%, 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, or 5%.

[0056] In the case where the viscosity of the composition of the present invention needs to be kept low, for the composition that response speed is fast, preferably above-mentioned lower limit is high and upper limit is high. Further, the resistivity value, VHR of the composition of the present invention are high reliability compositions, and in the case where driving voltage is not restricted, preferably above-mentioned lower limit is high and upper limit is high. In addition, when wanting to increase dielectric anisotropy in order to keep driving voltage low, preferably make above-mentioned lower limit low and upper limit low.

[0057] When reliability is important, R L1 and R L2 Both are alkyl groups. When emphasis is placed on reducing the volatility of the compound, an alkoxy group is preferred. When emphasis is placed on reducing the viscosity, at least one of the groups is preferably an alkenyl group.

[0058] The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3, preferably 0 or 1, and preferably 1 when compatibility with other liquid crystal molecules is important.

[0059] About R L1 and R L2 When the ring structure to which it is attached is a phenyl group (aromatic), linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, and alkenyl groups having 4 to 5 carbon atoms are preferred. When the ring structure to which it is attached is a saturated ring structure such as cyclohexane, pyran, and dioxane, linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, and linear alkenyl groups having 2 to 5 carbon atoms are preferred. To stabilize the nematic phase, the total number of carbon atoms and oxygen atoms, when present, is preferably 5 or less, and linear chain is preferred.

[0060] The alkenyl group is preferably selected from the group represented by any one of formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

[0061] [Chemistry 5]

[0062]

[0063] When response speed is important, m L1 It is preferably 0, and in order to improve the upper limit temperature of the nematic phase, it is preferably 2 or 3, and in order to achieve a balance between them, it is preferably 1. In addition, in order to satisfy the characteristics required as a composition, it is preferable to combine compounds with different values.

[0064] In the case of increasing Δn, A L1 、A L2 and A L3 It is preferably aromatic, and in order to improve the response speed, it is preferably aliphatic, and preferably each independently represents trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, and more preferably represents the following structure,

[0065] [Chemistry 6]

[0066]

[0067] More preferably, it represents trans-1,4-cyclohexylene or 1,4-phenylene.

[0068] When response speed is important, Z L1 and Z L2 The number of halogen atoms in the molecule of the compound represented by the general formula (L) is preferably 0 or 1.

[0069] More specifically, general formula (L) preferably contains compounds represented by general formulae (C1) to (C3). The compounds represented by general formulae (C1) to (C3) may be used alone or in combination of two or more.

[0070] [Chemistry 7]

[0071]

[0072] In the above formula, R d and P eEach independently represents an alkyl group having 1 to 12 carbon atoms, which may be linear or have a methyl or ethyl branch, or may have a 3- to 6-membered ring structure. Any -CH2- present in the group may be substituted by -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, or -C≡C-, and any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group. Preferably, it is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxy group having 1 to 3 carbon atoms, or a linear alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms at a terminal. More preferably, at least one of them is a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 3-alkenyl group having 4 to 7 carbon atoms. When an asymmetric carbon is generated due to branching, the compound may be optically active or a racemic form.

[0073] Ring G, Ring H, Ring I and Ring J each independently represent trans-1,4-cyclohexylene, trans-decahydronaphthalene-trans-2,6-diyl, 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or methyl, naphthalene-2,6-diyl which may be substituted with 1 or more fluorine atoms, tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenylene which may be substituted with 1 to 2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl. In each compound, the number of trans-decahydronaphthalene-trans-2,6-diyl, naphthalene-2,6-diyl which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenylene which may be substituted with fluorine atoms, 1,3-dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl is preferably no more than one, and the other ring is preferably trans-1,4-cyclohexylene or 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or methyl.

[0074] L g , L h and L iis a connecting group, each independently representing a single bond, an ethylene group (-CH2CH2-), a 1,2-propylene group (-CH(CH3)CH2- and -CH2CH(CH3)-), a 1,4-butylene group, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C- or -CH=NN=CH-, preferably a single bond, an ethylene group, a 1,4-butylene group, -COO-, -OCO-, -OCF2-, -CF2O-, -CF=CF-, -C≡C- or -CH=NN=CH-, preferably at least one of (C2) and at least two of (C3) represent a single bond.

[0075] When the compounds represented by general formulae (C1) to (C3) are used in combination, the same options (ring G, L g , etc.) may represent the same substituent or different substituents.

[0076] In general formulae (C1) to (C3), the number of halogen atoms in the molecule is preferably 0 or 1.

[0077] The preferred lower limits of the content of the compounds represented by general formulae (C1) to (C3) relative to the total amount of the composition of the present invention are 1%, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. The preferred upper limits of the content are 85%, 75%, 65%, 55%, 45%, 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, and 5%.

[0078] In the case where the viscosity of the composition of the present invention needs to be kept low, for the composition having a fast response speed, preferably the above-mentioned lower limit is low, the upper limit is high. Further, in the case where the resistivity value, VHR of the composition of the present invention needs to be high, for the composition having high reliability, preferably the above-mentioned lower limit is high, the upper limit is high. In addition, when the driving voltage is low and the dielectric anisotropy is increased, preferably the above-mentioned lower limit is low, the upper limit is low.

[0079] More preferred embodiments of (C1) can be represented by the following general formulae (C1a) to (C1h).

[0080] [Chemistry 8]

[0081]

[0082] In the above formulas, Rf and R g Each independently represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxy group having 1 to 3 carbon atoms, or a linear alkyl group having 1 to 5 carbon atoms substituted at the end with an alkoxy group having 1 to 3 carbon atoms, at least one of which represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 3-alkenyl group having 4 to 7 carbon atoms. In the case where rings G1 to G3 are aromatic rings, the corresponding R f To exclude 1-alkenyl and alkoxy, when ring H1 to ring H3 are aromatic rings, the corresponding R g 1-Alkenyl and alkoxy are excluded.

[0083] Ring G1 and Ring H1 each independently represent trans-1,4-cyclohexylene, trans-decahydronaphthalene-trans-2,6-diyl, 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or methyl, naphthalene-2,6-diyl which may be substituted with 1 or more fluorine atoms, tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenylene which may be substituted with 1 to 2 fluorine atoms, 1,3-dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and each compound In the compound, the number of trans-decahydronaphthalene-trans-2,6-diyl, naphthalene-2,6-diyl which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenylene which may be substituted with fluorine atoms, 1,3-dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl is preferably no more than one. In this case, the other ring is trans-1,4-cyclohexylene or 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or methyl. Ring G2 and ring H2 each independently represent trans-1,4-cyclohexylene, trans-decahydronaphthalene-trans-2,6-diyl, 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or methyl groups, naphthalene-2,6-diyl which may be substituted with 1 or more fluorine atoms, or tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms. In each compound, the number of trans-decahydronaphthalene-trans-2,6-diyl, naphthalene-2,6-diyl which may be substituted with 1 or more fluorine atoms, or tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms is preferably 1 or less. In this case, the other ring is trans-1,4-cyclohexylene or 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or methyl groups. Ring G3 and ring H3 each independently represent a 1,4-phenylene group which may be substituted with 1 to 2 fluorine atoms or a methyl group, a naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, or a tetrahydronaphthalene-2,6-diyl group which may be substituted with 1 to 2 fluorine atoms. The number of the naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms or the tetrahydronaphthalene-2,6-diyl group which may be substituted with 1 to 2 fluorine atoms in each compound is preferably one or less.

[0084] The following compounds are more preferred.

[0085] [Chemistry 9]

[0086]

[0087] [Chemistry 10]

[0088]

[0089] [Chemistry 11]

[0090]

[0091] More preferred embodiments of (C2) can be represented by the following general formulae (C2a) to (C2m).

