Liquid crystal composition, light-absorbing anisotropic film, method for producing light-absorbing anisotropic film, optical laminate, and image display device

Abstract

The present invention addresses the problem of providing: a liquid crystal composition which has excellent solubility and from which it is possible to manufacture a light-absorbing anisotropic film having a high orientation degree; a light-absorbing anisotropic film; a method for producing the light-absorbing anisotropic film; an optical laminate; and an image display device. A liquid crystal composition according to the present invention contains a dichroic substance represented by formula (1) and a liquid crystal compound. In formula (1), Y represents an n-valent dye skeletal structure. n represents an integer of one or more. LB represents a divalent aliphatic hydrocarbon group having one or more carbon atoms, and at least one of -CH2- forming the aliphatic hydrocarbon group is optionally substituted with -CO-, -O-, -S-, -NH-, or -N(Q)-. Q represents a substituent. X represents a prescribed acid-cleavable group.

Description

Liquid crystal composition, optically absorbing anisotropic film, method for producing optically absorbing anisotropic film, optical laminate, and image display device

[0001] The present invention relates to a liquid crystal composition, an optically absorptive anisotropic film, a method for producing an optically absorptive anisotropic film, an optical laminate, and an image display device.

[0002] Conventionally, when light attenuation, polarization, scattering, or light blocking functions for irradiated light, including laser light or natural light, were required, devices operating on different principles for each function were used. Therefore, products corresponding to the above functions were also manufactured using different manufacturing processes for each function. For example, in liquid crystal displays (LCDs), linear polarizers and circular polarizers are used to control the optical rotation and birefringence of the display. Also, in organic light-emitting diodes (OLEDs), circular polarizers are used to prevent reflection of external light.

[0003] Conventionally, iodine has been widely used as a dichroic material in these polarizing plates (polarizing elements), but polarizing elements using an organic dye as a dichroic material instead of iodine have also been studied. For example, Patent Document 1 describes a light absorption anisotropic film formed using a liquid crystal composition containing a polymer liquid crystal compound and a dichroic material ([Claim 1]).

[0004] International Publication No. 2020 / 122116

[0005] The present inventors have studied the liquid crystal composition and optically absorptive anisotropic film described in Patent Document 1 and have found that there is room for improvement in achieving both the solubility of the liquid crystal composition and the degree of orientation of the optically absorptive anisotropic film.

[0006] Therefore, an object of the present invention is to provide a liquid crystal composition with excellent solubility that can be used to prepare an optically absorbing anisotropic film with a high degree of orientation, an optically absorbing anisotropic film, a method for manufacturing an optically absorbing anisotropic film, an optical laminate, and an image display device.

[0007] As a result of extensive research into the above-mentioned problems, the present inventors have found that the use of a dichroic substance having a specific acid-cleavable group together with a liquid crystal compound improves the solubility of the liquid crystal composition and increases the degree of orientation of the resulting optically absorptive anisotropic film, thereby completing the present invention. That is, the present inventors have found that the above-mentioned problems can be solved by the following configuration.

[0008] [1] A liquid crystal composition containing a dichroic substance represented by formula (1) described later and a liquid crystal compound. [2] The liquid crystal composition according to [1], wherein X in formula (1) described later represents an acid-cleavable group represented by any of formulas (A1) to (A5) described later. [3] The liquid crystal composition according to [2], wherein X in formula (1) described later represents an acid-cleavable group represented by formula (A2) described later. [4] The liquid crystal composition according to [2], wherein two R Ａ２ [5] The liquid crystal composition according to [3], wherein R in formula (A2) described later is a monovalent aliphatic hydrocarbon group. Ａ２The liquid crystal composition according to [4], wherein n in formula (1) described later represents an integer of 2 or greater. [7] The liquid crystal composition according to any one of [1] to [6], wherein the dichroic substance is represented by formula (2) described later. [8] The liquid crystal composition according to any one of [1] to [7], wherein the content of the dichroic substance is 4 to 80 mass % with respect to the total mass of the solid content of the liquid crystal composition. [9] An optically absorptive anisotropic film obtained by fixing the alignment state of the liquid crystal composition according to any one of [1] to [8].

[10] The optically absorptive anisotropic film according to [9], obtained by fixing the liquid crystal compound contained in the liquid crystal composition in a horizontally aligned state.

[11] The optically absorptive anisotropic film according to [9] or

[10] , wherein the angle θ between the central axis of transmittance of the optically absorptive anisotropic film and the normal direction to the surface of the optically absorptive anisotropic film is 0° or greater and 45° or less.

[12] A method for producing the optically absorptive anisotropic film according to any one of [9] to

[11] , comprising: a coating film formation step of applying the liquid crystal composition according to any one of [1] to [8] to form a coating film; a cleavage step of generating an acid in the coating film by light irradiation or heating after the coating film formation step to cleave the acid-cleavable group of the dichroic material represented by formula (1); an alignment step of aligning the dichroic material whose acid-cleavable group has been cleaved after the cleavage step; and a curing step of fixing the alignment state of the dichroic material to obtain the optically absorptive anisotropic film after the alignment step.

[13] An optical laminate comprising the optically absorptive anisotropic film according to any one of [9] to

[11] .

[14] An image display device comprising the optically absorptive anisotropic film according to any one of [9] to

[11] .

[0009] As will be described below, the present invention can provide a liquid crystal composition having excellent solubility that can be used to prepare an optically absorptive anisotropic film with a high degree of orientation, an optically absorptive anisotropic film, a method for producing an optically absorptive anisotropic film, an optical laminate, and an image display device.

[0010] 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.

[0011] 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).

[0012] 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.

[0013] [Liquid Crystal Composition] The liquid crystal composition of the present invention contains a dichroic substance represented by formula (1) described below and a liquid crystal compound.

[0014] In the present invention, as described above, by using a dichroic substance represented by Formula (1) described below together with a liquid crystal compound, the solubility of the liquid crystal composition is improved, and the degree of alignment of the resulting optically absorptive anisotropic film is also increased. The reason for this effect is unclear, but the inventors speculate as follows. First, the acid-cleavable group possessed by the dichroic substance represented by Formula (1) described below, i.e., the acid-cleavable group represented by any of Formulas (A1) to (A6) described below, is a flexible or bulky substituent. This is thought to suppress crystallization of the dichroic substance and improve the solubility of the liquid crystal composition. Furthermore, when preparing an optically absorptive anisotropic film, specifically, by subjecting a coating film formed by coating the liquid crystal composition to a treatment for cleaving the acid-cleavable group, the flexible or bulky substituent is eliminated, thereby accelerating crystallization of the dichroic substance and improving the degree of alignment of the resulting optically absorptive anisotropic film. The dichroic substance, liquid crystal compound, and optional components contained in the liquid crystal composition of the present invention are described in detail below.

[0015] [Dichroic Substance] <Dichroic Substance Represented by Formula (1)> The liquid crystal composition of the present invention contains a dichroic substance represented by the following formula (1). Here, the dichroic substance refers to a dye whose absorbance varies depending on the direction. The dichroic substance may or may not exhibit liquid crystallinity.

[0016] In the above formula (1), Y represents an n-valent dye skeleton structure. Here, the dye skeleton structure refers to a "structure having a maximum absorption wavelength in the visible light region (wavelength range of 380 nm to 780 nm)." The maximum absorption wavelength can be calculated from the absorption spectrum obtained by measuring the absorbance in the visible light region using an ultraviolet-visible spectrophotometer (for example, UV-1800 (manufactured by Shimadzu Corporation)). Examples of such a dye skeleton structure include, for example, -(L Ｂ -X) is preferably mentioned.

[0017] In the above formula (1), n ​​represents an integer of 1 or more. In the present invention, n is preferably an integer of 2 or more, more preferably an integer of 2 to 4, even more preferably 2 or 3, and particularly preferably 2, because this increases the degree of orientation of the optically absorptive anisotropic film to be produced.

[0018] In the above formula (1), L Ｂ represents a divalent aliphatic hydrocarbon group having one or more carbon atoms, and —CH ２ One or more of - may be substituted with -CO-, -O-, -S-, -NH- or -N(Q)-. Q represents a substituent. However, when n represents an integer of 2 or more, multiple L Ｂ may be the same or different. Examples of divalent aliphatic hydrocarbon groups having 1 or more carbon atoms include linear or branched alkylene groups having 1 to 20 carbon atoms, linear or branched alkenylene groups having 1 to 20 carbon atoms, and linear or branched alkynylene groups having 1 to 20 carbon atoms. As the linear or branched alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 12 carbon atoms is preferred, and an alkylene group having 1 to 10 carbon atoms is more preferred, and suitable examples 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 suitable examples include 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, an alkynylene group having 2 to 4 carbon atoms is more preferred, and a suitable example is an ethynylene group. As described above, -CH 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.

[0019] In the formula (1), X represents an acid-cleavable group represented by any one of the following formulae (A1) to (A6): When n represents an integer of 2 or more, the multiple Xs may be the same or different. In the formulae (A1) to (A6), * represents L Ｂ represents the bonding position with

[0020] In the above formulas (A1) to (A6), R Ａ１ represents a hydrogen atom or a monovalent hydrocarbon group, and some of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms, and some of the carbon atoms may be substituted with silicon or oxygen. Ａ１ may be the same or different, and may be bonded to each other to form a ring. Ａ２ represents a monovalent hydrocarbon group, in which some of the hydrogen atoms may be substituted with halogen atoms, and some of the carbon atoms may be substituted with silicon or oxygen. Ａ２ may be the same or different and may be bonded to each other to form a ring.

[0021] Here, R Ａ１ and R Ａ２Examples of the monovalent hydrocarbon group represented by include monovalent chain hydrocarbon groups, monovalent alicyclic hydrocarbon groups, and monovalent aromatic hydrocarbon groups. Examples of the monovalent chain hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; and alkynyl groups such as ethynyl, propynyl, and butynyl. Examples of the monovalent alicyclic hydrocarbon groups include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; and cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl. Examples of the monovalent aromatic hydrocarbon group include aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Of these, a monovalent chain hydrocarbon group is preferred, and an alkyl group is more preferred.

