Liquid crystal composition, liquid crystal compound, liquid crystal cured layer, optical film, polarizing plate, and image display device

Abstract

The present invention addresses the problem of providing: a liquid crystal composition in which the precipitation properties of a liquid crystal compound are suppressed; a liquid crystal compound; a liquid crystal cured layer; an optical film; a polarizing plate; and an image display device. This liquid crystal composition contains a first liquid crystal compound represented by formula (1) and a second liquid crystal compound represented by formula (2), wherein both the first liquid crystal compound and the second liquid crystal compound have a maximum absorption wavelength in the wavelength range of 280-420 nm.

Description

Liquid crystal composition, liquid crystal compound, cured liquid crystal layer, optical film, polarizing plate and image display device

[0001] The present invention relates to a liquid crystal composition, a liquid crystal compound, a cured liquid crystal layer, an optical film, a polarizing plate, and an image display device.

[0002] Optical films such as optical compensation sheets and retardation films are used in various image display devices to eliminate image coloration or widen the viewing angle. Stretched birefringent films have been used as optical films, but in recent years, it has been proposed to use optical films having an optically anisotropic layer made of a liquid crystal compound instead of stretched birefringent films.

[0003] As such an optical film, an optical film formed by polymerizing a compound containing a group represented by a predetermined formula and a polymerizable group is known (see, for example, Patent Document 1).

[0004] JP 2010-031223 A

[0005] The present inventors have studied liquid crystal compositions containing the compounds described in Patent Document 1 and have found that there is room for improvement in the precipitability of the liquid crystal compounds.

[0006] Therefore, an object of the present invention is to provide a liquid crystal composition, a liquid crystal compound, a cured liquid crystal layer, an optical film, a polarizing plate, and an image display device in which the precipitation tendency of the liquid crystal compound is suppressed.

[0007] As a result of intensive research to achieve the above object, the present inventors have found that the precipitation tendency of the liquid crystal compound can be suppressed by using a liquid crystal composition containing a predetermined liquid crystal compound having polymerizable groups at both ends and a liquid crystal compound having a different structure only at one end, and have completed the present invention. That is, the present inventors have found that the above object can be achieved by the following configuration.

[0008] [1] A liquid crystal composition comprising a first liquid crystal compound represented by formula (1) described later and a second liquid crystal compound represented by formula (2) described later, wherein both the first liquid crystal compound and the second liquid crystal compound have a maximum absorption wavelength in the wavelength range of 280 to 420 nm. [2] The liquid crystal composition according to [1], wherein M in formulas (1) and (2) described later represents a divalent mesogenic skeleton represented by formula (5) described later. [3] The liquid crystal composition according to [1] or [2], wherein the content of the second liquid crystal compound is 0.01 to 20 mass % with respect to the total mass of the first liquid crystal compound and the second liquid crystal compound. [4] A liquid crystal compound represented by formula (2) described later. [5] A cured liquid crystal layer obtained by fixing the alignment state of the liquid crystal composition according to any one of [1] to [3]. [6] An optical film having the cured liquid crystal layer described in [5]. [7] A polarizing plate having the optical film according to [6] and a polarizer. [8] An image display device having the optical film according to [6] or the polarizing plate according to [7].

[0009] According to the present invention, it is possible to provide a liquid crystal composition, a liquid crystal compound, a cured liquid crystal layer, an optical film, a polarizing plate, and an image display device in which the precipitation tendency of the liquid crystal compound is suppressed.

[0010] FIG. 1 is a schematic cross-sectional view showing an example of an optical film.

[0011] The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the upper and lower limits. In this specification, the upper or lower limit of a numerical range described in a stepwise manner may be replaced with the upper or lower limit of another stepwise manner. In this specification, the upper or lower limit of a numerical range described in a stepwise manner may be replaced with a value shown in the Examples. In this specification, each component may be a single substance corresponding to the component, or two or more substances may be used in combination. When two or more substances are used in combination for each component, the content of that component refers to the total content of the substances used in combination, unless otherwise specified. In addition, in this specification, "(meth)acrylate" is a notation representing "acrylate" or "methacrylate", "(meth)acrylic" is a notation representing "acrylic" or "methacrylic", and "(meth)acryloyl" is a notation representing "acryloyl" or "methacryloyl". In addition, the bonding direction of the divalent group (e.g., -O-CO-) represented in this specification is not particularly limited, and for example, "L １ -L ２ -L ３ In the bond ２ When is —O—CO—, L １ The position where it is bonded to the side is *1, L ３ If the position bonded to the side is *2, then L ２ may be *1-O-CO-*2 or *1-CO-O-*2.

[0012] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and the thickness direction retardation, respectively, at a wavelength λ. Unless otherwise specified, the wavelength λ is 550 nm. In the present invention, Re(λ) and Rth(λ) are values ​​measured at a wavelength λ using an AxoScan (manufactured by Axometrics). By inputting the average refractive index ((nx+ny+nz) / 3) and film thickness (d (μm)) into AxoScan, the following slow axis direction (°) is calculated: Re(λ) = R0(λ) Rth(λ) = ((nx+ny) / 2-nz)×d. Note that R0(λ) is displayed as a numerical value calculated by AxoScan, but it means Re(λ).

[0013] In this specification, examples of the substituent (monovalent substituent) include the substituents described below in Substituent Group A. In this specification, the phrase "optionally having a substituent" includes not only an embodiment in which no substituent is present, but also an embodiment in which one or more substituents are present. <Substituent Group A> Examples of the substituent include halogen atoms (for example, fluorine atoms, chlorine atoms, and bromine atoms, preferably chlorine atoms and fluorine atoms, and more preferably fluorine atoms); alkyl groups (preferably linear, branched, or cyclic alkyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as linear alkyl groups having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl), branched alkyl groups having 3 to 6 carbon atoms (for example, isopropyl, isobutyl, tert-butyl, sec-butyl, neopentyl, isohexyl, and 3-methylpentyl), and cyclic alkyl groups having 3 to 12 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl, and 1-adamantyl)); alkenyl groups (preferably alkenyl groups having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms, such as vinyl groups, allyl groups, 1-butenyl groups, and 2-butenyl groups); alkynyl groups (preferably alkynyl groups having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, such as ethynyl groups, 1-propynyl groups, propargyl groups, 1-butynyl groups, and 2-butynyl groups); aryl groups (preferably aryl groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenyl groups, oligoaryl groups (naphthyl groups, anthryl groups), phenanthrenyl groups, fluorenyl groups, pyrenyl groups, triphenylenyl groups, and biphenyl groups); Heteroaryl groups (preferably heterocyclic groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, a 2-pyrimidinyl group, a 1-pyridyl group, a 2-benzothiazolyl group, a 1-imidazolyl group, a 1-pyrazolyl group, or a benzotriazol-1-yl group);arylalkyl groups (preferably arylalkyl groups having 7 to 15 carbon atoms, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, indenyl group, fluorenyl group, anthracenylmethyl group (anthrylmethyl group), phenanthrenylmethyl group (phenanthrylmethyl group)); silyl groups (preferably silyl groups having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group); hydroxy groups; cyano groups; nitro groups; morpholino groups; Alkoxy groups (preferably alkoxy groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy, and cycloalkyloxy groups (for example, cyclopentyloxy and cyclohexyloxy)); aryloxy groups (preferably aryloxy groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenoxy and 1-naphthoxy); alkenyloxy groups (preferably alkenyloxy groups having 2 to 6 carbon atoms, for example, vinyloxy, 1-propenyloxy, 2-n-propenyloxy (allyloxy), 1-n-butenyloxy, and prenyloxy); heterocyclic oxy groups (preferably heterocyclic oxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 1-phenyltetrazole-5-oxy group or a 2-tetrahydropyranyloxy group); silyloxy groups (preferably silyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a trimethylsilyloxy group, a t-butyldimethylsilyloxy group or a diphenylmethylsilyloxy group); acyloxy groups (preferably acyloxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, a benzoyloxy group, a dodecanoyloxy group, an acryloyloxy group or a methacryloyloxy group);hydroxyalkyleneoxy groups (preferably hydroxyalkyleneoxy groups having 2 to 10 carbon atoms, for example, a hydroxyethyleneoxy group); alkoxycarbonyloxy groups (preferably alkoxycarbonyloxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or a cycloalkyloxycarbonyloxy group (for example, a cyclohexyloxycarbonyloxy group)); aryloxycarbonyloxy groups (preferably aryloxycarbonyloxy groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonyloxy group); carbamoyloxy groups (preferably carbamoyloxy groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, an N,N-dimethylcarbamoyloxy group, an N-butylcarbamoyloxy group, an N-phenylcarbamoyloxy group, or an N-ethyl-N-phenylcarbamoyloxy group); sulfamoyloxy groups (preferably sulfamoyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as an N,N-diethylsulfamoyloxy group or an N-propylsulfamoyloxy group); alkylsulfonyloxy groups (preferably alkylsulfonyloxy groups having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group or a cyclohexylsulfonyloxy group); arylsulfonyloxy groups (preferably arylsulfonyloxy groups having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenylsulfonyloxy group); acyl groups (preferably acyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a formyl group, an acetyl group, an acryloyl group, a methacryloyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group or a cyclohexanoyl group); an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, or a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group);an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, such as a phenoxycarbonyl group); a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N,N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, or N,N-dicyclohexylcarbamoyl group); an amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as an amino group, methylamino group, N,N-dimethylamino group, N,N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, or cyclohexylamino group); anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, an anilino group, an N-methylanilino group); heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, a 4-pyridylamino group); carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, an acetamido group, a benzamido group, a tetradecanamido group, a pivaloylamido group, a cyclohexanamido group); ureido group (preferably a ureido group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a ureido group, an N,N-dimethylureido group, an N-phenylureido group); imido group (preferably an imido group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, for example, an N-succinimido group, an N-phthalimido group); an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an octadecyloxycarbonylamino group, or a cyclohexyloxycarbonylamino group); an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, a phenoxycarbonylamino group);sulfonamido groups (preferably sulfonamido groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methanesulfonamido groups, butanesulfonamido groups, benzenesulfonamido groups, hexadecanesulfonamido groups, and cyclohexanesulfonamido groups); sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N,N-dipropylsulfamoylamino groups, and N-ethyl-N-dodecylsulfamoylamino groups); azo groups (preferably azo groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, phenylazo groups and 3-pyrazolylazo groups); alkylthio groups (preferably alkylthio groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylthio groups, ethylthio groups, octylthio groups, and cyclohexylthio groups); an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having 6 to 24 carbon atoms, for example, a phenylthio group); a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, for example, a 2-benzothiazolylthio group, a 2-pyridylthio group, or a 1-phenyltetrazolylthio group); an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms, for example, a dodecanesulfinyl group); an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, more preferably an arylsulfinyl group having 6 to 24 carbon atoms, for example, a phenylsulfinyl group); alkylsulfonyl groups (preferably alkylsulfonyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl, and cyclohexylsulfonyl groups); arylsulfonyl groups (preferably arylsulfonyl groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenylsulfonyl, and 1-naphthylsulfonyl groups);sulfamoyl groups (preferably sulfamoyl groups having 32 or less carbon atoms, more preferably 24 or less carbon atoms, for example, a sulfamoyl group, an N,N-dipropylsulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, an N-ethyl-N-phenylsulfamoyl group, an N-cyclohexylsulfamoyl group, or an N-(2-ethylhexyl)sulfamoyl group); phosphonyl groups (preferably phosphonyl groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a phenoxyphosphonyl group, an octyloxyphosphonyl group, or a phenylphosphonyl group); phosphinoylamino groups (preferably phosphinoylamino groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, a diethoxyphosphinoylamino group, or a dioctyloxyphosphinoylamino group); epoxy groups; —NHCOCH; ３ ;-SO ２ NHC ２ H ４ OCH ３ ;-NHSO ２ CH ３ and the like, and two or more of these may be combined. These substituents may be further substituted with other substituents. When two or more substituents are present, they may be the same or different. If possible, they may be bonded to each other to form a ring.