[0092] [Chemistry 12]

[0093]

[0094] In the above formula, ring G1, ring G2, ring G3, ring H1, ring H2, and ring H3 have the same meanings as described above; ring I1 has the same meaning as ring G1; ring I2 has the same meaning as ring G2; and ring I3 has the same meaning as ring G3. Furthermore, in each of the above compounds, the number of trans-decahydronaphthalene-trans-2,6-diyl, naphthalene-2,6-diyl which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenylene which may be substituted with fluorine atoms, 1,3-dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl is preferably one or less. In this case, the other ring is trans-1,4-cyclohexylene or 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or a methyl group.

[0095] The following compounds are more preferred.

[0096] [Chemistry 13]

[0097]

[0098] [Chemistry 14]

[0099]

[0100] Next, more preferred embodiments of (C3) can be represented by the following general formulae (C3a) to (C3f).

[0101] [Chemistry 15]

[0102]

[0103] In the above formula, ring G1, ring G2, ring H1, ring H2, ring I1, and ring I2 have the same meanings as described above, ring J1 has the same meaning as ring G1, and ring J2 has the same meaning as ring G2. Furthermore, in each of the above compounds, the number of trans-decahydronaphthalene-trans-2,6-diyl, naphthalene-2,6-diyl which may be substituted with one or more fluorine atoms, tetrahydronaphthalene-2,6-diyl which may be substituted with 1 to 2 fluorine atoms, 1,4-cyclohexenylene which may be substituted with fluorine atoms, 1,3-dioxane-trans-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl is preferably one or less. In this case, the other ring is trans-1,4-cyclohexylene or 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms or a methyl group.

[0104] The following compounds are more preferred.

[0105] [Chemistry 16]

[0106]

[0107] The compound represented by the general formula (L) is preferably the general formula (C1a) and (C2a), and more preferably the following general formula (i).

[0108] [Chemistry 17]

[0109]

[0110] (Where R i1 and R i2 Each independently represents R in the general formula (L) L1 and R L2 Same meaning, A i1 Indicates that L2 The same meaning,

[0111] n i1 Represents 1 or 2, when n i1 In the case of 2, there are multiple A i1 Can be the same or different.)

[0112] In the general formula (i), R i1 It is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R i2 It is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. When the response speed of the device is important, R i1 and R i2 At least one of the is an alkenyl group having 2 to 5 carbon atoms, more preferably an alkenyl group having 2 to 3 carbon atoms, preferably R i1 and R i2 Both are alkenyl groups having 2 to 5 carbon atoms, more preferably alkenyl groups having 2 to 3 carbon atoms. When light resistance, UV resistance, or heat resistance of the element is important, R i1 and R i2 At least one of the groups is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, preferably R i1 and R i2 Both are alkyl groups having 1 to 5 carbon atoms.

[0113] In general formula (i), regarding n i1 , when the response speed of the component is important, n i1Preferably, it is 1. When light resistance, UV resistance, or heat resistance of the element is important, n i1 Preferably 2.

[0114] The liquid crystal composition of the present invention preferably contains 1 to 80% by mass of the compound represented by general formula (i), and the lower limit of the content is preferably 1% by mass, preferably 2% by mass, preferably 3% by mass, preferably 4% by mass, preferably 5% by mass, preferably 10% by mass, preferably 15% by mass, preferably 20% by mass, preferably 25% by mass, and preferably 30% by mass, and the upper limit of the content is preferably 80% by mass, preferably 75% by mass, preferably 70% by mass, preferably 65% ​​by mass, preferably 60% by mass, preferably 55% by mass, and preferably 50% by mass.

[0115] Regarding the liquid crystal composition of the present invention, in the case of a liquid crystal composition having a negative dielectric anisotropy (Δε), it is preferred that one or more compounds represented by the general formula (N) are further contained. The compound represented by the general formula (N) is preferably a compound having a negative dielectric property, a negative sign of Δε, and an absolute value greater than 2, more preferably greater than 3. The compound represented by the general formula (N) can be used alone or in combination. There is no particular limitation on the type of compound that can be combined, and it is appropriately used in combination according to desired performance such as solubility at low temperatures, transition temperature, and birefringence.

[0116] [Chemistry 18]

[0117]

[0118] (Where R N1 and R N2 Each independently represents an alkyl group having 1 to 12 carbon atoms, and one or two or more non-adjacent -CH2- groups in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,

[0119] m N1 means 0, 1, 2 or 3,

[0120] A N1 、A N2 and A N3 Each independently expresses the freedom to choose

[0121] (a) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- groups in this group may be substituted with -O-),

[0122] (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= groups in this group may be substituted with -N=.) and

[0123] (c) 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl

[0124] In the group consisting of: the group (a), group (b) and group (c) are each independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, a cyano group or a fluorine atom; A N1 、A N2 and A N3 At least one of them represents 2,3-difluoro-1,4-phenylene, 1,7,8-trifluoronaphthalene-2,6-diyl or 3,4,5-trifluoronaphthalene-2,6-diyl,

[0125] Z N1 and Z N2 Each independently represents a single bond, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=NN=CH-, -CH=CH-, -C≡C- or -CF=CF-,

[0126] m N1 A for 2 or 3 N2 and Z N2 When there are multiple N2 and Z N2 Each independently may be the same or different.)

[0127] In the general formula (N), R N1 and R N2 Each independently is preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, further preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and particularly preferably an alkenyl group having 3 carbon atoms (propenyl).

[0128] Furthermore, when the ring structure to which it is attached is a phenyl group (aromatic), linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, and alkenyl groups having 4 to 5 carbon atoms are preferred. When the ring structure to which it is attached is a saturated ring structure such as cyclohexane, pyran, and dioxane, linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, and linear alkenyl groups having 2 to 5 carbon atoms are preferred. To stabilize the nematic phase, the total number of carbon atoms and oxygen atoms, when present, is preferably 5 or less, and linear chain is preferred.

[0129] The alkenyl group is preferably a group selected from any one of formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

[0130] [Chemistry 19]

[0131]

[0132] A N1 、A N2 、A N21 and A 23 Each independently, when increasing Δn is required, an aromatic group is preferred, and an aliphatic group is preferred for improving the response speed. It preferably represents trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2]octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, and more preferably represents the following structure,

[0133] [Chemistry 20]

[0134]

[0135] More preferably, it represents trans-1,4-cyclohexylene, 1,4-cyclohexenylene, or 1,4-phenylene.

[0136] Z N11 and Z N12 Each independently preferably represents -CH2O-, -CF2O-, -CH2CH2-, -CF2CF2-, or a single bond, more preferably -CH2O-, -CH2CH2-, or a single bond, and particularly preferably -CH2O- or a single bond.

[0137] m N1 It is preferably 0, 1 or 2. When the viscosity is to be reduced, m N1 It is preferably 0. If you want to increase the transition temperature, m N1Preferably 1.

[0138] The preferred lower limit of the content of the compound represented by formula (N) relative to the total amount of the composition of the present invention is 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%. The preferred upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, or 20%.

[0139] In the case where the viscosity of the composition of the present invention needs to be kept low, for the composition having a fast response speed, preferably the above-mentioned lower limit is low and the upper limit is low. Further, in the case where the resistivity value, VHR of the composition of the present invention require to be high, for the composition having high reliability, preferably the above-mentioned lower limit is low and the upper limit is low. In addition, when wanting to increase dielectric anisotropy in order to keep driving voltage low, preferably the above-mentioned lower limit is high and the upper limit is high.

[0140] As the general formula (N), it is preferable to contain the general formula (Ni).

[0141] [Chemistry 21]

[0142]

[0143] (Where R Ni1 、R Ni2 , Z Ni1 and m Ni1 Each independently represents R in the general formula (N) N1 、R N2 , Z N1 and m N1 The same meaning,

[0144] A Ni1 and A Ni2 Each independently expresses the freedom to choose

[0145] (a) 1,4-cyclohexylene (one -CH2- or two or more non-adjacent -CH2- groups in this group may be substituted with -O- and / or -S-),

[0146] (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= groups in the group may be substituted with -N=) and

[0147] (c) 1,4-cyclohexenylene, 1,4-bicyclo(2.2.2)octylene, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl

[0148] In the group consisting of the above, the hydrogen atoms on the group (a), group (b) and group (c) may be independently substituted by an alkyl group having 1 to 3 carbon atoms, an alkenyl group having 2 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkenyloxy group having 1 to 3 carbon atoms, CN or halogen.