[0022] Also, R Ａ１ and R Ａ２ In the monovalent hydrocarbon group represented by the formula (I), some of the hydrogen atoms of the hydrocarbon group are substituted with halogen atoms, and examples thereof include fluorinated alkyl groups in which some of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and specific examples thereof include -(CH ２ ) ｍ１ (CF ２ ) ｍ２ CF ２ X. Incidentally, m1 and m2 each independently represent an integer of 0 to 19, and X represents a hydrogen atom or a fluorine atom. Furthermore, m1 is preferably an integer of 1 to 10, and m2 is preferably an integer of 0 to 9. Similarly, examples of embodiments in which a portion of the carbon atoms is substituted with silicon or oxygen include embodiments in which a portion of the carbon atoms of an alkyl group is substituted with silicon or oxygen, and specifically, -(CH ２ ) ｍ３ Si(CH ３ ) ３ , -(CH２ ) ｍ３ Si(OSi(CH ３ ) ３ ) ３ In addition, m3 represents an integer of 1 to 10.

[0023] In the present invention, because the degree of orientation of the optically absorptive anisotropic film to be produced is higher, X in the above formula (1) preferably represents an acid-cleavable group represented by any one of the above formulae (A1) to (A5), and more preferably represents an acid-cleavable group represented by the above formula (A2).

[0024] In the present invention, the two R Ａ２ Preferably, each of R independently represents a linear or branched monovalent aliphatic hydrocarbon group. Ａ２ are preferably not bonded to each other to form a ring. Examples of the linear monovalent aliphatic hydrocarbon group include linear alkyl groups having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. Examples of the branched monovalent aliphatic hydrocarbon group include branched alkyl groups having 3 to 6 carbon atoms, such as an isopropyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a neopentyl group, an isohexyl group, and a 3-methylpentyl group.

[0025] Furthermore, in the present invention, the degree of orientation of the optically absorptive anisotropic film to be produced is further increased by adding R Ａ２ The molecular weight of the copolymer is preferably 300 or less, and more preferably 10 to 150.

[0026] A suitable example of the dichroic material represented by the above formula (1) is a compound represented by the following formula (2).

[0027] In the above formula (2), X and L Ｂ are the same as those in the formula (1), provided that the two Xs may be the same or different, and the two Ls may be the same or different. Ｂmay be the same or different.

[0028] In the above formula (2), n1 and n2 each independently represent an integer of 0 to 4. Here, n1 and n2 each independently represent an integer of 0 to 2, and more preferably 0 or 1.

[0029] In the above formula (2), k represents an integer of 1 to 4. Here, k is preferably an integer of 2 to 4, and more preferably 2 or 3.

[0030] In the above formula (2), Ar １ represents an (n1+2)-valent aromatic hydrocarbon group or an (n1+2)-valent heterocyclic group, provided that when k represents an integer of 2 to 4, a plurality of Ar １ may be the same or different. Here, examples of the (n1+2)-valent aromatic hydrocarbon group include groups obtained by removing from an aromatic hydrocarbon ring the number of hydrogen atoms corresponding to the valence, i.e., the number of hydrogen atoms bonded to carbon atoms constituting the aromatic hydrocarbon ring, corresponding to the valence. Similarly, examples of the (n1+2)-valent heterocyclic group include groups obtained by removing from a heterocycle the number of hydrogen atoms corresponding to the valence, i.e., the number of hydrogen atoms bonded to carbon atoms or heteroatoms constituting the heterocycle, corresponding to the valence. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring. Examples of heterocyclic rings include a furan ring, a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.

[0031] In the above formula (2), Ar ２ represents an (n2+2)-valent aromatic hydrocarbon group or an (n2+2)-valent heterocyclic group. Here, the aromatic hydrocarbon group and the heterocyclic group include Ar １ Examples of the above-described examples are the same as those described above.

[0032] In the above formula (2), R １ and R ２ each independently represents a substituent, provided that when n1 represents an integer of 2 to 4, multiple R １may be the same or different, and when n2 represents an integer of 2 to 4, a plurality of R ２ may be the same or different. Examples of the substituent include those described in the above-mentioned substituent group A, and among them, an alkyl group or a halogen atom is preferred.

[0033] In the above formula (2), L Ｃ represents -N=N-, -N=CY-, -CY=CY-, -OCO-, -SCO- or -NHCO-, and Y represents a substituent. However, when k represents an integer of 2 to 4, a plurality of L Ｃ may be the same or different. Here, examples of the substituent represented by Y 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] Suitable examples of the dichroic substance represented by the formula (1), particularly the compound represented by the formula (2), include compounds represented by the following formulae B-1 to B-15. In the following formulae, Me represents a methyl group, and TMS represents a trimethylsilyl group (-Si(CH ３ ) ３ ) represents

[0035] In the present invention, the content of the dichroic substance represented by the above formula (1) is preferably 4 to 80 mass %, more preferably 5 to 40 mass %, and even more preferably 6 to 20 mass %, relative to the total mass of the solid content of the liquid crystal composition.

[0036] <Other Dichroic Substances> The liquid crystal composition of the present invention may contain other dichroic substances in addition to the dichroic substance represented by formula (1) above.

[0037] The other dichroic substances are not particularly limited, and examples thereof include visible light absorbing substances (dichroic dyes), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet absorbing substances, infrared absorbing substances, nonlinear optical substances, carbon nanotubes, and inorganic substances (e.g., quantum rods), and any conventionally known dichroic substances (dichroic dyes) can be used. Specifically, for example, paragraphs

[0067] to

[0071] of JP 2013-228706 A, paragraphs

[0008] to

[0026] of JP 2013-227532 A, paragraphs

[0008] to

[0015] of JP 2013-209367 A, paragraphs

[0045] to

[0058] of JP 2013-14883 A, paragraphs

[0012] to

[0029] of JP 2013-109090 A, paragraphs

[0009] to

[0017] of JP 2013-101328 A, Paragraphs

[0051] to

[0065] of JP 2013-37353 A, paragraphs

[0049] to

[0073] of JP 2012-63387 A, paragraphs

[0016] to

[0018] of JP 11-305036 A, paragraphs

[0009] to

[0011] of JP 2001-133630 A, paragraphs

[0030] to

[0169] of JP 2011-215337 A, paragraphs

[0021] to

[0075] of JP 2010-106242 A, paragraphs

[0016] to

[0018] of JP 2010-215846 A

[0011] to

[0025] paragraphs,

[0017] to

[0069] paragraphs of JP 2011-048311 A,

[0013] to

[0133] paragraphs of JP 2011-213610 A,

[0074] to

[0246] paragraphs of JP 2011-237513 A,

[0005] to

[0051] paragraphs of JP 2016-006502 A,

[0014] to

[0032] paragraphs of JP 2018-053167 A, and

[0014] to

[0033] paragraphs of JP 2020-11716 A paragraphs

[0005] to

[0041] of International Publication No. 2016 / 060173, paragraphs

[0008] to

[0062] of International Publication No. 2016 / 136561, paragraphs

[0014] to

[0033] of International Publication No. 2017 / 154835, paragraphs

[0014] to

[0033] of International Publication No. 2017 / 154695, paragraphs

[0013] to

[0037] of International Publication No. 2017 / 195833, paragraphs

[0014] to

[0034] of International Publication No. 2018 / 164252,Examples include those described in paragraphs

[0021] to

[0030] of International Publication No. 2018 / 186503, paragraphs

[0043] to

[0063] of International Publication No. 2019 / 189345, paragraphs

[0043] to

[0085] of International Publication No. 2019 / 225468, paragraphs

[0050] to

[0074] of International Publication No. 2020 / 004106, and paragraphs

[0015] to

[0038] of International Publication No. 2021 / 044843.

[0038] As another dichroic substance, a dichroic azo dye compound is preferred. A dichroic azo dye compound refers to an azo dye compound whose absorbance varies depending on the direction. A dichroic azo dye compound may or may not exhibit liquid crystallinity. When a dichroic azo dye compound exhibits liquid crystallinity, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystal phase is exhibited is preferably room temperature (approximately 20 to 28°C) to 300°C, and more preferably 50 to 200°C from the viewpoints of handleability and manufacturing suitability.

[0039] In the present invention, from the viewpoint of adjusting color hue, it is preferable to use at least one dye compound (first dichroic azo dye compound) having a maximum absorption wavelength in the wavelength range of 560 to 700 nm, and at least one dye compound (second dichroic azo dye compound) having a maximum absorption wavelength in the wavelength range of 455 nm or more and less than 560 nm.

[0040] In the present invention, three or more kinds of dichroic azo dye compounds may be used in combination. For example, from the viewpoint of making the light absorption anisotropic film closer to black, it is preferable to use a first dichroic azo dye compound, a second dichroic azo dye compound, and at least one dye compound (third dichroic azo dye compound) having a maximum absorption wavelength in the wavelength range of 380 nm or more and less than 455 nm in combination.

[0041] In the present invention, the dichroic azo dye compound preferably has a crosslinkable group, such as a (meth)acryloyl group, an epoxy group, an oxetanyl group, or a styryl group, with a (meth)acryloyl group being preferred.

[0042] The content of the other dichroic substance is not particularly limited, but is preferably 10 to 80 mass %, more preferably 15 to 60 mass %, and even more preferably 20 to 40 mass %, relative to the total mass of the solid content of the liquid crystal composition.

[0043] [Liquid Crystal Compound] The liquid crystal composition of the present invention contains a liquid crystal compound. This allows the dichroic material to be aligned with a higher degree of orientation while suppressing precipitation of the dichroic material. As the liquid crystal compound, either a polymer liquid crystal compound or a low molecular weight liquid crystal compound can be used, with the polymer liquid crystal compound being preferred because it allows for a higher degree of orientation. Furthermore, the liquid crystal compound may be a combination of a polymer liquid crystal compound and a low molecular weight liquid crystal compound. Here, "polymer liquid crystal compound" refers to a liquid crystal compound having a repeating unit in its chemical structure. Furthermore, "low molecular weight liquid crystal compound" refers to a liquid crystal compound having no repeating unit in its chemical structure. Examples of polymer liquid crystal compounds include the thermotropic liquid crystal polymers described in JP 2011-237513 A and the polymer liquid crystal compounds described in paragraphs

[0012] to

[0042] of WO 2018 / 199096 A. Examples of low molecular weight liquid crystal compounds include those described in paragraphs

[0072] to

[0088] of JP 2013-228706 A, and among them, liquid crystal compounds exhibiting smectic properties are preferred. Examples of such liquid crystal compounds include those described in paragraphs

[0019] to

[0140] of WO 2022 / 014340 A, the disclosures of which are incorporated herein by reference. It should be noted that the liquid crystal compound is preferably a liquid crystal compound that does not exhibit dichroism in the visible light region.