[0014] [Liquid Crystal Composition] The liquid crystal composition of the present invention contains a first liquid crystal compound represented by formula (1) and a second liquid crystal compound represented by formula (2) described below. In addition, in the liquid crystal composition of the present invention, both the first liquid crystal compound and the second liquid crystal compound have a maximum absorption wavelength in the wavelength range of 280 to 420 nm. The "maximum absorption wavelength" of the liquid crystal compound can be calculated from the absorption spectrum obtained by measuring the absorbance in the wavelength range of 200 to 800 nm using an ultraviolet-visible spectrophotometer (e.g., UV-1800 (Shimadzu Corporation)). The "maximum absorption wavelength" of each component in the mixture can be calculated from the maximum value of the ultraviolet-visible absorption spectrum of each separated peak using a liquid high-performance chromatography system equipped with a photodiode array detector (e.g., Prominence series (Shimadzu Corporation)). The solvent used is not particularly limited as long as it is a solvent commonly used as an eluent for liquid high-performance chromatography, and may contain an additive such as a weak acid or a weak base as a buffer. As the eluent, methanol, acetonitrile, tetrahydrofuran, water, etc. are preferred, as the weak acid for the buffer, acetic acid, phosphoric acid, etc. are preferred, and as the weak base, triethylamine, etc. are preferably used.

[0015] As described above, in the present invention, when a liquid crystal composition containing a predetermined liquid crystal compound having polymerizable groups at both ends and a liquid crystal compound having a structure different from that of the first liquid crystal compound only at one end, i.e., a liquid crystal composition containing a first liquid crystal compound and a second liquid crystal compound, is used, the precipitation tendency of the liquid crystal compound is suppressed. Although the details are not clear, the inventors speculate as follows. Specifically, the second liquid crystal compound has the same structure as the first liquid crystal compound except for T (e.g., a hydroxy group) in formula (2) described below, and therefore is able to suppress crystallization of the first liquid crystal compound without interfering with the alignment of the first liquid crystal compound. The first and second liquid crystal compounds contained in the liquid crystal composition of the present invention are described in detail below.

[0016] [First Liquid Crystal Compound] The first liquid crystal compound is a liquid crystal compound represented by the following formula (1).

[0017] In the above formula (1), L １ and L ２ each independently represents a polymerizable group. The polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cation polymerization is preferred. As the radical polymerizable group, known radical polymerizable groups can be used, and preferred examples include an acryloyloxy group or a methacryloyloxy group. In this case, the polymerization rate of an acryloyloxy group is generally known to be fast, and an acryloyloxy group is preferred from the viewpoint of improving productivity, but a methacryloyloxy group can also be used as the polymerizable group. As the cationically polymerizable group, known cationically polymerizable groups can be used, and specific examples include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, and a vinyloxy group. Among these, an alicyclic ether group or a vinyloxy group is preferred, and an epoxy group, an oxetanyl group, or a vinyloxy group is particularly preferred. Particularly preferred examples of the polymerizable group include polymerizable groups represented by any of the following formulas (P-1) to (P-20):

[0018]

[0019] In the above formula (1), SP １ and SP ２ each independently represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, provided that —CH ２One or more of the - may be substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-. Q represents a substituent. Examples of the divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include a linear or branched alkylene group having 1 to 20 carbon atoms, a linear or branched alkenylene group having 1 to 20 carbon atoms, and a linear or branched alkynylene group having 1 to 20 carbon atoms. The linear or branched alkylene group having 1 to 20 carbon atoms is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and suitable examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. As the linear or branched alkenylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 10 carbon atoms is preferred, and an alkenylene group having 2 to 4 carbon atoms is more preferred, and a suitable example thereof is an ethenylene group. As the linear or branched alkynylene group having 1 to 20 carbon atoms, an alkynylene group having 2 to 10 carbon atoms is preferred, and an alkynylene group having 2 to 4 carbon atoms is more preferred, and a suitable example thereof is an ethynylene group. As mentioned above, -CH constituting the aliphatic hydrocarbon group ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-. Examples of the substituent represented by Q include the substituents described in the above-mentioned substituent group A. Among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.

[0020] In the above formula (1), M represents a divalent mesogenic skeleton having three or more aromatic or aliphatic rings, each of which may have a substituent. Examples of the aromatic ring include aromatic rings having 6 to 20 carbon atoms. Specific examples include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; and aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring. Of these, a benzene ring (e.g., a 1,4-phenyl group) is preferred. Examples of the aliphatic ring include a cycloalkane ring, specifically a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosane ring. Of these, a cyclohexane ring is preferred, a 1,4-cyclohexylene group is more preferred, and a trans-1,4-cyclohexylene group is even more preferred. Examples of the substituent that the aromatic ring or the aliphatic ring may have include the substituents described in the above-mentioned substituent group A, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.

[0021] In M in the above formula (1), the number of aromatic rings or aliphatic rings is not particularly limited as long as the total number of rings is 3 or more, but it is preferably 3 to 10 rings, more preferably 3 to 7 rings, and even more preferably 3 to 5 rings.

[0022] In the present invention, it is preferable that M in the above formula (1) represents a divalent mesogenic skeleton represented by the following formula (5), because this facilitates the development of liquid crystal properties and the provision of optical properties. In the following formula (5), * represents SP １ or SP ２ represents the bonding position with

[0023] In the above formula (5), B １ and B ２ each independently represents an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent, and -CH ２One or more of - may be substituted with -O-, -S- or -NH-.

[0024] B １ and B ２ Examples of the aromatic ring having 6 to 20 carbon atoms represented by one embodiment of the formula (1) include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; and aromatic heterocycles such as a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring. Of these, a benzene ring (for example, a 1,4-phenyl group) is preferred.

[0025] B １ and B ２ The divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms represented by one embodiment of the formula (1) is preferably a 5-membered or 6-membered ring. The alicyclic hydrocarbon group may be saturated or unsaturated, but is preferably a saturated alicyclic hydrocarbon group. １ and G ２ For example, the description of paragraph

[0078] of JP 2012-21068 A can be referred to for the divalent alicyclic hydrocarbon group represented by the formula (I), the contents of which are incorporated herein by reference. Furthermore, the alicyclic hydrocarbon group is preferably a cycloalkane ring. Specific examples of the cycloalkane ring include a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclododecane ring, and a cyclodocosane ring. Of these, a cyclohexane ring is preferred, a 1,4-cyclohexylene group is more preferred, and a trans-1,4-cyclohexylene group is even more preferred.