[0149] A Ni1 and A Ni2 Independently of each other, trans-1,4-cyclohexylene and 1,4-phenylene are preferred. When the viscosity is to be reduced, trans-1,4-cyclohexylene is more preferred. When the birefringence anisotropy is to be increased, 1,4-phenylene is more preferred. In addition, each group is preferably unsubstituted.

[0150] Furthermore, as the general formula (N), it is preferred that one or two or more compounds selected from the general formula (V) or the general formula (VI) be contained.

[0151] [Chemistry 22]

[0152]

[0153] Where R 51 and R 61 Independently represent R in the general formula (N) N1 Same meaning, R 52 and R 62 Independently represent R in the general formula (N) N2 Same meaning.

[0154] A 51 、A 52 、A 53 、A 61 、A 62 and A 63 Each independently represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group, or a 1,4-cyclohexenylene group. One or two or more hydrogen atoms present on the 1,4-phenylene group may be independently substituted with a halogen. In the present invention, each independently represents a trans-1,4-cyclohexylene group and a 1,4-phenylene group. When the viscosity is to be reduced, the trans-1,4-cyclohexylene group is preferred. When the birefringence is to be increased, the 1,4-phenylene group is preferred.

[0155] Z 51 , Z 52 , Z 61 and Z 62They independently represent a single bond, -CH2CH2-, -(CH2)4-, -OCH2-, -CH2O-, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=NN=CH-, -CH=CH-, -C≡C- or -CF=CF-. In the present invention, they independently represent -CH2O-, -OCH2- or a single bond.

[0156] a 51 、a 52 、a 61 and a 62 Independently represent 0, 1 or 2, a 51 +a 52 Indicates 0, 1, or 2, a 61 +a 62 Indicates 0, 1, or 2, in a 51 In the case of 2, there are 2 A 51 Can be the same or different, in a 52 In the case of 2, there are 2 A 52 Can be the same or different, in a 51 In the case of 2, there are 2 Z 51 Can be the same or different, in a 52 In the case of 2, there are 2 Z 52 Can be the same or different, in a 61 In the case of 2, there are 2 A 61 Can be the same or different, in a 62 In the case of 2, there are 2 A 62 Can be the same or different, in a 61 In the case of 2, there are 2 Z 61 Can be the same or different, in a 62 In the case of 2, there are 2 Z 62 In the present invention, independently of each other, when the viscosity is to be reduced, it is preferably 0, and when the transition temperature is to be increased, a 51 +a 52 and a 61 +a 62 Preferably 1 or 2.

[0157] As the general formula (V), it is preferred to include the general formula (N-1d).

[0158] [Chemistry 23]

[0159]

[0160] (Where R N11 and RN12 Respectively represent R in the general formula (N) N1 and R N1 Same meaning, n Nd11 Indicates 1 or 2.)

[0161] Furthermore, as the general formula (N), any one or more compounds represented by the following general formulae (N-1a) to (N-1g) may be contained.

[0162] [Chemistry 24]

[0163]

[0164] (Where R N11 and R N12 Indicates the same as R in the general formula (N) N1 and R N1 Same meaning, n Na11 Indicates 0 or 1, n Nb11 Indicates 1 or 2, n Nc11 Indicates 0 or 1, n Ne11 Indicates 1 or 2, n Nf11 Indicates 1 or 2, n Ng11 Indicates 1 or 2, A Ne11 represents trans-1,4-cyclohexylene or 1,4-phenylene, A Ng11 represents trans-1,4-cyclohexylene, 1,4-cyclohexenylene or 1,4-phenylene, and at least one of them represents 1,4-cyclohexenylene, Z Ne11 represents a single bond or an ethylene group and at least one represents an ethylene group. )

[0165] Regarding the liquid crystal composition of the present invention, in the case of a liquid crystal composition having a positive dielectric anisotropy (Δε), it is preferred that the composition further contain one or more compounds selected from the group of compounds represented by the following general formulae (A1) to (A3) and (B1) to (B3). The compound selected from the group of compounds represented by the general formulae (A1) to (A3) and (B1) to (B3) is preferably a compound having a positive dielectric property, and the sign of Δε is positive and the absolute value thereof is greater than 2. The compound selected from the group of compounds represented by the general formulae (A1) to (A3) and (B1) to (B3) can be used alone or in combination. There is no particular limitation on the type of compound that can be combined, and they are appropriately used in combination according to the desired performance such as solubility at low temperatures, transition temperature, birefringence, etc.

[0166] The compounds represented by general formulae (A1) to (A3) are so-called fluorine-based (halogen-based) p-type compounds.

[0167] [Chemistry 25]

[0168]

[0169] (Where R b represents an alkyl group having 1 to 12 carbon atoms, which may be linear, may have a methyl or ethyl branch, or may have a 3- to 6-membered ring structure, any -CH2- present in the group may be substituted by -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, or -C≡C-, any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, and when an asymmetric carbon is generated due to the branching, the compound may be optically active or a racemic form,

[0170] Ring A, Ring B, and Ring C each independently represent a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-trans-2,6-diyl group, a 1,4-phenylene group which may be substituted with one or more fluorine atoms, a naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, a tetrahydronaphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, a 1,4-cyclohexenylene group which may be substituted with a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, a pyrimidine-2,5-diyl group, or a pyridine-2,5-diyl group.

[0171] L a , L b and L c Each independently represents a single bond, an ethylene group (-CH2CH2-), a 1,2-propylene group (-CH(CH3)CH2- and -CH2CH(CH3)-), a 1,4-butylene group, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C- or -CH=NN=CH-,

[0172] Ring Z represents a substituent represented by general formulae (La) to (Lc),

[0173] [Chemistry 26]

[0174]

[0175] (where Y a ~Y j each independently represents a hydrogen atom or a fluorine atom,

[0176] P a represents a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group or a difluoromethyl group, or an alkoxy group, an alkyl group, an alkenyl group or an alkenyloxy group having 2 or 3 carbon atoms substituted with 2 or more fluorine atoms.

[0177] R bPreferred are linear alkyl groups having 1 to 7 carbon atoms, linear 1-alkenyl groups having 2 to 7 carbon atoms, linear 3-alkenyl groups having 4 to 7 carbon atoms, and alkyl groups having 1 to 5 carbon atoms substituted at the terminal with an alkoxy group having 1 to 3 carbon atoms.

[0178] Ring A, Ring B, and Ring C are preferably trans-1,4-cyclohexylene, trans-decahydronaphthalene-trans-2,6-diyl, naphthalene-2,6-diyl which may be substituted with fluorine atoms, or 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms. In particular, when Ring B is trans-1,4-cyclohexylene or trans-decahydronaphthalene-trans-2,6-diyl, Ring A is preferably trans-1,4-cyclohexylene. When Ring C is trans-1,4-cyclohexylene or trans-decahydronaphthalene-trans-2,6-diyl, Ring B and Ring A are preferably trans-1,4-cyclohexylene. Furthermore, in (A3), Ring A is preferably trans-1,4-cyclohexylene.

[0179] L a , L b and L c Preferred are single bonds, ethylene, 1,4-butylene, -COO-, -OCF2-, -CF2O-, -CF=CF-, or -C≡C-, and particularly preferred are single bonds or ethylene. Preferably, at least one of (A2) and at least two of (A3) represent single bonds.

[0180] Among the ring Z, Y in (La) is preferably a and Y b At least one of them is a fluorine atom, preferably Y in (Lb) d ~Y f At least one of them is a fluorine atom, especially Y d A fluorine atom is more preferred.

[0181] Terminal group P a A fluorine atom, a trifluoromethoxy group or a difluoromethoxy group is preferred, and a fluorine atom is particularly preferred.

[0182] When the compounds represented by the general formulae (A1) to (A3) are used in combination, the same options (ring A, L a , etc.) may represent the same substituent or different substituents.