[0044] The content of the liquid crystal compound is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass, and even more preferably 200 to 900 parts by mass, relative to 100 parts by mass of the content of the dichroic substance (including the content of other dichroic substances if contained). When the content of the liquid crystal compound is within the above range, the degree of orientation of the dichroic substance is further improved. The liquid crystal compound may be contained alone, or two or more types may be contained. When two or more types of liquid crystal compounds are contained, the content of the liquid crystal compound refers to the total content of the liquid crystal compounds.

[0045] [Acid Generator] <Thermal Acid Generator> The liquid crystal composition of the present invention preferably contains a thermal acid generator, specifically for the reason that when an optically absorptive anisotropic film is produced, the acid-cleavable group of the dichroic material represented by the above formula (1) can be easily cleaved in a coating film formed by coating the liquid crystal composition. The thermal acid generator is not particularly limited as long as it is a compound that generates an acid by heat, and examples thereof include onium salts such as sulfonium salts, ammonium salts, and phosphonium salts, and ester compounds such as carboxylate compounds, sulfonate compounds, and phosphate compounds.

[0046] Examples of acids generated from a thermal acid generator upon heating include sulfonic acid, phosphoric acid, and carboxylic acid, with sulfonic acid being preferred and aromatic sulfonic acid being more preferred. The pKa of the acid generated from a thermal acid generator is preferably −15 to 3, more preferably −10 to 0.

[0047] The acid generation temperature of the thermal acid generator is preferably 40 to 300°C, more preferably 80 to 260°C, even more preferably 100 to 220°C, and particularly preferably 120 to 200°C. The acid generation temperature is determined as the peak temperature of the lowest exothermic peak when the thermal acid generator is heated to 500°C at 5°C / min in a pressure-resistant capsule. An example of an instrument used to measure the acid generation temperature is the Q2000 (manufactured by TA Instruments). In addition, the acid generation temperature of the thermal acid generator is preferably lower than the boiling point of the solvent contained in the thermosetting photosensitive composition.

[0048] Suitable commercially available thermal acid generators include the San-Aid SI series manufactured by Sanshin Chemical Industry Co., Ltd., the CPI series manufactured by San-Apro Co., Ltd., and the K-PURE TAG series manufactured by King Co., Ltd. Also usable are known thermal acid generators described in JP-A Nos. 2003-277353, 2-001470, 2-255646, 3-011044, 2003-183313, 2003-277352, 58-037003, and 58-198532.

[0049] When the liquid crystal composition of the present invention contains a thermal acid generator, the content of the thermal acid generator is preferably 1 to 10 mass %, more preferably 2 to 5 mass %, based on the total mass of the solid content of the liquid crystal composition of the present invention.

[0050] <Photoacid Generator> The liquid crystal composition of the present invention preferably contains a photoacid generator, specifically for the reason that, when preparing an optically absorptive anisotropic film, the acid-cleavable group of the dichroic material represented by Formula (1) can be easily cleaved in a coating film formed by coating the liquid crystal composition. The photoacid generator is not particularly limited, and a compound that generates an acid in response to actinic rays with a wavelength of 300 nm or more, preferably 300 to 450 nm, is preferred. Photoacid generators that are not directly sensitive to actinic rays with a wavelength of 300 nm or more can also be used in combination with a sensitizer, as long as they are sensitive to actinic rays with a wavelength of 300 nm or more and generate an acid when used in combination with a sensitizer. As the photoacid generator, a photoacid generator that generates an acid with a pKa of 4 or less is preferred, a photoacid generator that generates an acid with a pKa of 3 or less is more preferred, and a photoacid generator that generates an acid with a pKa of 2 or less is even more preferred. In the present invention, pKa basically refers to the pKa in water at 25°C. For those that cannot be measured in water, measurements are made after changing to a solvent suitable for measurement. Specifically, the pKa values ​​listed in chemical handbooks and the like can be used as a reference. Acids with a pKa of 3 or less are preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.

[0051] Examples of photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferred, and onium salt compounds and oxime sulfonate compounds are more preferred. The photoacid generators can be used alone or in combination of two or more.

[0052] When the liquid crystal composition of the present invention contains a photoacid generator, the content of the photoacid generator is preferably 1 to 10 mass %, more preferably 2 to 5 mass %, based on the total mass of the solid content of the liquid crystal composition of the present invention.

[0053] [Polymerization Initiator] The liquid crystal composition of the present invention may contain a polymerization initiator. There are no particular limitations on the polymerization initiator, but it is preferably a photosensitive compound, i.e., a photopolymerization initiator. As the photopolymerization initiator, various compounds can be used without particular limitations. Examples of photopolymerization initiators include α-carbonyl compounds (U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (U.S. Pat. No. 2,722,512), polynuclear quinone compounds (U.S. Pat. Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazole dimers and p-aminophenyl ketones (U.S. Pat. No. 3,549,367). ), acridine and phenazine compounds (JP 60-105667 A and U.S. Pat. No. 4,239,850 A), oxadiazole compounds (U.S. Pat. No. 4,212,970 A), o-acyloxime compounds (JP 2016-27384 A

[0065] ), and acylphosphine oxide compounds (JP 63-40799 A, JP 5-29234 A, JP 10-95788 A, and JP 10-29997 A). Commercially available photopolymerization initiators can also be used, including Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01, and Irgacure-OXE-02 manufactured by BASF.

[0054] When the liquid crystal composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, based on the total mass of the solid content of the liquid crystal composition.

[0055] [Solvent] The liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability and the like. Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetylacetone, etc.), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, cyclopentyl methyl ether, dibutyl ether, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, tetralin, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, 1,1,2,2-tetrachloroethane, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, diethyl carbonate, ethyl acetoacetate, n-pentyl acetate, ethyl benzoate, benzyl benzoate, butyl carbitol acetate, diethylene glycol monoethyl ether acetate, Examples of suitable solvents include organic solvents such as ethanol, isopropanol, butanol, cyclohexanol, furfuryl alcohol, 2-ethylhexanol, octanol, benzyl alcohol, ethanolamine, ethylene glycol, propylene glycol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, phenols (e.g., phenol, cresol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, 1,2-dimethoxyethane, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc.), and heterocyclic compounds (e.g., pyridine, 2,6-lutidine, etc.), as well as water. These solvents may be used alone or in combination of two or more.

[0056] When the liquid crystal composition of the present invention contains a solvent, the content of the solvent is preferably 60 to 99.5 mass %, more preferably 70 to 99 mass %, and particularly preferably 75 to 98 mass %, relative to the total mass (100 mass %) of the liquid crystal composition.

[0057] [Interfacial Modifier] The liquid crystal composition of the present invention may contain an interfacial modifier. There are no particular limitations on the interfacial modifier, and polymer-based interfacial modifiers and low-molecular-weight interfacial modifiers can be used, including compounds described in paragraphs

[0253] to

[0293] of JP-A No. 2011-237513. Silicon-based polymers can also be used as interfacial modifiers. Fluorine (meth)acrylate-based polymers described in paragraphs

[0018] to

[0043] of JP-A No. 2007-272185 can also be used as interfacial modifiers. Examples of the interface improver include compounds described in paragraphs

[0079] to

[0102] of JP-A-2007-069471, polymerizable liquid crystal compounds represented by formula (4) described in JP-A-2013-047204 (particularly compounds described in paragraphs

[0020] to

[0032] ), polymerizable liquid crystal compounds represented by formula (4) described in JP-A-2012-211306 (particularly compounds described in paragraphs

[0022] to

[0029] ), and liquid crystal alignment promoters represented by formula (4) described in JP-A-2002-129162 (particularly compounds described in paragraphs

[0032] to

[0032] ). The compounds described in paragraphs

[0076] to

[0078] and

[0082] to

[0084] of the present invention, the compounds represented by formulas (4), (II) and (III) described in JP-A-2005-099248 (particularly the compounds described in paragraphs

[0092] to

[0096] ), the compounds described in paragraphs

[0013] to

[0059] of Japanese Patent No. 4,385,997, the compounds described in paragraphs

[0018] to

[0044] of Japanese Patent No. 5,034,200, and the compounds described in paragraphs

[0019] to

[0038] of Japanese Patent No. 4,895,088 can also be used. The interfacial modifiers may be used alone or in combination of two or more.

[0058] When the liquid crystal composition of the present invention contains an interfacial modifier, the content of the interfacial modifier is preferably 0.005 to 15% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.015 to 3% by mass, based on the total mass of the solid content of the liquid crystal composition. When multiple interfacial modifiers are used in combination, the total amount of the multiple interfacial modifiers is preferably in the above-mentioned range.

[0059] [Alignment Agent] The liquid crystal composition of the present invention preferably contains an alignment agent. Examples of the alignment agent include those described in paragraphs

[0042] to

[0076] of JP-A No. 2013-543526, paragraphs

[0089] to

[0097] of JP-A No. 2016-523997, and paragraphs

[0153] to

[0170] of JP-A No. 2020-076920. These may be used alone or in combination of two or more.

[0060] In the present invention, the aligning agent is preferably an onium compound represented by the following formula (B1), because this increases the degree of alignment of the light absorption anisotropic layer that is formed.

[0061] In the formula (B1), ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle, and X represents an anion. １ represents a divalent linking group. ２ represents a single bond or a divalent linking group. １ represents a divalent linking group having a 5-membered or 6-membered ring as a partial structure. Z represents a divalent linking group having an alkylene group having 2 to 20 carbon atoms as a partial structure. P １ and P ２ each independently represents a monovalent substituent having a polymerizable ethylenically unsaturated bond.

[0062] Ring A represents a quaternary ammonium ion consisting of a nitrogen-containing heterocycle. Examples of Ring A include a pyridine ring, a picoline ring, a 2,2'-bipyridyl ring, a 4,4'-bipyridyl ring, a 1,10-phenanthroline ring, a quinoline ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazine ring, a triazole ring, and a tetrazole ring, and are preferably a quaternary imidazolium ion or a quaternary pyridinium ion.

[0063] X represents an anion. Examples of X include halogen anions (e.g., fluorine ion, chloride ion, bromide ion, iodide ion, etc.), sulfonate ions (e.g., methanesulfonate ion, trifluoromethanesulfonate ion, methyl sulfate ion, vinyl sulfonate ion, allyl sulfonate ion, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion, p-vinylbenzenesulfonate ion, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, etc.), sulfate ion, carbonate ion, nitrate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, benzoate ion, p-vinylbenzoate ion, formate ion, trifluoroacetate ion, phosphate ion (e.g., hexafluorophosphate ion), hydroxide ion, etc. Preferred are halogen anions, sulfonate ions, and hydroxide ions. Particularly preferred are chloride ions, bromide ions, iodide ions, methanesulfonate ions, vinylsulfonate ions, p-toluenesulfonate ions, and p-vinylbenzenesulfonate ions.