[0026] In addition, in the above formula (5), B １ and B ２ With regard to the above, examples of the substituent that the aromatic ring having 6 to 20 carbon atoms or the divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms may have include the substituents described in the above-mentioned substituent group A, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.

[0027] In the above formula (5), D １ , D ２ , D ３ and D ４each independently represents a single bond, or —CO—, —O—, —S—, —C(═S)—, or —CR １ R ２ -, -CR ３ =CR ４ -, -NR ５ -, or a divalent linking group formed by a combination of two or more thereof, R １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. Specific examples of the divalent linking group include -CO-, -O-, -CO-O-, -C(=S)O-, and -CR １ R ２ -, -CR １ R ２ -CR １ R ２ -, -O-CR １ R ２ -, -CR １ R ２ -O-CR １ R ２ -, -CO-O-CR １ R ２ -, -O-CO-CR １ R ２ -, -CR １ R ２ -O-CO-CR １ R ２ -, -CR １ R ２ -CO-O-CR １ R ２ -, -NR ５ -CR １ R ２ -, and -CO-NR ５ -, etc. １ , R ２ and R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. Among these, any of —CO—, —O—, and —CO—O— is preferred.

[0028] In the above formula (5), m1 and m2 each independently represent an integer of 1 to 3. When m1 represents 2 or 3, a plurality of B １ and D１ may be the same or different, and when m2 represents 2 or 3, a plurality of B ２ and D ２ may be the same or different. Here, m1 and m2 are each preferably 1 or 2, and more preferably 2.

[0029] In the formula (5), Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulae (Ar-1) to (Ar-7): In the following formulae (Ar-1) to (Ar-7), * represents D in the formula (5). １ or D ２ represents the bonding position with

[0030] In the above formula (Ar-1), Q １ represents N or CH, and Q ２ is -S-, -O-, or -N(R ６ )-, R ６ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Y １ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and -CH ２ One or more of - may be replaced by -O-, -S- or -NH-. ６ Specific examples of the alkyl group having 1 to 6 carbon atoms represented by one embodiment of the formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. １ Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by one embodiment of the formula (I) include aryl groups such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group. １Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by one embodiment of the formula (1) include heteroaryl groups such as a thienyl group, a thiazolyl group, a furyl group, and a pyridyl group, as well as groups formed by removing one hydrogen atom from an indole ring, a benzofuran ring, a benzothiophene ring, a benzimidazole ring, a benzothiazole ring, and a benzoxazole ring. １ The aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y is preferably a group obtained by removing one hydrogen atom from a benzofuran ring or a benzothiazole ring. １ Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms represented by one embodiment of the formula (1) include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. １ Examples of the substituent that may be possessed by the group include the substituents described in the above-mentioned substituent group A, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a nitro group, a cyano group, or a halogen atom is preferable.

[0031] In addition, in the above formulas (Ar-1) to (Ar-7), Z １ , Z ２ and Z ３ each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent aromatic heterocyclic group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ７ , -NR ８ R ９ , -SR １０ , -COOR １１ , or -COR １２ represents R ７ ~R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Z １ and Z ２may be bonded to each other to form an aromatic ring. As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, specifically, a methyl group, an ethyl group, an isopropyl group, a tert-pentyl group (1,1-dimethylpropyl group), a tert-butyl group, or a 1,1-dimethyl-3,3-dimethyl-butyl group is further preferred, and a methyl group, an ethyl group, or a tert-butyl group is particularly preferred. Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include monocyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, methylcyclohexyl, and ethylcyclohexyl groups; monocyclic unsaturated hydrocarbon groups such as cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, and cyclodecadiene; bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl, and tricyclo[5.2.1.0]diene; ２，６ ] decyl group, tricyclo[3.3.1.1 ３，７ ]decyl group, tetracyclo[6.2.1.1 ３，６ .0 ２，７ ] dodecyl group, adamantyl group, and other polycyclic saturated hydrocarbon groups. Specific examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group, with an aryl group having 6 to 12 carbon atoms (particularly a phenyl group) being preferred. Specific examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom, a chlorine atom, and a bromine atom being preferred. On the other hand, R ７ ~R １０Specific examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

[0032] Z １ and Z ２ As described above, may be bonded to each other to form an aromatic ring. For example, Z １ and Z ２ Examples of the structure in which the groups bond to each other to form an aromatic ring include a group represented by the following formula (Ar-1a): In the following formula (Ar-1a), * represents D in the above formula (A). １１ or X １ represents the bonding position with In the above formula (Ar-1a), Q １ , Q ２ and Y １ The examples of the alkyl group include those described above in relation to formula (Ar-1).

[0033] In addition, in the above formulas (Ar-2) and (Ar-3), A ３ and A ４ are each independently —O—, —N(R １３ represents a group selected from the group consisting of —, —S—, and —CO—; R １３ represents a hydrogen atom or a substituent. １３ Examples of the substituent represented by one embodiment of the formula (I) include the substituents described in the above-mentioned Substituent Group A, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable.

[0034] In the formula (Ar-2), X represents a nonmetallic atom of Groups 14 to 16. However, the nonmetallic atom may have a hydrogen atom or a substituent bonded thereto. Examples of the nonmetallic atom of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a hydrogen atom, or a nitrogen atom bonded to a substituent [=N-R Ｎ１ , R Ｎ１ represents a hydrogen atom or a substituent.], a carbon atom to which a hydrogen atom or a substituent is bonded [═C—(RＣ１ ) ２ , R Ｃ１ represents a hydrogen atom or a substituent.] Examples of the substituent include the substituents described in the above-mentioned substituent group A, and among them, preferred examples include an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, and a hydroxyl group.

[0035] In addition, in the above formula (Ar-3), D ７ and D ８ each independently represents a single bond, or —CO—, —O—, —S—, —C(═S)—, or —CR １ R ２ -, -CR ３ =CR ４ -, -NR ５ -, or a divalent linking group formed by a combination of two or more thereof, R １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. Here, the divalent linking group is D in the above formula (5). １ and D ２ Examples of the above-described examples are the same as those described above.

[0036] In addition, in the above formula (Ar-3), SP ３ and SP ４ each independently represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, provided that —CH ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. Examples of the substituent represented by Q include the substituents described in the above-mentioned substituent group A, and among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferred. Here, the divalent aliphatic hydrocarbon group is a group represented by the formula (1) SP １ and SP ２ Examples of the above-described examples are the same as those described above.

[0037] In addition, in the above formula (Ar-3), L ３ and L ４ Each independently represents a monovalent organic group. Examples of the monovalent organic group include the substituents described in the above-mentioned Substituent Group A and the above-mentioned polymerizable groups. Among these, alkyl groups, aryl groups, heteroaryl groups, alkoxy groups, cyano groups, carboxy groups, and polymerizable groups are preferred. The alkyl group may be linear, branched, or cyclic, but linear groups are preferred. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but monocyclic groups are preferred. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10. The heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the heteroaryl group are preferably nitrogen atoms, sulfur atoms, or oxygen atoms. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12. The alkyl group, aryl group, and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include those described in the above-mentioned substituent group A, and among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferred. Examples of the polymerizable group include preferably the polymerizable group represented by any one of the above-mentioned formulas (P-1) to (P-20).

[0038] In the above formulas (Ar-4) to (Ar-7), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. In addition, in the above formulas (Ar-4) to (Ar-7), Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Here, the aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring. In addition, Q ３represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of Ax and Ay include those described in paragraphs

[0039] to

[0095] of WO 2014 / 010325. ３ Specific examples of the alkyl group having 1 to 6 carbon atoms represented by include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Examples of the substituent include the substituents described in the above-mentioned substituent group A. Among these, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferred.

[0039] The first liquid crystal compound, for example, the general formula (1) described in JP-A-2010-084032 compounds (particularly, the compounds described in paragraphs

[0067] to

[0073] ), the general formula (II) described in JP-A-2016-053709 compounds (particularly, the compounds described in paragraphs

[0036] to

[0043] ), and the general formula (1) described in JP-A-2016-081035 compounds (particularly, the compounds described in paragraphs

[0043] to

[0055] ), paragraphs

[0025] to

[0056] of WO 2021 / 060427 include compounds described therein.

[0040] [Second Liquid Crystal Compound] The second liquid crystal compound is a liquid crystal compound represented by the following formula (2).

[0041] In the above formula (2), M and SP １ , SP ２ and L １ and have the same meanings as those explained in the above formula (1). The first liquid crystal compound and the second liquid crystal compound contained in the liquid crystal composition of the present invention are defined as M and SP in the above formulas (1) and (2). １ , SP ２ and L １ represent the same thing. For example, L in the above formula (1) １ is an acryloyloxy group, L in the above formula (2) １also represents an acryloyloxy group, and SP in the above formula (1) １ is a propylene group, SP in the above formula (2) １ also represents a propylene group.

[0042] Meanwhile, T in the above formula (2) represents a hydroxy group, a halogen atom, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or a substituent represented by the following formula (3) or (4). In the following formulas (3) and (4), * represents SP ２ represents the bonding position with

[0043] In the above formulas (3) and (4), X － represents a counter anion. Examples of the counter anion include alkylborate anions, arylborate anions, perchlorate ions, and halogen anions. Among these, halogen anions (particularly F － and Cl － ) is preferred.