[0183] In addition, among the general formulae (A1) to (A3), the general formulae (i) and (ii) of the present invention are excluded.

[0184] The preferred lower limits of the content of the compounds represented by general formulae (A1) to (A3) relative to the total amount of the composition of the present invention are 1%, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. The preferred upper limits of the content are 85%, 75%, 65%, 55%, 45%, 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, and 5%.

[0185] In the case where the viscosity of the composition of the present invention needs to be kept low, for the composition having a fast response speed, preferably make the above-mentioned lower limit high, make the upper limit high. Further, in the case where the resistivity value, VHR of the composition of the present invention needs to be high, for the composition having high reliability, preferably make the above-mentioned lower limit low, make the upper limit low. In addition, when wanting to increase dielectric anisotropy in order to keep driving voltage low, preferably make the above-mentioned lower limit high, make the upper limit high.

[0186] More preferred embodiments of the general formulae (A1) to (A3) can be represented by the following general formulae (A1a) to (A3c).

[0187] [Chemistry 27]

[0188]

[0189] (Where A, B, C, Y a and Y b Indicates A, B, C, Y in general formula (A1) to (A3) a and Y b Same meaning.)

[0190] The following compounds are more preferred.

[0191] [Chemistry 28]

[0192]

[0193] [Chemistry 29]

[0194]

[0195] The compounds represented by general formulae (B1) to (B3) are so-called cyanide-based p-type compounds.

[0196] [Chemistry 30]

[0197]

[0198] (Where Rc represents an alkyl group having 1 to 12 carbon atoms, which may be linear, may have a methyl or ethyl branch, or may have a 3- to 6-membered ring structure, any -CH2- present in the group may be substituted by -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, or -C≡C-, any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, and when an asymmetric carbon is generated due to the branching, the compound may be optically active or a racemic form,

[0199] Ring D, Ring E, and Ring F each independently represent a trans-1,4-cyclohexylene group, a trans-decahydronaphthalene-trans-2,6-diyl group, a 1,4-phenylene group which may be substituted with one or more fluorine atoms, a naphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, a tetrahydronaphthalene-2,6-diyl group which may be substituted with one or more fluorine atoms, a 1,4-cyclohexenylene group which may be substituted with a fluorine atom, a 1,3-dioxane-trans-2,5-diyl group, a pyrimidine-2,5-diyl group, or a pyridine-2,5-diyl group.

[0200] L d , L e and L f Each independently represents a single bond, an ethylene group (-CH2CH2-), a 1,2-propylene group (-CH(CH3)CH2- and -CH2CH(CH3)-), a 1,4-butylene group, -COO-, -OCO-, -OCF2-, -CF2O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, -C≡C-, -OCH2-, -CH2O- or -CH=NN=CH-,

[0201] Ring Y is an aromatic ring and represents a substituent represented by the following general formulas (Ld) to (Lf),

[0202] [Chemistry 31]

[0203]

[0204] (where Y k ~Y q Each independently represents a hydrogen atom or a fluorine atom.)

[0205] Terminal group P b Represents cyano (-CN), cyanooxy (-OCN) or -C≡CCN.)

[0206] R c Preferred are linear alkyl groups having 1 to 7 carbon atoms, linear 1-alkenyl groups having 2 to 7 carbon atoms, linear 3-alkenyl groups having 4 to 7 carbon atoms, and alkyl groups having 1 to 5 carbon atoms substituted at the terminal with an alkoxy group having 1 to 3 carbon atoms.

[0207] Ring D, Ring E, and Ring F are preferably trans-1,4-cyclohexylene, trans-decahydronaphthalene-trans-2,6-diyl, naphthalene-2,6-diyl which may be substituted with fluorine atoms, or 1,4-phenylene which may be substituted with 1 to 2 fluorine atoms. In particular, when Ring E is trans-1,4-cyclohexylene or trans-decahydronaphthalene-trans-2,6-diyl, Ring D is preferably trans-1,4-cyclohexylene. When Ring F is trans-1,4-cyclohexylene or trans-decahydronaphthalene-trans-2,6-diyl, Ring D and Ring E are preferably trans-1,4-cyclohexylene. Furthermore, in (B3), Ring D is preferably trans-1,4-cyclohexylene.

[0208] L d , L e and L f Preferred are single bonds, ethylene groups, -COO-, -OCF2-, -CF2O-, -CF=CF-, or -C≡C-, and particularly preferred are single bonds, ethylene groups, or -COO-. Furthermore, it is preferred that at least one of (B2) and at least two of (B3) represent single bonds.

[0209] In the ring Y, Y in (Le) m A fluorine atom is preferred.

[0210] Terminal group P b Preferred is a cyano group.

[0211] When the compounds represented by general formulae (B1) to (B3) are used in combination, the same options (ring D, L) in different molecules are d , etc.) may represent the same substituent or different substituents.

[0212] In addition, among the general formulae (B1) to (B3), the general formulae (i) and (ii) of the present invention are excluded.

[0213] The preferred lower limits of the content of the compounds represented by general formulae (B1) to (B3) relative to the total amount of the composition of the present invention are 1%, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, and 80%. The preferred upper limits of the content are 85%, 75%, 65%, 55%, 45%, 35%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, and 5%.

[0214] In the case where the viscosity of the composition of the present invention needs to be kept low, for the composition having a fast response speed, preferably the above-mentioned lower limit is low, the upper limit is high. Further, in the case where the resistivity value, VHR of the composition of the present invention needs to be high, for the composition having high reliability, preferably the above-mentioned lower limit is low, the upper limit is high. In addition, when the driving voltage is low and the dielectric anisotropy is increased, preferably the above-mentioned lower limit is high, the upper limit is high.

[0215] More preferred embodiments of the general formulae (B1) to (B3) can be represented by the following general formulae (B1a) to (B2c).

[0216] [Chemistry 32]

[0217]

[0218] (Where A, B, Y k and Y l Represents A, B, Y in general formula (B1) to (B3) k and Y l Same meaning.)

[0219] The following compounds are more preferred.

[0220] [Chemistry 33]

[0221]

[0222] [Chemistry 34]

[0223]

[0224] The liquid crystal composition of the present invention preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (L), and a compound represented by the general formula (N). It preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (i), and a compound represented by the general formula (N).

[0225] The liquid crystal composition of the present invention preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (L), and a compound represented by the general formula (Ni) at the same time, and preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (L), a compound represented by the general formula (Ni), and a compound selected from the general formula (V) or the general formula (VI) at the same time.

[0226] The liquid crystal composition of the present invention preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (L), and a compound selected from the general formula (V) or the general formula (VI). It preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (L), and a compound represented by the general formula (V).

[0227] The liquid crystal composition of the present invention preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (L), and a compound selected from the group of compounds represented by the general formulas (A1) to (A3) and (B1) to (B3). It preferably contains three or more dichroic pigments selected from disazo compounds and triazo compounds, a compound represented by the general formula (i), and a compound selected from the group of compounds represented by the general formulas (A1) to (A3) and (B1) to (B3).

[0228] The preferred lower limit of the total content of the compounds represented by general formula (L) and general formula (N) relative to the total amount of the main liquid crystal composition is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100%. The preferred upper limit of the content is 100%, 99%, 98%, or 95%.

[0229] The preferred lower limit of the total content of the compounds represented by general formula (L), general formulae (A1) to (A3), and general formulae (B1) to (B3) relative to the total amount of the main liquid crystal composition is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100%. The preferred upper limit of the content is 100%, 99%, 98%, or 95%.

[0230] The preferred lower limit of the total content of the compounds represented by General Formula (L), General Formulae (A1a) to (A3c), and General Formulae (B1a) to (B2c) relative to the total amount of the main liquid crystal composition is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, or 100%. The preferred upper limit of the content is 100%, 99%, 98%, or 95%.

[0231] The composition of the present invention preferably does not contain a compound having a structure in which heteroatoms such as oxygen atoms are bonded to each other, such as a peracid (—CO—OO—) structure, in the molecule.