[0064] L １ represents a divalent linking group. １ Examples of the group include an alkylene group, —O—, —S—, —CO—, and —SO ２ -, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, an alkynylene group, or a divalent linking group having 1 to 20 carbon atoms formed in combination with an arylene group. １is preferably -AL-, -O-AL-, -CO-O-AL-, or -O-CO-AL- having 1 to 10 carbon atoms, more preferably -AL- or -O-AL- having 1 to 10 carbon atoms, and most preferably -AL- or -O-AL- having 1 to 5 carbon atoms. AL represents an alkylene group.

[0065] L ２ represents a single bond or a divalent linking group. ２ Examples of the group include an alkylene group, —O—, —S—, —CO—, and —SO ２ -, -NRa- (wherein Ra is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), an alkenylene group, a divalent linking group having 1 to 10 carbon atoms formed in combination with an alkynylene group or an arylene group, a single bond, -O-, -O-CO-, -CO-O-, -O-AL-O-, -O-AL-O-CO-, -O-AL-CO-O-, -CO-O-AL-O-, -CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO-, -O-CO-AL-CO-O-, and the like. AL represents an alkylene group. L2 is preferably a single bond, -AL-, -O-AL-, or -NRa-AL-O- having 1 to 10 carbon atoms, more preferably a single bond, -AL-, -O-AL-, or -NRa-AL-O- having 1 to 5 carbon atoms, and most preferably a single bond, or -O-AL- or -NRa-AL-O- having 1 to 5 carbon atoms.

[0066] Y １ represents a divalent linking group having a 5-membered or 6-membered ring as a partial structure. １Examples of the aromatic ring include a cyclohexyl ring, an aromatic ring, a heterocyclic ring, etc. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring, with a benzene ring, a biphenyl ring, and a naphthalene ring being particularly preferred. The heteroatom constituting the heterocycle is preferably a nitrogen atom, an oxygen atom, or a sulfur atom, and examples thereof include a furan ring, a thiophene ring, a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an imidazoline ring, an imidazolidine ring, a pyrazole ring, a pyrazoline ring, a pyrazolidine ring, a triazole ring, a furazan ring, a tetrazole ring, a pyran ring, a dioxane ring, a dithiane ring, a thiine ring, a pyridine ring, a piperidine ring, an oxazine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring, and a triazine ring. The heterocycle is preferably a 6-membered ring. Y １ The divalent linking group having a 5- or 6-membered ring as a partial structure represented by the following formula may further have a substituent (for example, the above-mentioned substituent W).

[0067] Y １ The divalent linking group represented by the formula (I) is preferably a divalent linking group having two or more five-membered or six-membered rings, and more preferably has a structure in which two or more rings are linked by a linking group. Examples of the linking group include L １ and L ２ Examples of the linking group include -C≡C-, -CH=CH-, -CH=N-, -N=CH-, and -N=N-.

[0068] Z represents a divalent linking group having an alkylene group having 2 to 20 carbon atoms as a partial structure and formed by combining -O-, -S-, -CO-, or -SO2-, and the alkylene group may have a substituent. Examples of the divalent linking group include an alkyleneoxy group and a polyalkyleneoxy group. The alkylene group represented by Z preferably has 2 to 16 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms.

[0069] P １ and P２ each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated group. Examples of the monovalent substituent having a polymerizable ethylenically unsaturated group include the following formulae (M-1) to (M-8). That is, the monovalent substituent having a polymerizable ethylenically unsaturated group may be a substituent consisting only of an ethenyl group, as in (M-8).

[0070]

[0071] In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. Among the formulas (M-1) to (M-8), (M-1), (M-2) and (M-8) are preferred, with (M-1) or (M-8) being more preferred. In particular, P １ As for P, (M-1) is preferable. ２ As the ring A, (M-1) or (M-8) is preferable, and in the compound in which the ring A is a quaternary imidazolium ion, P ２ is preferably (M-8) or (M-1), and in compounds where ring A is a quaternary pyridinium ion, P2 is preferably (M-1).

[0072] Examples of the onium compound represented by formula (B1) include the onium salts described in paragraphs

[0052] to

[0058] of JP-A No. 2012-208397, the onium salts described in paragraphs

[0024] to

[0055] of JP-A No. 2008-026730, and the onium salts described in JP-A No. 2002-37777.

[0073] In the present invention, the aligning agent is preferably a boronic acid compound represented by the following formula (B2), because this increases the degree of alignment of the optically absorptive anisotropic layer that is formed.

[0074] In (B2) above, R １ and R ２ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ３ represents a substituent.

[0075] R１ and R ２ Examples of the aliphatic hydrocarbon group represented by one embodiment of the formula include substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms (e.g., methyl, ethyl, isopropyl, etc.), substituted or unsubstituted cyclic alkyl groups having 3 to 20 carbon atoms (e.g., cyclohexyl, etc.), and alkenyl groups having 2 to 20 carbon atoms (e.g., vinyl, etc.). １ and R ２ Examples of the aryl group represented by one embodiment of R include a substituted or unsubstituted phenyl group having 6 to 20 carbon atoms (for example, a phenyl group, a tolyl group, etc.), and a substituted or unsubstituted naphthyl group having 10 to 20 carbon atoms. １ and R ２ Examples of the heterocyclic group represented by one embodiment of R include substituted or unsubstituted 5- or 6-membered ring groups containing at least one heteroatom (e.g., nitrogen atom, oxygen atom, sulfur atom, etc.), and specific examples include a pyridyl group, an imidazolyl group, a furyl group, a piperidyl group, and a morpholino group. １ and R ２ may be linked together to form a ring, for example, R １ and R ２ The isopropyl groups may be linked to form a 4,4,5,5-tetramethyl-1,3,2-dioxaborolane ring.

[0076] R １ and R ２ is preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or a ring formed by linking these groups, and more preferably a hydrogen atom.

[0077] R ３The substituent represented by is preferably a substituent containing a functional group capable of bonding to a (meth)acrylic group. Here, examples of the functional group capable of bonding to a (meth)acrylic group include a vinyl group, an acrylate group, a methacrylate group, an acrylamide group, a styryl group, a vinyl ketone group, a butadiene group, a vinyl ether group, an oxiranyl group, an aziridinyl group, and an oxetane group. Among these, a vinyl group, an acrylate group, a methacrylate group, a styryl group, an oxiranyl group, or an oxetane group is preferred, and a vinyl group, an acrylate group, an acrylamide group, or a styryl group is more preferred.

[0078] R ３is preferably a substituted or unsubstituted aliphatic hydrocarbon group, an aryl group, or a heterocyclic group having a functional group capable of bonding to a (meth)acrylic group. Examples of the aliphatic hydrocarbon group include a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, n-propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group, eicosyl group, isopropyl group, isobutyl group, sec-butyl group, tert Examples of the aryl group include substituted or unsubstituted phenyl groups having 6 to 50 carbon atoms (e.g., phenyl, tolyl, styryl, 4-benzoyloxyphenyl, 4-phenoxycarbonylphenyl, 4-biphenyl, 4-(4-octyloxybenzoyloxy)phenoxycarbonylphenyl), and substituted or unsubstituted naphthyl groups having 10 to 50 carbon atoms (e.g., unsubstituted naphthyl).Examples of heterocyclic groups include substituted or unsubstituted 5- or 6-membered ring groups containing at least one heteroatom (e.g., nitrogen atom, oxygen atom, sulfur atom, etc.), and examples thereof include pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, thiadiazole, indole, carbazole, benzofuran, dibenzofuran, thianaphthene, dibenzothiophene, indazole, benzimidazole, anthranil, benzisoxazole, benzoxazole, benzothiazole, purine, pyridine, pyridazine, pyrimidine, pyrazine, triazine, quinoline, acridine, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthyridine, phenanthroline, pteridine, morpholine, and piperidine groups.

[0079] Examples of the boronic acid compound represented by formula (B2) include the boronic acid compounds represented by general formula (I) described in paragraphs 0023 to 0032 of JP-A No. 2008-225281. Preferred examples of the compound represented by formula (B2) include the compounds exemplified below.

[0080]

[0081] When the liquid crystal composition of the present invention contains an alignment agent, the content of the alignment agent is preferably 0.2 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of the liquid crystal compound and the dichroic substance contained in the liquid crystal composition.

[0082] [Other Components] The liquid crystal composition of the present invention may contain other components in addition to the above-mentioned components, such as an adhesion improver and a plasticizer.

[0083] [Light-absorbing anisotropic film] The light-absorbing anisotropic film of the present invention is a light-absorbing anisotropic film formed using the liquid crystal composition of the present invention described above, and is preferably a light-absorbing anisotropic film obtained by fixing the alignment state of the liquid crystal composition of the present invention described above. The alignment state of the liquid crystal composition (particularly the liquid crystal compound) may be any of horizontal alignment, vertical alignment, tilt alignment, and twist alignment.

[0084] The optically absorptive anisotropic film of the present invention is preferably an optically absorptive anisotropic film obtained by fixing the liquid crystal compound contained in the liquid crystal composition of the present invention in a horizontally aligned state. Here, "horizontal alignment" refers to a state in which the major surface of the optically absorptive anisotropic film (or, when the optically absorptive anisotropic film is formed on a member such as a support or an alignment film, the surface of the member) is parallel to the long axis direction of the liquid crystal compound. Strict parallelism is not required, and in this specification, it refers to an alignment in which the angle between the long axis direction of the liquid crystal compound and the major surface of the optically absorptive anisotropic film is less than 10°. In the optically absorptive anisotropic film, the angle between the long axis direction of the liquid crystal compound and the major surface of the optically absorptive anisotropic film is preferably 0 to 5°, more preferably 0 to 3°, and even more preferably 0 to 2°.