[0044] In the above formulas (3) and (4), R Ｔ１ ~R Ｔ３ R each independently represents an alkyl group having 1 to 6 carbon atoms. Ｔ４ and R Ｔ５ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. ２ One or more of the - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. Examples of the substituent include those described in the above-mentioned substituent group A, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, or a halogen atom is preferable. In addition, R Ｔ１ ~R Ｔ３ is R Ｔ１ ~R Ｔ３ Two or three of these may be bonded to each other to form a ring.

[0045] In the above formulas (3) and (4), A represents a 5- or 6-membered nitrogen-containing aromatic ring which may have a substituent. Specific examples of the 5-membered nitrogen-containing aromatic ring include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, and a thiazole ring. Specific examples of the 6-membered nitrogen-containing aromatic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring. Examples of the substituent that the 5- or 6-membered nitrogen-containing aromatic ring may have include the substituents described in the above-mentioned substituent group A, and among them, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an amino group, or a halogen atom is preferred.

[0046] Suitable examples of the second liquid crystal compound include specific compounds (2-1) to (2-11) represented by the following formulae:

[0047] In the present invention, from the viewpoint of a balance between suppression of precipitation of the liquid crystal compound and the stretching property (degree of cross-linking) of the cured liquid crystal layer, the content of the second liquid crystal compound is preferably 0.01 to 20 mass %, more preferably 0.05 to 15 mass %, and even more preferably 0.1 to 10 mass %, based on the total mass of the first liquid crystal compound and the second liquid crystal compound.

[0048] [Other Polymerizable Compounds] From the viewpoints of alignment temperature and solubility, the liquid crystal composition of the present invention preferably contains, in addition to the first liquid crystal compound and the second liquid crystal compound described above, another polymerizable compound having one or more polymerizable groups. Here, the polymerizable group contained in the other polymerizable compound is not particularly limited, and suitable examples thereof include the polymerizable groups represented by any of the above formulae (P-1) to (P-20).

[0049] The other polymerizable compound is preferably an other polymerizable compound having 2 to 4 polymerizable groups, more preferably an other polymerizable compound having 2 polymerizable groups, for the reason that the durability of the formed liquid crystal cured layer is further improved.

[0050] Examples of such other polymerizable compounds include compounds represented by formulae (M1), (M2), and (M3) described in paragraphs

[0030] to

[0033] of JP2014-077068A, and more specifically, specific examples described in paragraphs

[0046] to

[0055] of the same publication.

[0051] [Polymerization Initiator] The liquid crystal composition of the present invention preferably contains a polymerization initiator. The polymerization initiator used is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation. Examples of the photopolymerization initiator include α-carbonyl compounds (described in U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Pat. No. 2,722,512), polynuclear quinone compounds (described in U.S. Pat. Nos. 3,046,127 and 2,951,758), and mixtures of triarylimidazole dimers and p-aminophenyl ketones. (described in U.S. Pat. No. 3,549,367), acridine and phenazine compounds (described in JP-A-60-105667 and U.S. Pat. No. 4,239,850), oxadiazole compounds (described in U.S. Pat. No. 4,212,970), acylphosphine oxide compounds (described in JP-B-63-40799, JP-B-5-29234, JP-A-10-95788, and JP-A-10-29997), etc. In the present invention, the polymerization initiator is preferably an oxime-type polymerization initiator, and specific examples thereof include the initiators described in paragraphs

[0049] to

[0052] of WO 2017 / 170443.

[0052] [Solvent] The liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability in forming a cured liquid crystal layer. Specific examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, etc.), and the like. These may be used alone or in combination of two or more.

[0053] [Leveling Agent] The liquid crystal composition of the present invention preferably contains a leveling agent from the viewpoint of facilitating alignment control. Such a leveling agent is preferably a fluorine-based leveling agent or a silicon-based leveling agent because of its high leveling effect relative to the amount added, and more preferably a fluorine-based leveling agent from the viewpoint of being less likely to cause bleeding (bloom, bleed). Specific examples of the leveling agent include compounds described in paragraphs

[0079] to

[0102] of JP-A No. 2007-069471, compounds represented by general formula (I) described in JP-A No. 2013-047204 (particularly compounds described in paragraphs

[0020] to

[0032] ), and compounds represented by general formula (I) described in JP-A No. 2012-211306 (particularly compounds

[0022] to

[0029] ). Examples of the compound include the compounds described in the paragraphs

[0076] to

[0078] and

[0082] to

[0084] ), liquid crystal alignment promoters represented by general formula (I) described in JP-A-2002-129162 (particularly the compounds described in paragraphs

[0076] to

[0078] and

[0082] to

[0084] ), and compounds represented by general formulas (I), (II), and (III) described in JP-A-2005-099248 (particularly the compounds described in paragraphs

[0092] to

[0096] ). The compound may also function as an alignment control agent, which will be described later.

[0054] [Alignment Control Agent] The liquid crystal composition of the present invention may contain an alignment control agent, if necessary. The alignment control agent can form various alignment states such as homogeneous alignment, homeotropic alignment (vertical alignment), tilted alignment, hybrid alignment, and cholesteric alignment, and can also realize a specific alignment state by controlling it more uniformly and more precisely.

[0055] As the alignment control agent that promotes homogeneous alignment, for example, a low molecular weight alignment control agent or a high molecular weight alignment control agent can be used. For low molecular weight alignment control agents, for example, the descriptions in paragraphs

[0009] to

[0083] of JP 2002-20363 A, paragraphs

[0111] to

[0120] of JP 2006-106662 A, and paragraphs

[0021] to

[0029] of JP 2012-211306 A can be referred to, the contents of which are incorporated herein by reference. Furthermore, for polymer orientation control agents, reference can be made to, for example, paragraphs

[0021] to

[0057] of JP-A No. 2004-198511 and paragraphs

[0121] to

[0167] of JP-A No. 2006-106662, the contents of which are incorporated herein by reference.

[0056] Examples of alignment control agents that form or promote homeotropic alignment include boronic acid compounds and onium salt compounds. Specific examples of such compounds include those described in JP-A-2008-225281, paragraphs

[0023] to

[0032] , JP-A-2012-208397, paragraphs

[0052] to

[0058] , JP-A-2008-026730, paragraphs

[0024] to

[0055] , and JP-A-2016-193869, paragraphs

[0043] to

[0055] , and the like, the contents of which are incorporated herein by reference.

[0057] On the other hand, cholesteric alignment can be achieved by adding a chiral dopant to the liquid crystal composition of the present invention, and the rotation direction of the cholesteric alignment can be controlled by the direction of the chirality. The pitch of the cholesteric alignment can be controlled depending on the alignment control force of the chiral dopant.

[0058] When an alignment control agent is contained, its content is preferably 0.01 to 10 mass %, more preferably 0.05 to 5 mass %, based on the total mass of solids in the composition. When the content is within this range, a desired alignment state can be achieved, and a uniform, highly transparent cured product can be obtained without precipitation, phase separation, alignment defects, etc.

[0059] [Other Components] The liquid crystal composition of the present invention may contain components other than the above-mentioned components, such as a surfactant, a tilt angle control agent, an alignment aid, a plasticizer, and a crosslinking agent.

[0060] [Liquid Crystal Compound] The liquid crystal compound of the present invention is a compound represented by the above formula (2), in which M in formula (2) represents a divalent mesogenic skeleton represented by the above formula (5).

[0061] [Liquid Crystal Cured Layer] The liquid crystal cured layer of the present invention is a liquid crystal cured layer obtained by fixing the alignment state of the liquid crystal composition of the present invention described above. Examples of methods for forming the liquid crystal cured layer include a method in which the liquid crystal composition of the present invention described above is used to achieve a desired alignment state, and then the liquid crystal composition is fixed by polymerization. While the polymerization conditions are not particularly limited, it is preferable to use ultraviolet light for polymerization by light irradiation. The irradiation dose is 10 mJ / cm. ２ ~50 J / cm ２ is preferred, and 20 mJ / cm ２ ~5 J / cm ２ More preferably, 30 mJ / cm ２ ~3 J / cm ２ is more preferably 50 mJ / cm ２ ~1000mJ / cm ２ is particularly preferred. In order to promote the polymerization reaction, the polymerization may be carried out under heating conditions. The liquid crystal cured layer can be formed on any support or alignment film in an optical film described later, or on a polarizer in a polarizing plate described later.

[0062] The orientation state of the liquid crystal compound in the cured liquid crystal layer of the present invention may be any of horizontal, vertical, tilted, and twisted orientations, and is preferably fixed in a state of horizontal orientation relative to the main surface of the cured liquid crystal layer. In this specification, "horizontal orientation" refers to a state in which the major axis direction of the liquid crystal compound is parallel to the main surface of the cured liquid crystal layer (or, when the cured liquid crystal layer is formed on a member such as a support or an alignment film, the surface of the member). Strict parallelism is not required, and in this specification, it refers to an orientation in which the angle between the major axis direction of the liquid crystal compound and the main surface of the cured liquid crystal layer is less than 10°. In the cured liquid crystal layer, the angle between the major axis direction of the liquid crystal compound and the main surface of the cured liquid crystal layer is preferably 0 to 5°, more preferably 0 to 3°, and even more preferably 0 to 2°.

[0063] The liquid crystal cured layer of the present invention is preferably an optically anisotropic layer, more preferably a positive A plate or a positive C plate, and even more preferably a positive A plate.