[0232] When reliability and long-term stability of the composition are important, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and most preferably substantially free of the compound, relative to the total mass of the composition.

[0233] When emphasis is placed on stability against UV irradiation, the content of the compound substituted with a chlorine atom is preferably 15% or less, preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially free of the compound, relative to the total mass of the composition.

[0234] It is preferred to increase the content of compounds whose intramolecular ring structures are all 6-membered rings. Relative to the total mass of the aforementioned composition, the content of compounds whose intramolecular ring structures are all 6-membered rings is preferably set to 80% or more, more preferably to 90% or more, and even more preferably to 95% or more. It is most preferred that the composition is essentially composed only of compounds whose intramolecular ring structures are all 6-membered rings.

[0235] In order to suppress the deterioration of the composition due to oxidation, it is preferred to reduce the content of the compound having a cyclohexenylene group as a ring structure. The content of the compound having a cyclohexenylene group is preferably set to 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially free of the compound relative to the total mass of the composition.

[0236] When emphasis is placed on improving viscosity and Tni, it is preferred to reduce the content of the compound having a 2-methylbenzene-1,4-diyl group in which a hydrogen atom may be substituted by a halogen. The content of the compound having the 2-methylbenzene-1,4-diyl group in the molecule is preferably set to 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and even more preferably substantially free of the compound relative to the total mass of the composition.

[0237] In the present application, “substantially free of content” means that the content does not contain any substance other than substances that are unintentionally contained.

[0238] When the compound contained in the composition of the present invention has an alkenyl group as a side chain, when the aforementioned alkenyl group is bonded to cyclohexane, the number of carbon atoms of the alkenyl group is preferably 2 to 5, and when the aforementioned alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5. It is preferred that the unsaturated bond of the aforementioned alkenyl group is not directly bonded to benzene.

[0239] In order to improve the stability of the liquid crystal composition of the present invention, it is preferable to add a stabilizer such as an antioxidant, an ultraviolet (UV) absorber, a light stabilizer, or an infrared absorber. Examples of the antioxidant include hydroquinone derivatives, nitrosoamine-based polymerization inhibitors, and hindered phenol-based antioxidants. More specifically, examples include tert-butylhydroquinone, methylhydroquinone, "Q-1300" and "Q-1301" manufactured by Wako Pure Chemical Industries, Ltd., and "IRGANOX 1010," "IRGANOX 1035," "IRGANOX 1076," "IRGANOX 1098," "IRGANOX 1135," "IRGANOX 1330," "IRGANOX 1425," "IRGANOX 1520," "IRGANOX 1726," "IRGANOX 245," "IRGANOX 259," "IRGANOX 3114," "IRGANOX 3790," "IRGANOX 5057," and "IRGANOX 565" manufactured by BASF.

[0240] As UV absorbers, from the perspective of excellent absorption of ultraviolet rays with a wavelength of 370 nm or less and good liquid crystal display properties, those with low absorption of visible light with a wavelength of 400 nm or more are preferred. More specifically, examples include hindered phenol compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylate compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, and triazine compounds. Examples of hindered phenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate. Examples of the benzotriazole compounds include 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2,2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol), (2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene. , 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, (2-(2'-hydroxy-3',5'-di-tert-pentylphenyl)-5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], TINUVIN 109, TINUVIN 171, TINUVIN 326, TINUVIN 327, TINUVIN 328, TINUVIN 770, TINUVIN 900, TINUVIN 928 manufactured by BASF Japan Co., Ltd., and KEMISORB 71, KEMISORB 73, and KEMISORB 74 manufactured by Chemiprokasei Kaisha Co., Ltd. can also be preferably used.

[0241] The amount of the stabilizer added is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.0% by mass, 0.05 to 0.5% by mass, more preferably 0.1 to 1.0% by mass, and even more preferably 0.1 to 0.5% by mass relative to the polymerizable liquid crystal composition.

[0242] In addition to the above-mentioned compounds, the liquid crystal composition of the present invention may further contain a compound selected from common nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, chiral agents, and polymerizable compounds.

[0243] The liquid crystal composition of the present invention can use a compound having an asymmetric atom as a chiral agent for inducing helical pitch, an axially asymmetric compound, or a mixture thereof. The chiral agent for inducing helical pitch is preferably a compound having an asymmetric carbon atom, preferably a molecular structure having one or two or more 1,4-phenylene groups (one or two of the hydrogen atoms in this group may be substituted with fluorine, methyl, or methoxy groups). To improve or adjust the temperature dependence of the helical pitch, a mixture of multiple chiral agents can be used.

[0244] The liquid crystal composition of the present invention may contain a polymerizable compound used in PS-type, PSA-type, PSVA-type, etc., as the polymerizable compound. For example, a polymerizable compound composed of two or three 1,4-phenylene groups is preferred, and the polymerizing group is preferably an acrylate or methacrylate. Specifically, the polymerizable compound represented by Formulas (RM-001) to (RM-007) may be appropriately contained in the range of 0% to 5% by mass.

[0245] The following polymerizable compounds may be appropriately contained within a range of 0% by mass to 5% by mass.

[0246] [Chemistry 35]

[0247]

[0248] The hydrogen or fluorine atoms in the 1,4-phenylene group that constitutes the molecular structure of the polymerizable compound may be arbitrarily replaced with fluorine atoms, methyl groups, or methoxy groups. Furthermore, the polymerizable compound used in the present invention may include an alkylene group, generally referred to as a spacer, between the ring and the polymerizing group, as in RM-005. The alkylene group preferably has 1 to 10 carbon atoms.

[0249] When the liquid crystal composition of the present invention contains 1% to 5% by mass of a polymerizable compound, the spacer is preferably an alkylene group having 1 to 6 carbon atoms. From the perspective of improving solubility, it is further preferred to combine multiple polymerizable compounds. When the liquid crystal composition of the present invention contains 0.1% to 1% by mass of a polymerizable compound, it is preferred to contain one or more polymerizable compounds represented by formulas (RM-001) to (RM-007).

[0250] The liquid crystal composition of the present invention is a nematic liquid crystal composition having a positive or negative dielectric anisotropy (Δε). When the liquid crystal composition has a negative dielectric anisotropy, the dielectric anisotropy (Δε) at 25°C is -2.0 to -6.0, more preferably -2.0 to -5.0, and particularly preferably -2.5 to -5.0.

[0251] When the liquid crystal composition of the present invention has positive dielectric anisotropy, the dielectric anisotropy (Δε) at 25° C. is 2.0 to 20.0, preferably 2.0 to 15.0, more preferably 2.0 to 10.0, and particularly preferably 2.0 to 9.0.

[0252] The birefringence anisotropy (Δn) of the liquid crystal composition of the present invention at 25° C. is 0.070 to 0.200, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12.

[0253] The viscosity (η) of the liquid crystal composition of the present invention at 20°C is 10 to 100 mPa·s, preferably 10 to 90 mPa·s, preferably 10 to 80 mPa·s, preferably 10 to 70 mPa·s, preferably 10 to 60 mPa·s, further preferably 10 to 50 mPa·s, preferably 10 to 40 mPa·s, and particularly preferably 10 to 30 mPa·s.

[0254] The rotational viscosity (γ1) of the liquid crystal composition of the present invention at 25°C is 40 to 250 mPa·s, preferably 40 to 200 mPa·s, preferably 40 to 160 mPa·s, preferably 40 to 140 mPa·s, preferably 40 to 140 mPa·s, preferably 40 to 130 mPa·s, preferably 40 to 125 mPa·s, more preferably 40 to 120 mPa·s, further preferably 40 to 115 mPa·s, more preferably 40 to 110 mPa·s, and particularly preferably 40 to 100 mPa·s.

[0255] The nematic phase-isotropic liquid phase transition temperature (T ni ) is preferably above 80°C, preferably above 90°C, preferably above 100°C, preferably above 110°C, preferably above 120°C, and particularly preferably adjusted to 90°C to 115°C.