[0085] The optically absorptive anisotropic film of the present invention is preferably an optically absorptive anisotropic film obtained by fixing the liquid crystal compound contained in the liquid crystal composition of the present invention in a vertically aligned state. That is, the angle θ between the central axis of transmittance of the optically absorptive anisotropic film and the normal direction to the surface of the optically absorptive anisotropic film is preferably 0° or more and 45° or less, more preferably 0° or more and less than 45°, even more preferably 0° or more and 35° or less, and particularly preferably 0° or more and less than 35°. Here, the central axis of transmittance of the optically absorptive anisotropic film refers to the direction that exhibits the highest transmittance when the transmittance is measured by varying the tilt angle (polar angle) and tilt direction (azimuthal angle) relative to the normal direction to the surface of the optically absorptive anisotropic film. Specifically, the Mueller matrix at a wavelength of 550 nm is measured using an AxoScan (OPMF-2, manufactured by Axometrics). More specifically, during measurement, the azimuth angle at which the central transmittance axis is tilted is first determined, and then, within a plane (a plane containing the central transmittance axis and perpendicular to the film surface) containing the normal direction of the optically absorptive anisotropic film along that azimuth angle, the Mueller matrix at a wavelength of 550 nm is measured while changing the polar angle, which is the angle with respect to the normal direction to the optically absorptive anisotropic film surface, in 1° increments from -70 to 70°, to derive the transmittance of the optically absorptive anisotropic film. The resulting direction with the highest transmittance is designated the central transmittance axis. The central transmittance axis refers to the direction of the absorption axis (the molecular long axis direction) of the dichroic material contained in the optically absorptive anisotropic film.

[0086] The thickness of the optically absorptive anisotropic film of the present invention is preferably 1.5 μm or more, more preferably 2 to 10 μm, and even more preferably 2 to 8 μm, because this results in a higher degree of orientation. Here, the thickness of the optically absorptive anisotropic film is measured by cutting the film with a microtome to prepare a cross-sectioned sample, and then observing the cross-section with a scanning electron microscope from the normal direction to the cross-section.

[0087] [Method for producing an optically absorbing anisotropic film] The method for producing an optically absorbing anisotropic film of the present invention preferably includes a coating film formation step of coating the liquid crystal composition of the present invention described above to form a coating film, a cleavage step of generating an acid in the coating film by light irradiation or heating after the coating film formation step to cleave the acid-cleavable group (X in the above formula (1)) of the dichroic material represented by the above formula (1), an alignment step of aligning the dichroic material whose acid-cleavable group has been cleaved after the cleavage step, and a curing step of fixing the orientation state of the dichroic material to obtain an optically absorbing anisotropic film after the alignment step. Hereinafter, each step of the method for producing an optically absorbing anisotropic film of the present invention will be described.

[0088] [Coating Film Forming Step] The coating film forming step is a step of forming a coating film by applying the liquid crystal composition of the present invention described above. The liquid crystal composition can be easily applied by using a liquid crystal composition containing the above-described solvent or by using a liquid crystal composition that has been converted into a molten liquid or the like by heating or the like. Examples of methods for applying the liquid crystal composition include known methods such as roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spraying, and inkjet printing.

[0089] [Cleavage Step] The cleavage step is a step of generating an acid in the coating film by light irradiation or heating, thereby cleaving the acid-cleavable group (X in the above formula (1)) of the dichroic material represented by formula (1). The method for generating an acid in the coating film is not particularly limited, but examples include a method of adding an acid to the coating film; a method of forming a coating film using a liquid crystal composition containing an acid generator, and then heating or irradiating the coating film with light to generate an acid; and the like. The acid is preferably an acid having a pKa of 3 or less, more preferably a sulfonic acid or a phosphonic acid, and more preferably a sulfonic acid. When a coating film is formed using a liquid crystal composition containing a thermal acid generator, the temperature to which the coating film is heated varies depending on the type of thermal acid generator, and is not particularly limited, but is preferably 40 to 300°C, more preferably 80 to 260°C, even more preferably 100 to 220°C, and particularly preferably 120 to 200°C. When a coating film is formed using a liquid crystal composition containing a photoacid generator, the conditions for irradiating the coating film with light are not particularly limited, and examples thereof include a method of irradiating with ultraviolet light. As a light source, a lamp that emits ultraviolet light, such as a high-pressure mercury lamp or a metal halide lamp, can be used. 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 to 1000 mJ / cm ２ is particularly preferred.

[0090] [Orientation Step] The orientation step is a step of orienting the dichroic substance contained in the coating film (after cleavage of the acid-cleavable group in the case of the coating film). The orientation step may include a drying treatment. Components such as the solvent can be removed from the coating film by the drying treatment. The drying treatment may be performed by leaving the coating film at room temperature for a predetermined time (e.g., natural drying), or by heating and / or blowing air. Here, the dichroic substance contained in the liquid crystal composition may be aligned by the above-mentioned coating film formation step or drying treatment. For example, in an embodiment in which the liquid crystal composition is prepared as a coating liquid containing a solvent, the coating film is dried to remove the solvent from the coating film, thereby obtaining a coating film having optical absorption anisotropy (i.e., an uncured optical absorption anisotropic film).

[0091] The orientation step preferably includes a heat treatment. This allows the dichroic material contained in the coating film to be oriented, and the heat-treated coating film can be suitably used as an optically absorptive anisotropic film. From the viewpoint of manufacturability, the heat treatment is preferably performed at a temperature of 10 to 250°C, more preferably 25 to 190°C. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.

[0092] The orientation step may include a cooling treatment carried out after the heating treatment. The cooling treatment is a treatment in which the coated film after heating is cooled to about room temperature (20 to 25°C). This allows the orientation of the dichroic material contained in the coated film to be fixed. The cooling method is not particularly limited and can be carried out by a known method. By the above steps, an optically absorptive anisotropic film can be obtained. In this embodiment, drying treatment and heating treatment are mentioned as methods for orienting the dichroic material contained in the coated film, but the method is not limited thereto and can be carried out by a known orientation treatment.

[0093] [Curing Step] The curing step is a step of fixing the alignment state of the dichroic material after the alignment step, thereby obtaining an optically absorptive anisotropic film. The curing step is carried out, for example, by heating and / or light irradiation (exposure). Among these, the curing step is preferably carried out by light irradiation. Various light sources such as infrared, visible light, or ultraviolet light can be used as the light source for curing, but ultraviolet light is preferred. Furthermore, ultraviolet light may be irradiated while heating during curing, or ultraviolet light may be irradiated through a filter that transmits only specific wavelengths. Furthermore, exposure may be carried out under a nitrogen atmosphere. When the curing of the optically absorptive anisotropic film proceeds by radical polymerization, exposure under a nitrogen atmosphere is preferred because inhibition of polymerization by oxygen is reduced.

[0094] [Optical Laminate] The optical laminate of the present invention has the optically absorptive anisotropic film of the present invention described above. The optical laminate of the present invention may also have a substrate supporting the optically absorptive anisotropic film of the present invention described above. The optical laminate of the present invention may also have a λ / 4 plate on the optically absorptive anisotropic film. The optical laminate of the present invention may also have an alignment film between the substrate and the optically absorptive anisotropic film. The optical laminate of the present invention may also have a barrier layer between the optically absorptive anisotropic film and the λ / 4 plate. Each layer constituting the optical laminate of the present invention will now be described.

[0095] [Substrate] The substrate can be selected depending on the application of the optically absorptive anisotropic film, and examples include glass and polymer films. The light transmittance of the substrate is preferably 80% or more. When a polymer film is used as the substrate, it is preferable to use an optically isotropic polymer film. Specific examples and preferred embodiments of the polymer are described in paragraph

[0013] of JP-A-2002-22942. Furthermore, even if a conventionally known polymer is prone to exhibiting birefringence, such as polycarbonate or polysulfone, it is also possible to use one in which the exhibiting property has been reduced by molecular modification as described in WO 2000 / 26705.

[0096] [Light-Absorption Anisotropic Film] The light-absorption anisotropic film has been described above, and therefore its description will be omitted.

[0097] [λ / 4 Plate] A "λ / 4 plate" is a plate having a λ / 4 function, specifically a plate having the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). For example, specific examples of a λ / 4 plate having a single-layer structure include a stretched polymer film and a retardation film having an optically anisotropic layer having a λ / 4 function on a support, and specific examples of a λ / 4 plate having a multi-layer structure include a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate. The λ / 4 plate and the optically absorptive anisotropic film may be provided in contact with each other, or another layer may be provided between the λ / 4 plate and the optically absorptive anisotropic film. Examples of such layers include an adhesive layer or bonding layer for ensuring adhesion, and a barrier layer.

[0098] [Barrier Layer] When the optical laminate of the present invention has a barrier layer, the barrier layer is provided between the optically absorptive anisotropic film and the λ / 4 plate. When a layer other than the barrier layer (for example, an adhesive layer or a bonding layer) is provided between the optically absorptive anisotropic film and the λ / 4 plate, the barrier layer can be provided, for example, between the optically absorptive anisotropic film and the other layer. The barrier layer is also called a gas barrier layer (oxygen barrier layer), and has the function of protecting the optically absorptive anisotropic film from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers. For the barrier layer, reference can be made to, for example, paragraphs

[0014] to

[0054] of JP 2014-159124 A, paragraphs

[0042] to

[0075] of JP 2017-121721 A, paragraphs

[0045] to

[0054] of JP 2017-115076 A, paragraphs

[0010] to

[0061] of JP 2012-213938 A, and paragraphs

[0021] to

[0031] of JP 2005-169994 A.

[0099] [Alignment Film] The optical laminate of the present invention may have an alignment film between the substrate and the optically absorptive anisotropic film. The alignment film may be any layer that can achieve the desired alignment state for the dichroic material contained in the liquid crystal composition of the present invention on the alignment film. The alignment film can be formed by methods such as rubbing an organic compound (preferably a polymer) onto the film surface, oblique vapor deposition of an inorganic compound, formation of a layer with microgrooves, or accumulation of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate) by the Langmuir-Blodgett method (LB film). Furthermore, alignment films that exhibit alignment function upon application of an electric field, application of a magnetic field, or light irradiation are also known. Among these, in the present invention, alignment films formed by rubbing treatment are preferred in terms of ease of control of the pretilt angle of the alignment film, and photo-alignment films formed by light irradiation are also preferred in terms of uniformity of alignment.