[0064] Here, a positive A plate (positive A plate) and a positive C plate (positive C plate) are defined as follows. When the refractive index in the in-plane slow axis direction of the film (the direction in which the in-plane refractive index is maximum) is nx, the refractive index in the in-plane direction perpendicular to the in-plane slow axis is ny, and the refractive index in the thickness direction is nz, a positive A plate satisfies the relationship of formula (A1), and a positive C plate satisfies the relationship of formula (C1). Note that a positive A plate has a positive Rth, and a positive C plate has a negative Rth. Formula (A1) nx>ny≒nz Formula (C1) nz>nx≒ny Note that the above "≒" encompasses not only the case where both are completely identical, but also the case where both are substantially identical. Regarding "substantially the same," for a positive A plate, "ny ≒ nz" includes, for example, a case where (ny - nz) x d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm, and "nx ≒ nz" includes, for example, a case where (nx - nz) x d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm. Also, for a positive C plate, "nx ≒ ny" includes, for example, a case where (nx - ny) x d (where d is the film thickness) is 0 to 10 nm, preferably 0 to 5 nm.

[0065] When the liquid crystal cured layer of the present invention is a positive A plate, from the viewpoint of functioning as a λ / 4 plate, Re(550) is preferably 100 to 180 nm, more preferably 120 to 160 nm, even more preferably 130 to 150 nm, and particularly preferably 130 to 145 nm. Here, the "λ / 4 plate" is a plate having a λ / 4 function, specifically, a plate having a function of converting linearly polarized light of a certain wavelength into circularly polarized light (or circularly polarized light into linearly polarized light).

[0066] When the liquid crystal composition of the present invention contains a dichroic material, the liquid crystal cured layer of the present invention can be used as a polarizer (light absorption anisotropic film).

[0067] [Optical Film] The optical film of the present invention is an optical film having the liquid crystal cured layer of the present invention. The structure of the optical film will be described with reference to FIG. 1. FIG. 1 is a schematic cross-sectional view showing an example of an optical film. Note that FIG. 1 is a schematic view, and the thickness relationships and positional relationships of the layers do not necessarily correspond to the actual ones, and the support and alignment film shown in FIG. 1 are both optional components.

[0068] The optical film 10 shown in FIG. 1 includes, in this order, a support 16, an alignment film 14, and a cured liquid crystal layer 12 formed from the cured liquid crystal composition of the present invention. The cured liquid crystal layer 12 may also be a laminate of two or more different cured liquid crystal layers. For example, when the polarizing plate of the present invention (described later) is used as a circular polarizing plate, or when the optical film of the present invention is used as an optical compensation film for an IPS (In-Plane-Switching) or FFS (Fringe-Field-Switching) liquid crystal display device, a laminate of a positive A plate and a positive C plate is preferred. The cured liquid crystal layer may also be peeled from the support and used alone as an optical film. Various components used in the optical film are described in detail below.

[0069] [Liquid Crystal Cured Layer] The liquid crystal cured layer of the optical film of the present invention is the liquid crystal cured layer of the present invention described above. In the optical film, the thickness of the liquid crystal cured layer is not particularly limited, but is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[0070] [Support] As described above, the optical film may have a support as a substrate for forming the liquid crystal cured layer. Such a support is preferably transparent. Specifically, it is preferable that the light transmittance is 80% or more.

[0071] Examples of such a support include glass substrates and polymer films. Examples of materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamide; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; and polymers obtained by mixing these polymers. In addition, the polarizer described below may also serve as such a support.

[0072] The thickness of the support is not particularly limited, but is preferably 5 to 60 μm, and more preferably 5 to 40 μm.

[0073] [Alignment film] In the optical film, the liquid crystal cured layer is preferably formed on the surface of an alignment film (particularly, a photo-alignment film described later). When the optical film has any of the above-mentioned supports, the alignment film may be sandwiched between the support and the liquid crystal cured layer. In addition, the above-mentioned support may also serve as the alignment film.

[0074] The alignment film may be any film that functions to horizontally align the liquid crystal compound contained in the composition. Alignment films are generally primarily composed of polymers. Polymer materials for alignment films are described in numerous literature, and many commercially available products are available. Preferred polymer materials for alignment films are polyvinyl alcohol, polyimide, or derivatives thereof, with modified or unmodified polyvinyl alcohol being more preferred. Examples of alignment films that may be included in the optical film include the alignment film described in International Publication No. 01 / 88574, page 43, line 24 to page 49, line 8; the alignment film made of modified polyvinyl alcohol described in paragraphs

[0071] to

[0095] of Japanese Patent No. 3907735; and the liquid crystal alignment film formed using the liquid crystal aligning agent described in Japanese Patent Publication No. 2012-155308.

[0075] It is preferable to use a photo-alignment film as the alignment film, since the surface of the alignment film is not in contact with any object during the formation of the alignment film, and it is possible to prevent deterioration of the surface condition. The photo-alignment film is not particularly limited, but it can be an alignment film formed from a polymer material such as a polyamide compound and a polyimide compound described in paragraphs

[0024] to

[0043] of International Publication No. 2005 / 096041; a liquid crystal alignment film formed from a liquid crystal alignment agent having a photo-alignment group described in Japanese Patent Laid-Open No. 2012-155308; and a product name LPP-JP265CP manufactured by Rolic Technologies, Inc., or the like.

[0076] The thickness of the alignment film is not particularly limited, but from the viewpoint of reducing surface irregularities that may be present on the support and forming a liquid crystal cured layer with a uniform film thickness, the thickness is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[0077] [Another liquid crystal cured layer] In the optical film, the liquid crystal cured layer is preferably formed on the surface of another liquid crystal cured layer. Here, the other liquid crystal cured layer may be, for example, a liquid crystal cured layer obtained by fixing the alignment state of a composition obtained by removing the specific compound A from the liquid crystal composition of the present invention described above. Specifically, it may be a liquid crystal cured layer obtained by fixing the alignment state of a composition containing the above-mentioned liquid crystal compound, a polymerization initiator, a leveling agent, a solvent, etc.

[0078] [Ultraviolet Absorber] In consideration of the influence of external light (especially ultraviolet light), the optical film preferably contains an ultraviolet (UV) absorber. The ultraviolet absorber may be contained in the cured liquid crystal layer, or may be contained in a member other than the cured liquid crystal layer constituting the optical film. A suitable example of the member other than the cured liquid crystal layer is a support. As the ultraviolet absorber, any conventionally known material capable of exhibiting ultraviolet absorption properties can be used. Among such ultraviolet absorbers, benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorbers are preferred from the viewpoint of high ultraviolet absorption and obtaining ultraviolet absorption ability (ultraviolet blocking ability) used in image display devices. Furthermore, in order to widen the ultraviolet absorption width, it is also preferable to use two or more ultraviolet absorbers with different maximum absorption wavelengths in combination.

[0079] Examples of ultraviolet absorbers include the compounds described in paragraphs

[0258] to

[0259] of JP 2012-18395 A and the compounds described in paragraphs

[0055] to

[0105] of JP 2007-72163 A. Commercially available products that can be used include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, and Tinuvin 1577 (all manufactured by BASF).

[0080] [Polarizing Plate] The polarizing plate of the present invention comprises the optical film of the present invention described above and a polarizer. Furthermore, when the liquid crystal cured layer of the present invention described above is a λ / 4 plate (positive A plate), the polarizing plate of the present invention can be used as a circular polarizing plate. Furthermore, when the liquid crystal cured layer of the present invention described above is a λ / 4 plate (positive A plate), the angle between the slow axis of the λ / 4 plate and the absorption axis of the polarizer described below is preferably 30 to 60°, more preferably 40 to 50°, even more preferably 42 to 48°, and particularly preferably 45°. Here, the "slow axis" of the λ / 4 plate refers to the direction in which the refractive index is maximized in the plane of the λ / 4 plate, and the "absorption axis" of the polarizer refers to the direction in which the absorbance is highest. Furthermore, the polarizing plate of the present invention can also be used as an optical compensation film for an IPS-type or FFS-type liquid crystal display device. When the polarizing plate of the present invention is used as an optical compensation film for an IPS-type or FFS-type liquid crystal display device, the above-mentioned liquid crystal cured layer of the present invention can be at least one plate of a laminate of a positive A plate and a positive C plate, and is preferably a positive A plate. In this case, it is preferable that the angle between the slow axis of the positive A plate and the absorption axis of the polarizer described below is perpendicular or parallel. Specifically, it is more preferable that the angle between the slow axis of the positive A plate and the absorption axis of the polarizer described below is 0 to 5° or 85 to 95°. Furthermore, when the polarizing plate of the present invention is formed by laminating a polarizer, a positive C plate, and a positive A plate in this order, it is more preferable that the angle between the slow axis of the positive A plate and the absorption axis of the polarizer is parallel. Similarly, when the polarizing plate of the present invention is formed by laminating a polarizer, a positive A plate, and a positive C plate in this order, it is more preferable that the angle between the slow axis of the positive A plate and the absorption axis of the polarizer is perpendicular. When the polarizing plate of the present invention is used in a liquid crystal display device described later, the angle between the slow axis of the cured liquid crystal layer and the absorption axis of the polarizer described later is preferably parallel or perpendicular. In this specification, "parallel" does not require strict parallelism, but means that the angle between one axis and the other is less than 10°.Furthermore, in this specification, "orthogonal" does not require that they be strictly orthogonal, but rather means that the angle between one side and the other is greater than 80° and less than 100°.