[0256] The liquid crystal composition of the present invention exhibits black color, a dichroic pigment, and unprecedentedly high solubility. Consequently, precipitation is suppressed or eliminated at temperatures below 25°C or -20°C, enabling use over a wide temperature range. Consequently, it is readily applicable to display devices for automotive applications, where adaptability to harsh environments is crucial, portable devices such as smartphones and tablets, and dimming devices such as window glass. Furthermore, it exhibits excellent light resistance, UV resistance, and heat resistance, resulting in no or suppressed color shifts.

[0257] Devices using the liquid crystal composition of the present invention exhibit excellent black color. Rather than the conventional dull black, they achieve a metallic black with a vibrant, transparent appearance, resulting in high contrast. Furthermore, conventional problems such as inability to use at low temperatures are avoided or minimized. Furthermore, they exhibit excellent light resistance, UV resistance, and heat resistance, with no or minimal color change.

[0258] Regarding the liquid crystal composition of the present invention, in the case of a liquid crystal composition with negative dielectric anisotropy, a liquid crystal display element with APL (antiparallel) and VA (vertical alignment) is preferred. In order to obtain a high contrast, it is further preferred to twist the orientation axis by 90°, and further preferred to twist it by 240°. In the case of wanting to obtain a higher contrast, it is technically more difficult, and it is preferred to twist it by 250°, 260°, or 270°, and it is also preferred to twist it by 360°.

[0259] In addition, in the case of a liquid crystal composition having negative dielectric anisotropy, the pretilt angle is preferably 80° to 90°.

[0260] When the liquid crystal composition of the present invention is a liquid crystal composition having positive dielectric constant anisotropy, it is preferably a so-called TN type or STN type liquid crystal display element. In order to obtain a high contrast, it is further preferred to twist the orientation axis by 180°, and further preferably by 240°, 250°, 260°, 270°, or 360° or more.

[0261] Furthermore, when the liquid crystal composition has positive dielectric anisotropy, the pretilt angle is preferably 1° to 15°.

[0262] The liquid crystal composition of the present invention can be used in a liquid crystal display element or a light-adjusting element.

[0263] In addition, the liquid crystal display element using the liquid crystal composition of the present invention is useful for active matrix driven liquid crystal display elements, and can be used for liquid crystal display elements for PSA mode, PSVA mode, VA mode, PS-IPS mode, TN mode, STN mode, IPS mode or PS-FFS mode.

[0264] The two substrates of the liquid crystal cell used in the element can be made of glass or a flexible transparent material such as plastic, and the other can be made of an opaque material such as silicon. The transparent substrate with a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) onto a transparent substrate such as a glass plate. To improve the contrast of the element, it is preferable to use a substrate that has been subjected to an anti-glare treatment such as AR coating.

[0265] The color filter can be made, for example, by a pigment dispersion method, a printing method, an electrodeposition method or a dyeing method. Taking the method of making a color filter by a pigment dispersion method as an example, a curable coloring composition for a color filter is applied to the transparent substrate, patterned, and then cured by heating or light irradiation. By performing this process on the three colors of red, green and blue respectively, a pixel portion for a color filter can be made. In addition, a pixel electrode having active elements such as a TFT, a thin film diode, a metal insulator metal resistor element, etc. can also be provided on the substrate.

[0266] The substrates are positioned facing each other with the transparent electrode layer facing inward. The spacing between the substrates can be adjusted using spacers. The thickness of the resulting light-adjusting layer is preferably adjusted to a value between 1 and 100 μm, more preferably between 1.5 and 10 μm. When using a polarizing plate, the product of the liquid crystal refractive index anisotropy Δn and the cell thickness d is preferably adjusted to maximize contrast.

[0267] When the liquid crystal composition contains a chiral agent, the twist pitch (p) of the liquid crystal composition is preferably 2 μm to 20 μm. More specifically, the twist pitch (p) is appropriately adjusted depending on the mode of the liquid crystal display element, such as TN mode or STN mode.

[0268] In addition, when the liquid crystal composition contains a chiral agent, it is preferred that the relationship between the twist pitch (p) and the cell thickness d, i.e., the d / p value, satisfies 0.5 to 2.2. Specifically, according to the twist angle, the relationship between the twist pitch (p) and the cell thickness (d) is adjusted in such a way that the d / p value becomes the most suitable. The most suitable d / p value is a region where orientation defects such as anti-phase twist domains and stripe domains do not appear. For example, in the case of a twist of 240°, the most suitable d / p value exists in the range of 0.45 to 0.66. It is preferred to observe the domains by visual inspection, microscopy, etc., and adjust in such a way that no orientation defects occur.

[0269] In addition, when there are two polarizing plates, the polarization axis of each polarizing plate can also be adjusted to adjust the viewing angle and contrast to be good. Further, a phase difference film for expanding the viewing angle can also be used. As spacers, for example, glass particles, plastic particles, aluminum oxide particles, photoresist materials, etc. can be listed. Then, a sealant such as an epoxy-based heat-curing composition is screen-printed on the substrate in the form of a liquid crystal injection port, the substrates are bonded to each other, and heating is used to heat-cure the sealant.

[0270] As a method for sandwiching the liquid crystal composition between two substrates, a common vacuum injection method, an ODF method, or the like can be used.

[0271] In the device of the present invention, a film that filters light having a wavelength of 400 nm or less may be laminated and used as an ultraviolet filter in the liquid crystal cell.

[0272] The device of the present invention can be used as a single-layer liquid crystal cell or as a stack of two or three liquid crystal cells. When stacking multiple cells, it is preferred to stack the vertical alignment cells treated with antiparallel alignment at 90° to improve contrast.

[0273] Example

[0274] The present invention will be further described in detail with reference to the following examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples and comparative examples means "mass %".

[0275] The following abbreviations are used in describing the liquid crystal compounds in the Examples.

[0276] (Ring structure)

[0277] [Chemistry 36]

[0278]

[0279] (Side chain structure and connection structure)

[0280] [Table 1]

[0281] The record in the formula Substituents and linkers represented by 1- <![CDATA[CH3-]]> 2- <![CDATA[C2H5-]]> 3- <![CDATA[n-C3H7-]]> 4- <![CDATA[n-C4H9-]]> 5- <![CDATA[n-C5H 11 -]]> V- <![CDATA[CH2=CH-]]> V2- <![CDATA[CH2=CH-CH2-CH2-]]> 1V2- <![CDATA[CH3-CH=CH-CH2-CH2-]]> -1 <![CDATA[-CH3]]> -2 <![CDATA[-C2H5]]> -3 <![CDATA[-n-C3H7]]> -O2 <![CDATA[-OC2H5]]> -V0 <![CDATA[-CH=CH2]]> -V1 <![CDATA[-CH=CH-CH3]]> -2V <![CDATA[-CH2-CH2-CH=CH2]]> -F -F -OCF3 <![CDATA[-OCF3]]> -CN -CN - single bond -E- -COO- -CH2CH2- <![CDATA[-CH2CH2-]]> -CFFO- <![CDATA[-CF2O-]]> -T- -C≡C- -O1- <![CDATA[-OCH2-]]> -1O- <![CDATA[-CH2O-]]>

[0282] The properties measured in the examples are as follows.

[0283] T ni : Nematic-isotropic liquid phase transition temperature (℃)

[0284] The measurement was performed using a heating stage manufactured by Mettler and a Nikon polarizing microscope.

[0285] Δn: Refractive index anisotropy at 25°C

[0286] Measured using an Abbe refractometer.

[0287] Δε: Dielectric anisotropy at 25°C

[0288] The measurement was performed using an LCR meter manufactured by Agilent.

[0289] η: Volume flow viscosity [mPa·s] (20°C)

[0290] Measured using an E-type viscometer.

[0291] Solubility: Approximately 0.5 g of the liquid crystal composition was placed in a test tube, degassed, filled with nitrogen, capped, and stored in a thermostatic chamber. After 240 hours, the presence of precipitation was visually observed. No precipitation was scored as "○"; observed precipitation was scored as "×". Storage temperatures were -25°C, -15°C, and 0°C.