[0100] <Rubbing Treatment Alignment Film> Polymer materials used for the alignment film formed by rubbing treatment are described in numerous literatures, and many commercially available products are available. In the present invention, polyvinyl alcohol or polyimide, and derivatives thereof are preferably used. For details of the alignment film, see WO 2001 / 88574 A1, page 43, line 24 to page 49, line 8. The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

[0101] <Photo-alignment film> Photo-alignment materials used for alignment films formed by light irradiation are described in many documents, etc. In the present invention, for example, azo compounds described in JP-A Nos. 2006-285197, 2007-76839, 2007-138138, 2007-94071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, Japanese Patent Nos. 3883848 and 4151746, and compounds described in JP-A No. 2002-229039 are used. Preferred examples include aromatic ester compounds of the above, maleimide and / or alkenyl-substituted nadimide compounds having a photo-alignable unit described in JP-A Nos. 2002-265541 and 2002-317013, photo-crosslinkable silane derivatives described in Japanese Patent Nos. 4205195 and 4205198, and photo-crosslinkable polyimides, polyamides, or esters described in Japanese Patent Publication Nos. 2003-520878, 2004-529220, or Japanese Patent No. 4162850. Azo compounds, photo-crosslinkable polyimides, polyamides, or esters are more preferred.

[0102] A photo-alignment film formed from the above materials is irradiated with linearly polarized or non-polarized light to produce a photo-alignment film. In this specification, "linearly polarized light irradiation" and "non-polarized light irradiation" refer to operations for causing a photoreaction in the photo-alignment material. The wavelength of the light used varies depending on the photo-alignment material used, and is not particularly limited as long as it is the wavelength necessary for the photoreaction. The peak wavelength of the light used for photoirradiation is preferably 200 nm to 700 nm, and ultraviolet light with a peak wavelength of 400 nm or less is more preferred.

[0103] Examples of light sources used for light irradiation include commonly used light sources, such as lamps such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps, various lasers [e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium-cadmium lasers, and YAG (yttrium aluminum garnet) lasers], light-emitting diodes, and cathode ray tubes.

[0104] As a means for obtaining linearly polarized light, a method using a polarizing plate (e.g., an iodine polarizing plate, a dichroic dye polarizing plate, and a wire grid polarizing plate), a method using a prism element (e.g., a Glan-Thompson prism) or a reflective polarizer utilizing the Brewster angle, or a method using light emitted from a polarized laser light source can be employed. Alternatively, a filter or a wavelength conversion element may be used to selectively irradiate only light of a required wavelength.

[0105] When the light to be irradiated is linearly polarized, the light is irradiated from the top or back surface of the alignment film perpendicularly or obliquely to the surface of the alignment film. The incident angle of the light varies depending on the photo-alignment material, but is preferably 0 to 90° (perpendicular), more preferably 40 to 90°. When the light is non-polarized, the alignment film is irradiated with non-polarized light obliquely. The incident angle is preferably 10 to 80°, more preferably 20 to 60°, and even more preferably 30 to 50°. The irradiation time is preferably 1 to 60 minutes, more preferably 1 to 10 minutes.

[0106] When patterning is required, a method of irradiating light using a photomask the number of times required to form a pattern, or a method of writing a pattern by laser light scanning can be used.

[0107] [Uses] The optical laminate of the present invention can be used as a polarizing element (polarizing plate), for example, as a linear polarizing plate or a circular polarizing plate. When the laminate of the present invention does not have an optically anisotropic layer such as the λ / 4 plate, the laminate can be used as a linear polarizing plate. On the other hand, when the laminate of the present invention has the λ / 4 plate, the laminate can be used as a circular polarizing plate.

[0108] [Image Display Device] The image display device of the present invention has the above-described optically absorptive anisotropic film or the above-described laminate. The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as "EL") display panel, and a plasma display panel. Of these, a liquid crystal cell or an organic EL display panel is preferred, and a liquid crystal cell is more preferred. That is, the image display device of the present invention is preferably 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, and more preferably a liquid crystal display device.

[0109] [Liquid Crystal Display Device] A preferred example of a liquid crystal display device, which is an example of an image display device of the present invention, is one having the above-described optically absorptive anisotropic film and a liquid crystal cell. More preferably, the liquid crystal display device has the above-described laminate (excluding a λ / 4 plate) and a liquid crystal cell. In the present invention, of the optically absorptive anisotropic films (laminates) provided on both sides of the liquid crystal cell, it is preferable to use the optically absorptive anisotropic film (laminate) of the present invention as the front-side polarizing element, and it is even more preferable to use the optically absorptive anisotropic film (laminate) of the present invention as the front-side and rear-side polarizing elements. The liquid crystal cell constituting the liquid crystal display device will be described in detail below.

[0110] <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 (Opticaly Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. In a TN mode liquid crystal cell, when no voltage is applied, rod-shaped liquid crystal molecules are aligned substantially horizontally and further twisted at an angle of 60 to 120°. TN mode liquid crystal cells are most commonly used as color TFT (Thin Film Transistor) liquid crystal displays, and are described in numerous literature. In a VA mode liquid crystal cell, 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 JP-A-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). The liquid crystal cell may be any of a PVA (Patterned Vertical Alignment) type, an optical alignment type, and a PSA (Polymer-Sustained Alignment) type. Details of these modes are described in Japanese Patent Application Laid-Open No. 2006-215326 and Japanese National Publication of International Patent Application No. 2008-538819. In an IPS mode liquid crystal cell, 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 the IPS mode, a black display is achieved 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.

[0111] [Organic EL Display Device] An organic EL display device, which is an example of the image display device of the present invention, preferably has, from the viewing side, a light-absorbing anisotropic film, a λ / 4 plate, and an organic EL display panel, in this order. More preferably, it has, from the viewing side, the above-mentioned laminate having a λ / 4 plate and an organic EL display panel, in this order. In this case, the laminate is arranged in the following order from the viewing side: a substrate, an optional alignment film, a light-absorbing anisotropic film, an optional barrier layer, and a λ / 4 plate. The organic EL display panel is a display panel constructed using organic EL elements in which an organic light-emitting layer (organic electroluminescence layer) is sandwiched between electrodes (cathode and anode). The configuration of the organic EL display panel is not particularly limited, and any known configuration may be used.

[0112] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, and treatment procedures 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.

[0113] [Synthesis Example] [Synthesis of Dichroic Material B-1] Dichroic material B-1 represented by the following formula B-1 was synthesized according to the following scheme: In the following scheme, Ac represents an acetyl group.

[0114] Specifically, paraacetanilide (10 g) was dissolved in water (300 mL) and 12 mol / L (liter) hydrochloric acid (17 mL) and cooled in an ice bath. Sodium nitrite (3.3 g) was added and the mixture was stirred for 30 minutes. Further, amidosulfuric acid (0.5 g) was added, followed by m-toluidine (5.1 g) and stirring at room temperature for 1 hour. After stirring, the mixture was neutralized with hydrochloric acid, and the resulting solid was collected by suction filtration to obtain compound B-1a (6.4 g) represented by the above formula B-1a. Next, compound B-1a (6.4 g) was dissolved in methanol (50 mL), water (20 mL), and hydrochloric acid (10 mL), heated at 80°C for 8 hours, cooled to room temperature, and the resulting solid was collected by suction filtration to obtain compound B-1b (4.0 g) represented by the above formula B-1b. Next, compound B-1b (3.5 g) was dissolved in water (35 mL) and hydrochloric acid (2.0 mL) and cooled in an ice bath. Sodium nitrite (1.9 g) was added and the mixture was stirred for 120 minutes. Further, amidosulfuric acid (0.5 g) was added, and a solution of m-chlorophenol (4.5 g), 48% aqueous potassium hydroxide solution (4.0 g), and water (24 mL) was added and stirred at room temperature for 1 hour. After stirring, the mixture was neutralized with hydrochloric acid, and the resulting solid was collected by suction filtration to obtain compound B-1c (4.0 g) represented by the above formula B-1c. Separately, methanol (100 mL) and (+)-camphorsulfonic acid (0.1 g) were added to 6-chloro-2-hexanone (25 g), and trimethyl orthoformate (20 g) was added dropwise over 10 minutes while maintaining the temperature in a water bath, followed by stirring for 30 minutes. The reaction was terminated by adding 10 mL of saturated aqueous sodium bicarbonate, and 200 mL of hexane and 200 mL of water were added to perform a liquid separation operation. The resulting organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated to obtain compound B-1d (28 g) represented by formula B-1d. Next, compound B-1c (4.0 g), compound B-1d (2.0 g), potassium carbonate (1.5 g), and potassium iodide (0.4 g) were dissolved in N,N-dimethylacetamide (DMAc) (50 mL) and stirred at 85°C for 8 hours. After stirring, hydrochloric acid (1.0 g), water (10 mL), and methanol (50 mL) were added, and the resulting solid was suction filtered to obtain dichroic substance B-1 (4.5 g).

[0115] [Synthesis of Dichroic Material B-2] Dichroic material B-2 represented by the following formula B-2 was synthesized according to the following scheme.

[0116] Specifically, compound B-1b (3.5 g) was dissolved in water (35 mL) and hydrochloric acid (2.0 mL), cooled in an ice bath, and sodium nitrite (1.9 g) was added. The mixture was stirred for 120 minutes. After adding amidosulfuric acid (0.5 g), a solution of phenol (3.5 g), 48% aqueous potassium hydroxide solution (4.0 g), and water (24 mL) was added and stirred at room temperature for 1 hour. After stirring, the mixture was neutralized with hydrochloric acid, and the resulting solid was collected by suction filtration to obtain compound B-2a (3.6 g) represented by the above formula B-2a. Next, compound B-2a (3.6 g), paraoctyloxybenzoic acid (1.0 g), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1.0 g), and 4-N,N-dimethylaminopyridine (0.4 g) were dissolved in N,N-dimethylacetamide (DMAc) (30 mL) and stirred at 50°C for 8 hours. After stirring, methanol (50 mL) was added, and the resulting solid was suction filtered and purified using a silica gel column to obtain compound B-2b (1.1 g) represented by formula B-2b above. Next, compound B-2b (1.0 g), B-1d (0.4 g), potassium carbonate (0.4 g), and potassium iodide (0.1 g) were dissolved in N,N-dimethylacetamide (DMAc) (10 mL) and stirred at 85°C for 8 hours. After stirring, hydrochloric acid (0.4 g), water (4 mL), and methanol (10 mL) were added, and the resulting solid was filtered under suction to obtain dichroic substance B-2 (1.1 g).

[0117] [Synthesis of Dichroic Material B-3] Dichroic material B-3 represented by the following formula B-3 was synthesized according to the following scheme.