[0081] [Polarizer] The polarizer of the polarizing plate of the present invention is not particularly limited as long as it has the function of converting light into specific linearly polarized light, and conventionally known absorptive polarizers and reflective polarizers can be used. Examples of absorptive polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers include coated polarizers and stretched polarizers, and either type can be used. However, polarizers produced by adsorbing iodine or a dichroic dye onto polyvinyl alcohol and stretching the resulting film are preferred. Furthermore, methods for obtaining polarizers by stretching and dyeing a laminated film having a polyvinyl alcohol layer formed on a substrate are described in Japanese Patent Nos. 5,048,120, 5,143,918, 4,691,205, 4,751,481, and 4,751,486. These known techniques related to polarizers can also be preferably used. As the reflective polarizer, a polarizer in which thin films with different birefringence are laminated, a wire grid polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region is combined with a quarter-wave plate, etc. are used. Among them, a polyvinyl alcohol-based resin (-CH ２ A polymer containing —CHOH— as a repeating unit, particularly at least one selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer, is preferred.

[0082] In the present invention, the thickness of the polarizer is not particularly limited, but is preferably 3 μm to 60 μm, more preferably 5 μm to 30 μm, and even more preferably 5 μm to 15 μm.

[0083] [Adhesive Layer] The polarizing plate of the present invention may have an adhesive layer disposed between the liquid crystal cured layer in the optical film of the present invention and the polarizer. The adhesive layer used for laminating the liquid crystal cured layer and the polarizer refers to, for example, a substance having a ratio of storage modulus G' to loss modulus G" (tan δ = G" / G') measured with a dynamic viscoelasticity measuring device of 0.001 to 1.5, and includes so-called adhesives and substances that tend to creep. Adhesives that can be used in the present invention include, but are not limited to, polyvinyl alcohol-based adhesives.

[0084] [Image Display Device] The image display device of the present invention is an image display device having the optical film of the present invention or the polarizing plate of the present invention. The display element used in the image display device is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL (Electro Luminescence)") display panel, and a plasma display panel. Of these, a liquid crystal cell and an organic EL display panel are preferred, and a liquid crystal cell is more preferred. That is, as the image display device, a liquid crystal display device using a liquid crystal cell as the display element or an organic EL display device using an organic EL display panel as the display element is preferred, and a liquid crystal display device is more preferred.

[0085] [Liquid Crystal Display Device] A liquid crystal display device, which is an example of an image display device, is a liquid crystal display device having the above-described polarizing plate and a liquid crystal cell. Of the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the above-described polarizing plate as the front-side polarizing plate, and it is more preferable to use the above-described polarizing plate as the front-side and rear-side polarizing plates. The liquid crystal cell constituting the liquid crystal display device will be described in detail below.

[0086] <Liquid Crystal Cell> The liquid crystal cell used in the liquid crystal display device is preferably, but not limited to, a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, an FFS (Fringe-Field-Switching) mode, or a TN (Twisted Nematic) mode. In a TN mode liquid crystal cell, when no voltage is applied, the rod-shaped liquid crystal molecules are aligned substantially horizontally and further twisted at an angle of 60 to 120 degrees. TN mode liquid crystal cells are most commonly used in color TFT liquid crystal displays and are described in numerous literature. In a VA mode liquid crystal cell, the rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied. VA mode liquid crystal cells include (1) narrowly defined VA mode liquid crystal cells in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (described in Japanese Patent Application Laid-Open No. 2-176625), (2) multi-domain VA mode liquid crystal cells (described in SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845) in order to widen the viewing angle (MVA mode liquid crystal cells), (3) n-ASM mode liquid crystal cells in which rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (described in Proceedings of the Japan Liquid Crystal Symposium 58-59 (1998)), and (4) SURVIVAL mode liquid crystal cells (announced at LCD International 98). Furthermore, VA-mode liquid crystal cells may be any of PVA (Patterned Vertical Alignment) type, optical alignment type, and PSA (Polymer-Sustained Alignment) type. Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese Patent Application Laid-Open No. 2008-538819. In IPS-mode liquid crystal cells, rod-shaped liquid crystal molecules are aligned substantially parallel to the substrates, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. In IPS-mode cells, black is displayed when no electric field is applied, and the absorption axes of a pair of upper and lower polarizing plates are perpendicular to each other.Methods of using an optical compensation sheet to reduce light leakage in oblique directions during black display and improve the viewing angle are disclosed in JP-A Nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[0087] [Organic EL Display Device] An example of an organic EL display device, which is an example of an image display device, includes, from the viewing side, a polarizer, a λ / 4 plate (positive A plate) made of the above-mentioned liquid crystal cured layer, and an organic EL display panel, in this order. The organic EL display panel is a display panel configured using organic EL elements in which an organic light-emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration may be adopted.

[0088] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0089] [Synthesis Example] [Synthesis of Intermediate (A-H)] Intermediate (A-H) represented by the following formula (A-H) was synthesized according to the synthesis method for compound I-1-e described in WO 2019 / 111853.

[0090] [Synthesis of Intermediate (B-1)] Intermediate (B-1) represented by the following formula (B-1) was synthesized according to the following scheme.

[0091] Specifically, 7.88 g (40.6 mmol) of monotetrahydropyranyl-protected hydroquinone synthesized by the method described in JP 2010-031223 A, 10.0 g (36.9 mmol) of 6-bromohexacylbenzyl ether synthesized by the method described in Chemistry Letters (2000), (12), pp. 1352-1355, and 7.65 g (55.4 mmol) of potassium carbonate were dissolved or dispersed in 200 mL of dimethylacetamide. The mixture was then stirred at 100°C under a nitrogen atmosphere. The mixture was then cooled to room temperature, and purified water and methyl isobutyl ketone were added. The recovered organic layer was washed with aqueous sodium hydroxide and purified water, dehydrated, filtered, and concentrated under reduced pressure. Methanol was added to the residue, and the resulting precipitate was filtered and dried under vacuum to obtain 12.5 g (32.5 mmol, 88%) of intermediate (B-1).

[0092] [Synthesis of Intermediate (B-2)] Intermediate (B-2) represented by the following formula (B-2) was synthesized according to the following scheme.

[0093] Specifically, 12.0 g (31.2 mmol) of intermediate (B-1) was dissolved in 200 mL of tetrahydrofuran (hereinafter abbreviated as "THF"), and 50 mL of 2N aqueous hydrochloric acid was added thereto, followed by stirring under a nitrogen atmosphere at 60°C. 200 mL of saturated saline was added to the reaction solution, and the mixture was further stirred, and the separated organic layer was recovered. The recovered organic layer was dehydrated, filtered, and then concentrated under reduced pressure. Hexane was further added to the organic layer, and the mixture was stirred under ice cooling. The precipitated powder was filtered and then vacuum dried, yielding 7.5 g (25.0 mmol, 80%) of intermediate (B-2).

[0094] [Synthesis of Intermediate (B-3)] Intermediate (B-3) represented by the following formula (B-3) was synthesized according to the following scheme.

[0095] Specifically, 7.0 g (23.3 mmol) of intermediate (B-2) was dissolved in 100 mL of THF, and the mixture was ice-cooled to 0°C with stirring. 14.6 g (69.8 mmol) of cyclohexanedicarbonyl dichloride was then added as a powder. 4.72 g (46.6 mmol) of triethylamine was then added, and the mixture was stirred at 0°C for 2 hours. After the reaction, 50 mL of water was added, and the mixture was stirred for 1 hour. 200 mL of methanol was then added dropwise, and the precipitate was collected by filtration. The crude product was recrystallized from THF-methanol, yielding 5.2 g (11.4 mmol, 49%) of intermediate (B-3).

[0096] [Synthesis of Intermediate (BH)] Intermediate (BH) represented by the following formula (BH) was synthesized according to the following scheme.

[0097] Specifically, 5.0 g (11.0 mmol) of intermediate (B-3) was dissolved in 50 mL of THF, 0.5 g of 10% palladium carbon was added, and the mixture was stirred under a hydrogen atmosphere for 3 hours. The reaction solution was filtered through Celite, methanol was added, and the precipitate was filtered. 3.81 g (10.5 mmol, 95%) of intermediate (B-H) was obtained.

[0098] Example 1 Preparation of Liquid Crystal Composition 1 According to the following scheme, a liquid crystal composition 1 containing liquid crystal compounds (1-A), (1-B) and (1-C) represented by the following formulae (1-A), (1-B) and (1-C) was prepared.