[0292] Chromaticity: Chromaticity is the chromaticity of light transmitted through a test panel (cell thickness 10 μm) filled with a liquid crystal composition and using a DMS-501 spectrometer, the spectrum of the LED light source and the spectrum of light transmitted by the GH-LCD were converted to the chromaticity of the D65 light source and expressed using the CIE 1931 xy coordinate system.

[0293] Transmittance (off): Transmittance (%) at an applied voltage of 0 (V) when the electro-optical characteristics of the test panel injected with the liquid crystal composition were evaluated at 25°C using a white LED light source (DMS-501 manufactured by Autronic).

[0294] Transmittance (ON): Transmittance (%) at an applied voltage of 810 (V) when the electro-optical characteristics of the test panel injected with the liquid crystal composition were evaluated at 25°C using a white LED light source (DMS-501 manufactured by Autronic).

[0295] Pitch: A standard masterbatch and a sample of known pitch are injected into a wedge-shaped unit, and the pitch is calculated from the angle θ of the wedge-shaped unit and the interval between the disclination lines obtained based on the standard masterbatch.

[0296] (Comparative Example 1, Comparative Example 2, Example 1 and Example 2)

[0297] Using a yellow disazo compound (4-[4-{4-(4-ethylbenzyloxy)phenylazo}-2-methylphenylazo]-4'-ethoxycarbonylbiphenyl) as the azo dye (A), a red triazo compound (4-N,N-diethylamino-4'-[4-(3,5,5-trimethylhexyloxy)phenylazo}phenylazo]azobenzene) as the azo dye (B), a blue triazo compound (4-[4-{4-(1-heptyl-2,2,4,7-tetramethyl-1,2,3,4-tetrahydroquinolin-6-ylazo)naphthalen-1-ylazo}naphthalen-1-ylazo]benzoic acid 4-pentylphenyl ester) as the azo dye (C), and anthraquinone as a comparative dye, liquid crystal compositions of Comparative Example 1, Comparative Example 2, Example 1, and Example 2 shown in the following table were prepared, and their physical properties and characteristics were measured. The maximum absorption wavelength of azo dye (A) is 402 nm, the maximum absorption wavelength of azo dye (B) is 522 nm, and the maximum absorption wavelength of azo dye (C) is 636 nm. The maximum absorption wavelength of the dichroic dye was determined by adding 0.5% of each dichroic dye to 100% of a standard masterbatch (RD-001), injecting the dichroic dye into an antiparallel cell with a cell thickness of 10 μm, and measuring the absorbance using a spectrometer (DMS-501).

[0298] The proportions of the liquid crystal compositions in the table are expressed in parts by mass. Furthermore, these liquid crystal compositions were used to produce a vertically aligned test panel liquid crystal cell with a cell thickness d of 10 μm. The composition, physical properties, characteristics, and test results of the resulting liquid crystal compositions are shown in Table 2. The values ​​for Δn, Δε, and η represent the physical properties of the main liquid crystal (HLC).

[0299] [Table 2]

[0300]

[0301] According to Examples 1 and 2 and Comparative Examples 1 and 2, it can be seen that the addition of azo dyes results in higher solubility in the main liquid crystal composition than anthraquinone dyes. In addition, by including a compound corresponding to the general formula (Ni) having a negative dielectric anisotropy, the T can be increased without affecting the viscosity, dielectric anisotropy, and refractive index anisotropy. ni Furthermore, by containing the compound corresponding to the general formula (Ni), the low-temperature storage property is improved.

[0302] (Examples 6 to 10)

[0303] The liquid crystal compositions of Examples 6 to 10 shown in the following table were prepared, and their physical properties and characteristics were measured. The proportions of the liquid crystal compositions in the table are expressed in parts by mass. Furthermore, these liquid crystal compositions were used to produce liquid crystal cells for vertically aligned test panels with a cell thickness d of 10 μm. The composition of the combined liquid crystal compositions, their physical properties and characteristics, and the test results are shown in Table 3. The values ​​for Δn, Δε, and η represent the physical properties of the main liquid crystal (HLC).

[0304] [Table 3]

[0305]

[0306] The results of Examples 2, 7, and 8, and the results of Examples 6 and 9, show that the addition of the chiral agent increases the value of [off transmittance] - [on transmittance], thereby improving the contrast. Furthermore, compared to the antiparallel-oriented liquid crystal cells (Examples 2 and 6), the twist angle increases to 240° (Example 7) and 360° (Examples 8 and 9), indicating that the value of [off transmittance] - [on transmittance] increases, thereby improving the contrast. Furthermore, according to Example 10, the liquid crystal composition of the present invention exhibits good solubility even when the azo dye content is increased, thereby improving the contrast.

[0307] (Examples 11 to 15)

[0308] The liquid crystal compositions of Examples 11 to 15 shown in the following table were modulated, and their physical properties and characteristics were measured. The proportions of the liquid crystal compositions in the table are expressed in parts by mass. In addition, using these liquid crystal compositions, vertically oriented liquid crystal units for test panels with a unit thickness d of 10 μm or 5 μm were produced. In Examples 11, 14, and 15, the orientation axes of the two produced liquid crystal units were stacked in a manner orthogonal to each other at 90° to produce liquid crystal units for test panels. In addition, Examples 13 and 15 used substrates subjected to AR coating treatment. The composition of the combined liquid crystal compositions, their physical properties and characteristics, and the test results are shown in Table 4. Among them, the values ​​of Δn, Δε, and η are the physical property values ​​of the main liquid crystal (HLC).

[0309] [Table 4]

[0310]

[0311] The results of Examples 12 and 13, and Examples 14 and 15 show that contrast is improved by applying AR coating. Furthermore, the results of Examples 10, 11, 14, and 15 show that a two-layer structure with antiparallel cells arranged at 90° angles can achieve lower on-state transmittance than a single-layer structure.

[0312] (Examples 16 to 19)

[0313] The liquid crystal compositions of Examples 16 to 19 shown in the following table were modulated, and their physical properties and characteristics were measured. The proportions of the liquid crystal compositions in the table are expressed in parts by mass. In addition, using these liquid crystal compositions, vertically oriented liquid crystal units for test panels with a unit thickness d of 10 μm or 5 μm were produced. In Example 19, the orientation axes of the two produced liquid crystal units were stacked in a manner orthogonal to each other at 90° to produce a liquid crystal unit for a test panel. In addition, Example 18 used a substrate subjected to an AR coating treatment. The composition of the combined liquid crystal compositions, their physical properties and characteristics, and the test results are shown in Tables 5 and 6. Among them, the values ​​of Δn, Δε and η are the physical property values ​​of the main liquid crystal (HLC).

[0314] [Table 5]

[0315]

[0316] [Table 6]

[0317]

[0318] (Comparative Example 3, Examples 20 to 24)

[0319] Liquid crystal compositions of Examples 20 to 24 shown in the following table were prepared, and their physical properties and characteristics were measured. The proportions of the liquid crystal compositions in the table are expressed in parts by mass. Furthermore, these liquid crystal compositions were used to produce antiparallel cells with a cell thickness d of 10 μm or 6 μm, a horizontal orientation, and a twist angle of 0°, or an STN cell with a twist angle of 240°. The composition of the combined liquid crystal compositions, their physical properties and characteristics, and the test results are shown in Tables 7 and 8. The values ​​of Δn, Δε, and η are the physical properties of the main liquid crystal (HLC).

[0320] [Table 7]

[0321]

[0322] [Table 8]

[0323]

[0324] (Examples 25 and 26)

[0325] The liquid crystal compositions of Examples 25 and 26 shown in the following table were prepared, and their physical properties and characteristics were measured. The proportions of the liquid crystal compositions in the table are expressed in parts by mass. Furthermore, using these liquid crystal compositions, horizontally aligned test panel liquid crystal cells with a cell thickness d of 10 μm or 6 μm were produced. The composition of the combined liquid crystal compositions, their physical properties and characteristics, and the test results are shown in Tables 9 and 10. The values ​​of Δn, Δε, and η represent the physical properties of the main liquid crystal (HLC).