[0118] Specifically, 4-nitrophenol (27.8 g), 11-bromoundecanol (44.6 g), and potassium carbonate (30.4 g) were dissolved in N,N-dimethylacetamide (DMAc) (150 mL (milliliters)) and stirred at an external temperature of 105°C for 2 hours. The temperature was lowered to room temperature, and the mixture was separated and washed with ethyl acetate and a 10% aqueous ammonium chloride solution. The organic layer was dried over magnesium sulfate and then concentrated to obtain a white solid compound B-3a represented by the above formula B-3a. Next, DMAc (150 mL) was added to this white solid compound B-3a, and the mixture was stirred in an ice bath. While maintaining the temperature of the reaction system at 15°C or below, acrylic acid chloride (18.1 g) was added dropwise, and after the dropwise addition, the mixture was stirred at room temperature for 1 hour. Thereafter, ethyl acetate and a 10% aqueous ammonium chloride solution were added, and the mixture was separated and washed. The mixture was dried over magnesium sulfate and then concentrated to obtain a yellow solid B-3b represented by the above formula B-3b. Separately, Fe powder (89.4 g, 1.6 mol), ammonium chloride (8.9 g, 166 mmol), 2-propanol (210 mL), and pure water (88 mL) were mixed and refluxed at an external temperature of 105°C. Yellow solid B-3b dissolved in 2-propanol (88 mL) under heating was added dropwise to the refluxed system. After the dropwise addition was completed, the mixture was allowed to react for 30 minutes under reflux. After cooling to room temperature, the iron powder was removed by filtration through Celite. Ethyl acetate and water were added to the filtrate, and the organic layer was washed three times with water. The organic layer was dried over sodium sulfate and then concentrated. Purification using a column was performed to obtain 8.0 g of compound B-3c represented by the above formula B-3c. Separately, 2-aminothiophene was synthesized from 2-nitrothiophene according to a method described in a literature article (Journal of Medicinal Chemistry, 2005, Vol. 48, p. 5794). Compound B-3c (5.5 g) obtained above was added to a mixed solution of hydrochloric acid (15 mL), pure water (30 mL), and tetrahydrofuran (THF) (30 mL). The mixture was cooled to an internal temperature of 5°C or below, and sodium nitrite (1.4 g) dissolved in pure water (9 mL) was added dropwise. The mixture was stirred at an internal temperature of 5°C or below for 1 hour to prepare a diazonium solution. Next, 2-aminothiophene hydrochloride (2.4 g) was dissolved in pure water (12 mL) and hydrochloric acid (6 mL), and the diazonium solution prepared above was added dropwise at an internal temperature of 0°C. The reaction mixture was allowed to warm to room temperature and stirred for 2 hours.The precipitated solid was filtered off and dried to obtain 6.1 g of a reddish-orange solid B-3d represented by the above formula B-3d. The reddish-orange solid B-3d (5.6 g) obtained above was suspended and dissolved in acetic acid (100 mL), and sodium thiocyanate (1.5 g) was added at room temperature. The mixture was cooled with water and bromine (2.0 g, 24.8 mmol) was added dropwise while maintaining the internal temperature at 20°C or below. After stirring at room temperature for 2 hours, pure water (100 mL) was added, and the obtained solid was filtered off and dried to obtain 5.5 g of a black solid B-3e represented by the above formula B-3e. Levulinic acid (10 g), 2-(N-methylanilino)ethanol (8.0 g), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (6.0 g), and 4-N,N-dimethylaminopyridine (1.0 g) were dissolved in N,N-dimethylacetamide (DMAc) (30 mL) and stirred at 50°C for 2 hours. 10 mL of methanol was added to terminate the reaction, and 50 mL of ethyl acetate and 50 mL of water were added and the mixture was separated. The resulting organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated to obtain compound B-3g (15 g) represented by formula B-3g above. The black solid B-3e (4.7 g) obtained above was added to hydrochloric acid (6 mL) and acetic acid (6 mL), and an aqueous solution (5 mL) of sodium nitrite (0.72 g) was added dropwise at 0°C or below under ice-cooling. After stirring for 1 hour, amidosulfuric acid (0.52 mg) was added to obtain a diazonium solution. A 10 mL methanol solution of compound B-3g (2.8 g) was added dropwise to the diazonium solution while maintaining the temperature below 0°C. After warming to room temperature and stirring for 1 hour, pure water (30 mL) was added, and the resulting solid was filtered to obtain compound B-3f, a black-purple solid represented by the above formula B-3f. Methanol (10 mL), tetrahydrofuran (50 mL), and (+)-camphorsulfonic acid (0.05 g) were added to the resulting compound B-3f (2.5 g), and trimethyl orthoformate (1.0 g) was added dropwise over 10 minutes while maintaining the temperature in a water bath, followed by stirring for 120 minutes. 5 mL of saturated aqueous sodium bicarbonate was added to quench the reaction, and 20 mL of water and 30 mL of methanol were added. The resulting solid was suction filtered to obtain dichroic substance B-3 (2.4 g).

[0119] [Synthesis of Dichroic Material B-4] Dichroic material B-4 represented by the following formula B-4 was synthesized according to the following scheme.

[0120] Specifically, paraacetanilide (10 g) was dissolved in water (300 mL) and 12 mol / L (liter) hydrochloric acid (17 mL) and cooled in an ice bath. Sodium nitrite (3.3 g) was added and the mixture was stirred for 30 minutes. After adding amidosulfuric acid (0.5 g), a solution of phenol (4.0 g), 48% aqueous potassium hydroxide solution (4.0 g), and water (24 mL) was added and stirred at room temperature for 1 hour. After stirring, the mixture was neutralized with hydrochloric acid, and the resulting solid was collected by suction filtration to obtain compound B-4a (12 g) represented by the above formula B-4a. Next, compound B-4a (40 g) was suspended in methanol (700 mL), water (240 mL), and hydrochloric acid (46 g). The mixture was heated at 85°C for 8 hours, cooled to room temperature, sodium nitrite (11.9 g) was added, and the mixture was stirred for 30 minutes. After further addition of amidosulfuric acid (1.0 g), a solution of N,N-dimethylaniline (70 g), acetic acid (4.7 g), and methanol (320 mL) was added and stirred at room temperature for 1 hour. The resulting solid was collected by suction filtration to obtain compound B-4b (48 g) represented by formula B-4b above. Next, compound B-4b (5.0 g), compound B-1d (3.0 g), potassium carbonate (2.0 g), and potassium iodide (0.4 g) were dissolved in N,N-dimethylacetamide (DMAc) (20 mL) and stirred at 85°C for 8 hours. After stirring, hydrochloric acid (1.0 g), water (9 mL), and methanol (20 mL) were added, and the resulting solid was suction filtered to obtain dichroic substance B-4 (5.6 g).

[0121] [Synthesis of Dichroic Material B-5] Dichroic material B-5 represented by the following formula B-5 was synthesized according to the following scheme.

[0122] Specifically, ethylene glycol (100 mL) and (+)-camphorsulfonic acid (0.1 g) were first added to 6-chloro-2-hexanone (25 g). Trimethyl orthoformate (20 g) was added dropwise over 10 minutes while maintaining the temperature in a water bath, and the mixture was stirred for 30 minutes. 10 mL of saturated aqueous sodium bicarbonate was added to terminate the reaction, and 200 mL of hexane and 200 mL of water were added to separate the mixture. The resulting organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated to obtain compound B-5a (28 g) represented by formula B-5a. Next, compound B-2a (3.6 g), compound B-5a (2.0 g), potassium carbonate (1.0 g), and potassium iodide (0.3 g) were dissolved in N,N-dimethylacetamide (DMAc) (30 mL) and stirred at 85°C for 8 hours. After stirring, hydrochloric acid (1.0 g), water (8 mL), and methanol (30 mL) were added, and the resulting solid was filtered under suction to obtain dichroic substance B-5 (4.2 g).

[0123] [Synthesis of Dichroic Substances B-6 to B-14] Dichroic substances B-6 to B-14, respectively represented by the following formulae B-6 to B-14, were synthesized in the same manner as dichroic substances B-1 to B-5, except for the side chain structure.

[0124] [Synthesis of dichroic substances HB-1 to HB-3] Dichroic substances HB-1 to HB-3, respectively, represented by the following formulae HB-1 to HB-3, were synthesized in the same manner as dichroic substances B-1 to B-5, except for the side chain structure.

[0125] Example 1 An optical laminate of Example 1 was produced as follows.

[0126] [Preparation of Cellulose Acylate Film 1] Cellulose acylate film 1 was prepared as follows.

[0127] <Preparation of Core Layer Cellulose Acylate Dope> The following composition was charged into a mixing tank and stirred to dissolve each component, thereby preparing a cellulose acetate solution to be used as the core layer cellulose acylate dope. -------------------------------- Core Layer Cellulose Acylate Dope------------------------------------------------ - 100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.88 - 12 parts by mass of polyester compound B described in the examples of JP 2015-227955 A - 2 parts by mass of compound F below - 430 parts by mass of methylene chloride (first solvent) - 64 parts by mass of methanol (second solvent)------------------------------------------------

[0128] Compound F

[0129] <Preparation of Outer Layer Cellulose Acylate Dope> 10 parts by weight of the following matting agent solution was added to 90 parts by weight of the above core layer cellulose acylate dope to prepare a cellulose acetate solution to be used as the outer layer cellulose acylate dope.

[0130] Matting agent solution - Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass Methylene chloride (first solvent) 76 parts by mass Methanol (second solvent) 11 parts by mass The above-mentioned cellulose acylate dope for the core layer 1 part by mass

[0131] <Preparation of Cellulose Acylate Film 1> The core layer cellulose acylate dope and the outer layer cellulose acylate dope were filtered through a filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm. The core layer cellulose acylate dope and the outer layer cellulose acylate dope on both sides were simultaneously cast onto a drum at 20°C through a casting nozzle (band caster). The film was then peeled off while still containing approximately 20% solvent by weight. Both ends of the film in the width direction were fixed with tenter clips, and the film was stretched transversely at a stretch ratio of 1.1 times while being dried. The film was then transported between the rolls of a heat treatment device and further dried to produce an optical film with a thickness of 40 μm, designated as Cellulose Acylate Film 1. The in-plane retardation of the resulting Cellulose Acylate Film 1 was 0 nm.

[0132] [Preparation of Optical Laminate] An optical laminate including the cellulose acylate film 1, the photo-alignment layer PA1, the light absorption anisotropic film P1, and the oxygen barrier layer B1, arranged adjacently in this order, was prepared as follows.