[0099] Specifically, 9.0 g (23.7 mmol) of intermediate (A) represented by the above formula (A), 1.0 g (3.1 mmol) of intermediate (A-H) represented by the above formula (A-H), 40 mL of toluene, 15 mL of N,N-dimethylacetamide (DMAc), and 150 mg of 2,6-di-t-butyl-4-methylphenol were mixed at room temperature, and the internal temperature was cooled to 5°C. The mixture was added with thionyl chloride (SOCl ２) was added dropwise so that the internal temperature did not rise above 10°C. After stirring at 5°C for 1 hour, a tetrahydrofuran (THF) solution (50 mL) of 3.0 g (12.1 mmol) of the core body (1-1) represented by the above formula (1-1) was added. 11.6 mL (66.4 mmol) of N,N-diisopropylethylamine (DIPEA) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After stirring, 40 mL of 1N aqueous hydrochloric acid and 40 mL of ethyl acetate were added to stop the reaction, and the layers were separated. The organic layer was washed with 10% saline, and then 60 mL of isopropanol and 40 mL of methanol were added dropwise in that order. The mixture was then cooled to 5°C, and the precipitated crystals were collected by filtration. The product was analyzed by liquid chromatography mass spectrometry (LC-MS), and it was confirmed that the liquid crystal compounds (1-A) / (1-B) / (1-C) were contained in a mass ratio of 85 / 7 / 8. Furthermore, from the mass spectrometry (MS) spectrum of each component, it was confirmed that the molecular weights of the liquid crystal compounds (1-A) / (1-B) / (1-C) were 972.39 / 918.38 / 936.35 (M+), respectively. Furthermore, from the ultraviolet (UV) spectrum of each component, it was confirmed that the liquid crystal compounds (1-A) / (1-B) / (1-C) all had a maximum absorption wavelength at a wavelength of 355 nm.

[0100] Example 2 Preparation of Liquid Crystal Composition 2 According to the following scheme, a liquid crystal composition 2 containing liquid crystal compounds (1-A) and (2) represented by the following formulae (1-A) and (2) was prepared.

[0101] Specifically, 10 g (10.3 mmol) of compound (1-A) represented by the above formula (1-A) and synthesized by the method described in WO 2019 / 017445 was dissolved in 100 mL of THF, and 0.13 g (1.0 mmol) of dimethylaminopyridine (DMAP) and 1.0 mL of 1N hydrochloric acid were added and stirred at room temperature for 2 hours. After stirring, 100 mL of methanol was added, and the precipitated crystals were collected by filtration. The product was analyzed by LC-MS, and it was confirmed that the liquid crystal compound (1-A) / compound (2) was contained in a mass ratio of 99 / 1. Furthermore, from the MS spectrum, the molecular weight of the cationic component of liquid crystal compound (2) was confirmed to be 1095.48. Furthermore, from the UV spectrum of each component, it was confirmed that liquid crystal compound (2) had a maximum absorption wavelength at a wavelength of 355 nm.

[0102] Example 3 Preparation of Liquid Crystal Composition 3 According to the following scheme, liquid crystal composition 3 containing liquid crystal compounds (3-A), (3-B) and (3-C) represented by the following formulae (3-A), (3-B) and (3-C) was prepared.

[0103] Specifically, liquid crystal composition 3 was prepared in the same manner as liquid crystal composition 1, except that intermediate (B) represented by formula (B) was used instead of intermediate (A), intermediate (B-H) represented by formula (B-H) was used instead of intermediate (A-H), and core (2-1) represented by formula (2-1) was used instead of core (1-1). The product was analyzed by LC-MS, and it was confirmed that the liquid crystal compounds (3-A) / (3-B) / (3-C) were contained in a mass ratio of 83 / 8 / 9. Furthermore, the MS spectra of each component confirmed that the molecular weights of liquid crystal compounds (3-A) / (3-B) / (3-C) were 1128.41 / 1074.40 / 1092.37 (M+), respectively. Furthermore, the UV spectra of each component confirmed that liquid crystal compounds (3-A) / (3-B) / (3-C) all had a maximum absorption wavelength at a wavelength of 355 nm. Liquid crystal composition 3 was purified by column chromatography to isolate liquid crystal compounds (3-B) and (3-C). The MS spectrum of liquid crystal compound (3-B) had m / z: 1074.40 (100.0%), 1075.40 (66.6%), and the MS spectrum of liquid crystal compound (3-C) had m / z: 1092.37 (100.0%), 1093.37 (66.6%).

[0104] [Synthesis of Liquid Crystal Compound (3-A)] 1.2 g (26.8 mmol) of intermediate (B), 40 mL of toluene, 15 mL of N,N-dimethylacetamide (DMAc), and 150 mg of 2,6-di-t-butyl-4-methylphenol were mixed at room temperature and cooled to 5°C. 2.9 mL (40.2 mmol) of thionyl chloride (SOCl2) was added dropwise to the mixture so that the internal temperature did not rise above 10°C. After stirring at 5°C for 1 hour, a tetrahydrofuran (THF) solution (50 mL) of 4.0 g (12.2 mmol) of core body (2-1) was added. 11.6 mL (66.4 mmol) of N,N-diisopropylethylamine (DIPEA) was added dropwise, and the mixture was stirred at room temperature for 2 hours. After stirring, 40 mL of 1N aqueous hydrochloric acid and 40 mL of ethyl acetate were added to terminate the reaction, and the mixture was separated. The organic layer was washed with 10% saline, and then 60 mL of isopropanol and 40 mL of methanol were added dropwise in this order, followed by cooling to 5° C. and filtering out the precipitated crystals. The crude product was purified by column chromatography to obtain 5.0 g (4.4 mmol, 36%) of liquid crystal compound (3-A).

[0105] Example 4 Preparation of Liquid Crystal Composition 4 According to the following scheme, a liquid crystal composition 4 containing liquid crystal compounds (3-A) and (4) represented by the following formulae (3-A) and (4) was prepared.

[0106] Specifically, liquid crystal composition 4 was prepared in the same manner as liquid crystal composition 2, except that compound (3-A) represented by formula (3-A) was used instead of compound (1-A). The product was analyzed by LC-MS, and it was confirmed that the liquid crystal compounds (3-A) / (4) were contained in a mass ratio of 99 / 1. Furthermore, from the MS spectrum, it was confirmed that the molecular weight of the cationic component of compound (4) was 1251.50. Furthermore, from the UV spectrum of each component, it was confirmed that compound (4) had a maximum absorption wavelength at a wavelength of 355 nm.

[0107] Example 5 Preparation of Liquid Crystal Composition 5 According to the following scheme, liquid crystal composition 5 containing liquid crystal compounds (5-A), (5-B) and (5-C) represented by the following formulae (5-A), (5-B) and (5-C) was prepared.

[0108] Specifically, liquid crystal composition 5 was prepared in the same manner as liquid crystal composition 1, except that intermediate (B) was used instead of intermediate (A), intermediate (B-H) was used instead of intermediate (A-H), and core (3-1) represented by formula (3-1) was used instead of core (1-1). The product was analyzed by LC-MS, and it was confirmed that the liquid crystal compounds (5-A) / (5-B) / (5-C) were contained in a mass ratio of 82 / 9 / 9. Furthermore, MS spectra of each component confirmed that the molecular weights of liquid crystal compounds (5-A) / (5-B) / (5-C) were 1111.44 / 1057.43 / 1075.39 (M+), respectively. Furthermore, UV spectra of each component confirmed that liquid crystal compounds (5-A) / (5-B) / (5-C) all had a maximum absorption wavelength at a wavelength of 349 nm. Liquid crystal composition 5 was purified by column chromatography to isolate liquid crystal compounds (5-B) and (5-C). The MS spectrum of liquid crystal compound (5-B) had m / z: 1057.43 (100.0%), 1058.43 (67.4%), and the MS spectrum of liquid crystal compound (5-C) had m / z: 1075.39 (100.0%), 1076.40 (66.1%).

[0109] [Synthesis of Liquid Crystal Compound (5-A)] Liquid crystal compound (5-A) was synthesized in the same manner as liquid crystal compound (3-A), except that core body (2-1) was replaced with core body (3-1).

[0110] Example 6 Preparation of Liquid Crystal Composition 6 Liquid crystal composition 6 containing liquid crystal compounds (5-A) and (6) represented by the following formulae (5-A) and (6) was prepared according to the following scheme.

[0111] Specifically, liquid crystal composition 6 was prepared in the same manner as liquid crystal composition 2, except that liquid crystal compound (5-A) represented by formula (5-A) above was used instead of compound (1-A). The product was analyzed by LC-MS, and it was confirmed that the liquid crystal compounds (5-A) / (6) were contained in a mass ratio of 99 / 1. Furthermore, from the MS spectrum, it was confirmed that the molecular weight of the cationic component of compound (6) was 1234.53. Furthermore, from the UV spectrum of each component, it was confirmed that compound (6) had a maximum absorption wavelength at a wavelength of 349 nm.

[0112] Comparative Examples 1 and 2 In Comparative Examples 1 and 2, the above-described liquid crystal compound (3-A) and liquid crystal compound (5-A) were used, respectively.

[0113] [Evaluation] [Stretchability] A coating solution (liquid crystal composition) having the following composition was prepared and applied by bar coating onto rubbed PET (75 μm thick) manufactured by Fujifilm Corporation. The coating film was subjected to an alignment treatment at 140° C. to form a liquid crystal layer. The coating was then cooled to 60° C. and applied with an aligning current of 300 mJ / cm 2 . ２ The orientation was fixed by ultraviolet irradiation to form a liquid crystal cured layer, and an optical film for stretchability evaluation was obtained. The wavelength dispersion of the obtained optical film was measured using AxoScan (manufactured by Axometrics), and it was confirmed that all of the films had reverse wavelength dispersion.