[0326] [Table 9]

[0327]

[0328] [Table 10]

[0329]

[0330] (Examples 27 and 28)

[0331] A liquid crystal cell for a test panel of Example 27 was produced in the same manner as in Example 2. A liquid crystal cell for a test panel of Example 28 was produced in the same manner as in Example 2, except that a substrate to which a film that filters light of 400 nm or less was attached was used. Next, the voltage holding ratio (VHR) of the liquid crystal cells of Examples 27 and 28 was measured.

[0332] VHR is the value obtained by measuring the voltage holding ratio (%) relative to the initial applied voltage after UV irradiation using a xenon lamp. The measurement conditions are 5V, 60Hz, and 25°C. The UV irradiation conditions are an illumination of 500W / m 2 The irradiation time was 0 hour, 16 hours, 48 ​​hours, 96 hours and 160 hours, respectively, under the condition of applying 0V or 10V voltage.

[0333] The results of VHR (%) of Examples 27 and 28 are shown in Table 11 according to UV irradiation conditions.

[0334] [Table 11]

[0335]

[0336] Examples 27 and 28 show that Example 28, which includes a filter membrane, can suppress the decrease in voltage holding ratio after UV irradiation and improve reliability compared to Example 27. The suppression of the voltage holding ratio decrease in Example 28 becomes more significant as the UV irradiation time increases.

[0337] According to the above results, the liquid crystal composition of the present invention satisfies the requirements of high contrast, high solubility, high nematic-isotropic transition temperature (T NI ), a GH liquid crystal composition with low birefringence anisotropy (Δn) that is effective for high light resistance and high heat resistance and has both high solubility and high contrast, and the liquid crystal display element or dimming element using it meets the excellent properties required for practical use.

Claims

1. A liquid crystal composition comprising a dichroic pigment and a main liquid crystal composition, The dichroic pigments include compound A: 4-[4-{4-(4-ethylbenzyloxy)phenylazo}-2-methylphenylazo]-4'-ethoxycarbonylbiphenyl, compound B: 4-N,N-diethylamino-[4'-{4-(3,5,5-trimethylhexyloxy)phenylazo}phenylazo]azobenzene, and compound C: 4-[4-{4-(1-heptyl-2,2,4,7-tetramethyl-1,2,3,4- the main liquid crystal composition contains one or more compounds represented by general formulae (C1a) to (C1d), (C2a) to (C2d), and (C3b) to (C3e), and one or more compounds selected from the group consisting of compounds represented by general formulae (A1a) to (A3c) and (B1a) to (B2c), The lower limit of the total content of the compounds represented by general formulae (C1a) to (C1d), (C2a) to (C2d), (C3b) to (C3e), (A1a) to (A3c), and (B1a) to (B2c) relative to the total amount of the main liquid crystal composition is 95%. ni Above 90℃, In the formula, ring G1, ring G2, ring H1 and ring H2 each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group which may be substituted with 1 to 2 fluorine atoms or a methyl group. R f and R g Each independently represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxy group having 1 to 3 carbon atoms, or a linear alkyl group having 1 to 5 carbon atoms substituted at the end with an alkoxy group having 1 to 3 carbon atoms, at least one of which represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 3-alkenyl group having 4 to 7 carbon atoms, wherein When ring G1 to ring G2 are aromatic rings, the corresponding R f To exclude 1-alkenyl and alkoxy, when ring H1 to ring H2 are aromatic rings, the corresponding R g To exclude 1-alkenyl and alkoxy, In the formula, ring G1, ring G2, ring H1, ring H2, ring I1 and ring I2 each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group which may be substituted with 1 to 2 fluorine atoms or a methyl group, R f and R g Each independently represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxy group having 1 to 3 carbon atoms, or a linear alkyl group having 1 to 5 carbon atoms substituted at the end with an alkoxy group having 1 to 3 carbon atoms, at least one of which represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 3-alkenyl group having 4 to 7 carbon atoms, wherein when rings G1 and G2 are aromatic rings, the corresponding R f To exclude 1-alkenyl and alkoxy, when ring I1 to ring I2 are aromatic rings, the corresponding R g To exclude 1-alkenyl and alkoxy, In the formula, ring G2, ring H2, ring I2 and ring J2 each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group which may be substituted with 1 to 2 fluorine atoms or a methyl group, R f and R g Each independently represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, a linear alkoxy group having 1 to 3 carbon atoms, or a linear alkyl group having 1 to 5 carbon atoms substituted at the end with an alkoxy group having 1 to 3 carbon atoms, at least one of which represents a linear alkyl group having 1 to 7 carbon atoms, a linear 1-alkenyl group having 2 to 7 carbon atoms, or a linear 3-alkenyl group having 4 to 7 carbon atoms, wherein when ring G2 is an aromatic ring, the corresponding R f To exclude 1-alkenyl and alkoxy, when ring J2 is an aromatic ring, the corresponding R g To exclude 1-alkenyl and alkoxy, Where R b represents an alkyl group having 1 to 12 carbon atoms, which may be linear, may have a methyl or ethyl branch, or may have a 3- to 6-membered ring structure, any -CH2- present in the group may be substituted by -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, or -C≡C-, any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, and when an asymmetric carbon is generated due to the branching, the compound may be optically active or a racemic form, A, B and C each represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group which may be substituted with 1 to 2 fluorine atoms or a methyl group, Y a and Y b each independently represents a hydrogen atom or a fluorine atom, Where R c represents an alkyl group having 1 to 12 carbon atoms, which may be linear, may have a methyl or ethyl branch, or may have a 3- to 6-membered ring structure, any -CH2- present in the group may be substituted by -O-, -CH=CH-, -CH=CF-, -CF=CH-, -CF=CF-, or -C≡C-, any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, and when an asymmetric carbon is generated due to the branching, the compound may be optically active or a racemic form, A and B each represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group which may be substituted with 1 or 2 fluorine atoms, Y k and Y l Each independently represents a hydrogen atom or a fluorine atom.

2. The liquid crystal composition according to claim 1, wherein the mixing ratio of compound A, compound B and compound C is A:B:C, relative to the total amount of the dichroic pigment in the liquid crystal composition, is 10-60 wt %:10-60 wt %:10-60 wt %. 3 . The liquid crystal composition according to claim 1 , comprising 0.5 to 5 parts by weight of a dichroic dye based on 100 parts by weight of the liquid crystal composition. 4 . The liquid crystal composition according to claim 3 , wherein the chromaticity x and y are adjusted to be 0.310 to 0.370 under standard illuminant D65. The liquid crystal composition according to claim 1 , wherein the twist pitch p is 2 μm to 20 μm. The liquid crystal composition according to claim 1 , further comprising a polymerizable compound. 7 . The liquid crystal composition according to claim 1 , further comprising 0.05 to 0.5 wt % of a stabilizer.

8. The liquid crystal composition according to claim 1, wherein the nematic-isotropic transition temperature is 80°C to 120°C, the dielectric anisotropy is -2.0 to -6.0 or +3.0 to +20.0, and the birefringence is 0.070 to 0.

200. 9 . A device using the liquid crystal composition according to claim 1 . 10 . The device according to claim 9 , wherein the pretilt angle is 80° to 90° or 1° to 15°.

11. The element according to claim 10, wherein the relationship between the twist pitch p and the cell thickness d, that is, the value d / p satisfies 0.5 to 2.

2.

12. The device according to claim 9, wherein the substrate surface is subjected to an anti-glare treatment.

13. The device according to claim 9, wherein two liquid crystal cells having been subjected to antiparallel alignment treatment and vertically aligned are stacked so that their alignment axes intersect at 90 degrees. 14 . The device according to claim 9 , wherein a film for filtering light with a wavelength of 400 nm or less is laminated in the liquid crystal cell. The device according to claim 9 , which is used as a dimming device.

16. The element according to claim 9, which is used for a liquid crystal display element.

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