[0114] -------------------------------------------------- Coating liquid -------------------------------------------------- Liquid crystal compound (compound or composition shown in Table 1 below) 15.00 parts by mass Photopolymerization initiator (Irgacure 819, manufactured by BASF) 0.45 parts by mass Fluorine-containing compound A shown below 0.12 parts by mass Chloroform 35.00 parts by mass --------------------------------------------------

[0115] Fluorine-containing compound A

[0116] The obtained optical film was cut into a size of 1 cm x 5 cm to prepare a sample. The sample was gripped with a jig at 1 cm from the top end and 1 cm from the bottom end, and a tensile test was performed at a speed of 300 mm / sec in an atmosphere of 150°C using a thermal Tensilon (RTF-1310 manufactured by A&D Co., Ltd. and a thermostatic testing device TKC). The state of the cured liquid crystal layer in the sample was observed and the breaking elongation of the cured liquid crystal layer was measured based on the following formula. In the following formula, "gauge length at break" means the gauge length when the liquid crystal layer in the sample broke. Formula: Breaking elongation (%) = {(gauge length at break - gauge length before test) / (gauge length before test)} x 100 <Criteria> A: Breaking elongation is 30% or more B: Breaking elongation is 10% or more but less than 30% C: Breaking elongation is less than 10%

[0117] [Precipitation] 20 μL of the coating solution prepared above was dropped onto a glass plate, and after leaving it at 25° C. for 1 hour, the degree of precipitation of the solid film was visually observed. Specifically, the area of ​​the cloudy white part (whitened part) relative to the area of ​​the solid film was roughly calculated, and the precipitation was evaluated using an index of 1 to 3 according to the following criteria. The results are shown in Table 1 below. <Criteria> Precipitation 1: Whitening occurs at 75% or more and 100% or less. Precipitation 2: Whitening occurs at 25% or more and less than 75%. Precipitation 3: Whitening occurs at less than 25%.

[0118]

[0119] From the results shown in Table 1 above, it was found that when the second liquid crystal compound was not contained, the liquid crystal composition could not suppress the precipitation tendency, and the stretchability of the produced cured liquid crystal layer was also poor (Comparative Examples 1 and 2). In contrast, it was found that when the liquid crystal composition contained the first liquid crystal compound and the second liquid crystal compound, the precipitation tendency was suppressed, and the stretchability of the produced cured liquid crystal layer was also good (Examples 1 to 6).

[0120] 10 Optical film 12 Liquid crystal cured layer 14 Alignment film 16 Support

Claims

1. A liquid crystal composition comprising a first liquid crystal compound represented by the following formula (1) and a second liquid crystal compound represented by the following formula (2), wherein both of the first liquid crystal compound and the second liquid crystal compound have a maximum absorption wavelength in the wavelength range of 280 to 420 nm. In the formulae (1) and (2), M represents a divalent mesogenic skeleton having three or more aromatic or aliphatic rings which may have a substituent, and M in the formulae (1) and (2) represents the same as each other. １ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. １ represent the same thing. ２ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. ２ represent the same thing. １ represents a polymerizable group, and L in the formulas (1) and (2) １ represent the same thing. ２ represents a polymerizable group. T represents a hydroxy group, a halogen atom, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or a substituent represented by the following formula (3) or (4). In the formulas (3) and (4), * represents SP ２ represents the bonding position with X － represents a counter anion. Ｔ１ ~R Ｔ３ each independently represents an alkyl group having 1 to 6 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. Ｔ１ ~R Ｔ３ is R Ｔ１ ~R Ｔ３ Two or three of R may be bonded to each other to form a ring. Ｔ４ and R Ｔ５ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ２ One or more of - may be substituted by -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. A represents a 5- or 6-membered nitrogen-containing aromatic ring which may have a substituent.

2. The liquid crystal composition according to claim 1, wherein M in the formulas (1) and (2) represents a divalent mesogenic skeleton represented by the following formula (5): In the formula (5), * represents SP １ Or SP ２ It represents the bonding position with B. １ and B ２ each independently represents an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent, and -CH ２ One or more of - may be replaced by -O-, -S- or -NH-. １ , D ２ , D ３ and D. ４ each independently represents a single bond, -CO-, -O-, -S-, -C(=S)-, or -CR １ R ２ -, -CR ３ =CR ４ --, --NR ５ -, or a divalent linking group consisting of two or more of these, R １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms; m1 and m2 each independently represent an integer of 1 to 3; when m1 represents 2 or 3, a plurality of B １ and D. １ may be the same or different, and when m2 represents 2 or 3, a plurality of B ２ and D. ２ may be the same or different, and Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulae (Ar-1) to (Ar-7). In the formulae (Ar-1) to (Ar-7), * represents D １ Or D ２ It represents the bonding position with Q. １ represents N or CH. ２ is -S-, -O-, or -N(R ６ )-, R ６ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and -CH ２ One or more of - may be substituted with -O-, -S- or -NH-. １ , Z ２ and Z ３ each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent aromatic heterocyclic group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ７ , -NR ８ R ９ , -SR １０ , -COOR １１ or -COR １２ represents R ７ ~R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Z １ and Z ２ may be bonded to each other to form an aromatic ring. ３ and A ４ Each independently represents -O-, -N(R １３ ) represents a group selected from the group consisting of -, -S-, and -CO-; R １３ represents a hydrogen atom or a substituent. X represents a nonmetallic atom of Groups 14 to 16. However, the nonmetallic atom may be bonded to a hydrogen atom or a substituent. D ７ and D. ８ each independently represents a single bond, -CO-, -O-, -S-, -C(=S)-, or -CR １ R ２ -, -CR ３ =CR ４ --, --NR ５ -, or a divalent linking group consisting of two or more of these, R １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. ３ and S.P. ４ each independently represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. ３ and L ４ each independently represents a monovalent organic group. Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. The aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring. Q ３ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms.

3. The liquid crystal composition according to claim 1, wherein the content of the second liquid crystal compound is 0.01 to 20% by mass with respect to the total mass of the first liquid crystal compound and the second liquid crystal compound.

4. A liquid crystal compound represented by the following formula (2): In the formula (2), M represents a divalent mesogenic skeleton represented by the following formula (5): １ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. SP ２ represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. １ represents a polymerizable group. T represents a hydroxy group, a halogen atom, an alkylcarbonyloxy group having 1 to 6 carbon atoms, or a substituent represented by the following formula (3) or (4). In the formula (5), * represents SP １ Or SP ２ It represents the bonding position with B. １ and B ２ each independently represents an aromatic ring having 6 to 20 carbon atoms which may have a substituent, or a divalent alicyclic hydrocarbon group having 5 to 20 carbon atoms which may have a substituent, and -CH ２ One or more of - may be replaced by -O-, -S- or -NH-. １ , D ２ , D ３ and D. ４ each independently represents a single bond, -CO-, -O-, -S-, -C(=S)-, or -CR １ R ２ -, -CR ３ =CR ４ --, --NR ５ -, or a divalent linking group consisting of two or more of these, R １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms; m1 and m2 each independently represent an integer of 1 to 3; when m1 represents 2 or 3, a plurality of B １ and D. １ may be the same or different, and when m2 represents 2 or 3, a plurality of B ２ and D. ２ may be the same or different, and Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulae (Ar-1) to (Ar-7). In the formulae (Ar-1) to (Ar-7), * represents D １ Or D ２ It represents the bonding position with Q. １ represents N or CH. ２ is -S-, -O-, or -N(R ６ )-, R ６ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and -CH ２ One or more of - may be substituted with -O-, -S- or -NH-. １ , Z ２ and Z ３ each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent aromatic heterocyclic group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ７ , -NR ８ R ９ , -SR １０ , -COOR １１ or -COR １２ represents R ７ ~R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Z １ and Z ２ may be bonded to each other to form an aromatic ring. ３ and A ４ Each independently represents -O-, -N(R １３ ) represents a group selected from the group consisting of -, -S-, and -CO-; R １３ represents a hydrogen atom or a substituent. X represents a nonmetallic atom of Groups 14 to 16. However, the nonmetallic atom may be bonded to a hydrogen atom or a substituent. D ７ and D. ８ each independently represents a single bond, -CO-, -O-, -S-, -C(=S)-, or -CR １ R ２ -, -CR ３ =CR ４ --, --NR ５ -, or a divalent linking group consisting of two or more of these, R １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. ３ and S.P. ４ each independently represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. ３ and L ４ each independently represents a monovalent organic group; L ３ and L ４ And L in the formula (B) １ and L ２ At least one of these represents a polymerizable group. Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. The aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring. Q ３ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 20 carbon atoms. In the formulas (3) and (4), * represents SP ２ represents the bonding position with X － represents a counter anion. Ｔ１ ~R Ｔ３ each independently represents an alkyl group having 1 to 6 carbon atoms. ２ One or more of - may be substituted with -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. Ｔ１ ~R Ｔ３ is R Ｔ１ ~R Ｔ３ Two or three of R may be bonded to each other to form a ring. Ｔ４ and R Ｔ５ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ２ One or more of - may be substituted by -O-, -S-, -NH-, -N(Q)- or -CO-. Q represents a substituent. A represents a 5- or 6-membered nitrogen-containing aromatic ring which may have a substituent.

5. A liquid crystal cured layer obtained by fixing the alignment state of the liquid crystal composition according to any one of claims 1 to 3.

6. An optical film having the liquid crystal cured layer according to claim 5.

7. A polarizing plate comprising the optical film according to claim 6 and a polarizer.

8. An image display device comprising the optical film according to claim 6.

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