[0133] <Preparation of TAC Film with Photo-Alignment Layer> An alignment layer-forming coating solution PA1 having the following composition was continuously applied onto the cellulose acylate film 1 using a wire bar. The support on which the coating film was formed was dried with hot air at 140°C for 120 seconds, and then the coating film was irradiated with polarized ultraviolet light (10 mJ / cm ２ , using an ultra-high pressure mercury lamp) to form a photo-alignment layer PA1, thereby obtaining a TAC film with a photo-alignment layer.

[0134] -------------------------------------------------- Coating liquid PA1 for forming alignment layer -------------------------------------------------- Polymer A1 (shown below) 100.00 parts by mass Acid generator San-Aid SI-B3A 12.00 parts by mass DIPEA (N,N-diisopropylethylamine) 0.6 parts by mass Methyl ethyl ketone 665.00 parts by mass Butyl acetate 166.00 parts by mass --------------------------------------------------

[0135] Polymer A1

[0136] San-Aid SI-B3A

[0137] DIPEA

[0138] <Formation of Optically Absorbent Anisotropic Film P1> A liquid crystal composition P1 having the following composition was continuously applied onto the photo-alignment layer PA1 of the obtained TAC film with a photo-alignment layer using a wire bar to form a coating layer P1 (coating film formation process). The coating layer P1 was then heated at 140°C for 30 seconds and cooled to room temperature (23°C) (cleavage process). It was then heated at 80°C for 60 seconds and cooled again to room temperature (alignment process). Thereafter, an LED (Light Emitting Diode) lamp (center wavelength 365 nm) was used to illuminate the coating layer P1 at an illuminance of 200 mW / cm. ２ The optically absorptive anisotropic film P1 was formed on the photo-alignment layer PA1 by irradiating the film for 2 seconds under the irradiation condition of (a) and (b) (cure step). The optically absorptive anisotropic film P1 had a thickness of 2.0 μm. 0.054 parts by mass of polymerization initiator I1 (IRGACUREOXE-02, manufactured by BASF) 0.054 parts by mass of tetrahydrofuran 46.000 parts by mass of cyclohexane 47.000 parts by mass ――――――――――――――――――――――――――――――

[0139] Polymerizable boronic acid compound B1

[0140] Polymer liquid crystal compound L1

[0141] Low molecular liquid crystal compound LM1

[0142] Dichroic substance Y1 (dichroic substance B-1)

[0143] Dichroic substance M1

[0144] Dichroic substance C1

[0145] Surfactant F1

[0146] <Formation of oxygen barrier layer B1> Composition B1 for forming an oxygen barrier layer having the following composition was continuously applied onto the formed optically absorptive anisotropic film P1 using a wire bar. The composition was then dried with hot air at 100°C for 2 minutes to form a 1.1 μm thick polyvinyl alcohol (PVA) alignment layer (oxygen barrier layer B1) on the optically absorptive anisotropic film P1. ------------------------------------------------ Composition B1 for forming an oxygen barrier layer ------------------------------------------------ 3.80 parts by mass of modified polyvinyl alcohol shown below 0.20 parts by mass of initiator Irgcure 2959 Water 70 parts by mass Methanol 30 parts by mass

[0147] Modified Polyvinyl Alcohol

[0148] In this way, an optical laminate of Example 1 was obtained, which was provided with the cellulose acylate film 1, the photo-alignment layer PA1, the light absorption anisotropic film P1, and the oxygen barrier layer B1 adjacent to each other in this order.

[0149] [Examples 2 to 14 and Comparative Examples 1 to 3] Optical laminates were produced in the same manner as in Example 1, except that the dichroic material shown in Table 1 below was used instead of dichroic material Y1 (dichroic material B-1).

[0150] [Evaluation] The following evaluations were carried out using each of the prepared optical laminates. The optically absorptive anisotropic films contained in the laminates of each Example were evaluated for the degree of orientation described below, and it was found that the polymer liquid crystal compound and the dichroic material were horizontally aligned in all of the optically absorptive anisotropic films contained in the laminates of each Example.

[0151] [Orientation Degree] With a linear polarizer inserted on the light source side of an optical microscope (Nikon Corporation, product name "ECLIPSE E600 POL"), each optical laminate of the Examples and Comparative Examples was set on a sample stage, and the absorbance of the optically absorptive anisotropic film in the wavelength range of 380 nm to 780 nm was measured at 1 nm intervals using a multichannel spectrometer (Ocean Optics, product name "QE65000"), and the orientation degree in the wavelength range of 400 nm to 700 nm was calculated using the following formula. Based on the obtained orientation degree, the orientation degree was evaluated according to the following evaluation criteria: Orientation Degree: S = ((Az0 / Ay0) - 1) / ((Az0 / Ay0) + 2) In the above formula, "Az0" represents the absorbance for polarized light in the absorption axis direction of the optically absorptive anisotropic film, and "Ay0" represents the absorbance for polarized light in the transmission axis direction of the optically absorptive anisotropic film. AA: Degree of orientation is 0.95 or more A: Degree of orientation is 0.93 or more and less than 0.95 B: Degree of orientation is 0.90 or more and less than 0.83 C: Degree of orientation is less than 0.90

[0152] [Solubility] The liquid crystal compositions used in Examples 1 to 14 and Comparative Examples 1 to 3 were pressure filtered (Merck Millipore, 0.45 μm filter), and the filtrates and coating solutions were subjected to HPLC analysis (system: Shimadzu Corporation, column: Tosoh, TSKgel ODS-100Z 4.6 mm ID×15 cm 5 μm) to calculate the solubilities of dichroic substances B-1 to B-14 and HB-1 to HB-3. Solubility = concentration of dichroic substance in filtrate / concentration of dichroic substance in composition. The solubility was calculated using a calibration curve prepared by preparing dichroic substance solutions at concentrations of 10 mg / 10 mL, 1.0 mg / 10 mL, 0.10 mg / 10 mL, and 0.010 mg / 10 mL and measuring each solution by HPLC. The results were evaluated according to the following criteria. <Evaluation criteria> A: Solubility is 0.95 or more B: Solubility is 0.50 or more and less than 0.95 C: Solubility is less than 0.50

[0153]

[0154] The results shown in Table 1 above indicate that when dichroic substances HB-1 to HB-3, which do not fall under the category of dichroic substances represented by formula (1), are used, the solubility of the liquid crystal composition is poor when the degree of alignment of the optically absorptive anisotropic film is high, and the solubility of the liquid crystal composition is good when the degree of alignment of the optically absorptive anisotropic film is low (Comparative Examples 1 to 3). In contrast, when a dichroic substance represented by formula (1) is used, the solubility of the liquid crystal composition is excellent and the degree of alignment of the optically absorptive anisotropic film is also high (Examples 1 to 14). In particular, comparison of Examples 1 to 4 indicates that when n in formula (1) is an integer of 2 or more, the degree of alignment of the optically absorptive anisotropic film is higher. Furthermore, comparison of Example 10 with other Examples indicates that when X in formula (1) is an acid-cleavable group represented by any of formulas (A1) to (A5), the degree of alignment of the prepared optically absorptive anisotropic film is higher. Furthermore, comparison of Example 5 with other Examples indicates that when two R Ａ２ and each independently represent a linear or branched monovalent aliphatic hydrocarbon group, the solubility of the liquid crystal composition is improved. Ａ２It was found that when the molecular weight of the polymer is 300 or less, the degree of orientation of the optically absorptive anisotropic film is further increased.

[0155] [Example 15] An optical laminate of Example 15 was produced as follows. When the transmittance central axis angle θ of the laminate produced in Example 15 was measured by the method described above, it was found to be 0°.

[0156] [Preparation of Optically Anisotropic Film 2] The following liquid crystal composition P2 was continuously applied using a wire bar onto an alignment film PA1 obtained by the same process as in Example 1, heated at 120°C for 60 seconds, and then cooled to room temperature (23°C). Next, it was heated at 85°C for 60 seconds and cooled again to room temperature. Thereafter, an LED lamp (center wavelength 365 nm) was used to apply the liquid crystal composition P2 to the alignment film PA1, and the applied liquid crystal composition P2 was applied to the alignment film PA1 by the same process as in Example 1. The applied liquid crystal composition P2 was continuously applied using a wire bar, heated at 120°C for 60 seconds, and then cooled to room temperature (23°C). Then, the applied liquid crystal composition P2 was heated at 85°C for 60 seconds and then cooled again to room temperature. After that, the applied liquid crystal composition P2 was applied to the alignment film PA1 by the same process as in Example 1, and the applied liquid crystal composition P2 was heated at 85°C for 60 seconds and then cooled again to room temperature. Then, the applied liquid crystal composition P2 was applied to the alignment film PA1 by the same process as in Example 1. The ... then heated at 85°C for 60 seconds and then cooled again to room temperature. Then, the applied liquid crystal composition P2 was applied to the alignment film PA1 by the same process as in Example 1. ２ The alignment film PA1 was irradiated for 2 seconds under the irradiation conditions of 1.0 to 1.25, whereby an optically anisotropic film 2 was formed on the alignment film PA1. The thickness of the optically anisotropic film 2 was 3.5 μm. -------------------------------- Liquid Crystal Composition P2 -------------------------------------------------- 6.069 parts by mass of polymer liquid crystal compound L2 described below 3.843 parts by mass of low molecular weight liquid crystal compound LM2 described below 1.305 parts by mass of the acid-cleavable dichroic material Y1 described above 0.262 parts by mass of the dichroic material M1 described above 1.829 parts by mass of the dichroic material C1 described above 0.054 parts by mass of the acid generator San-Aid SI-B3A 0.004 parts by mass of interface improver B2 described below 0.224 parts by mass of alignment agent B3 described below 0.224 parts by mass of alignment agent B4 described below 0.187 parts by mass of polymerization initiator (IRGACUREOXE-02, manufactured by BASF) Cyclopentanone 77.400 parts by mass ・Benzyl alcohol 8.600 parts by mass ----------------------------------------------------------------

[0157] Polymer liquid crystal compound L2

[0158] Low molecular liquid crystal compound LM2

[0159] Interfacial improver B2

[0160] Orientation agent B3

[0161] Orientation agent B4

[0162] A polyvinyl alcohol (PVA) alignment layer (oxygen-blocking layer B1) was formed on the obtained optically anisotropic film 2 in the same manner as in Example 1. In this manner, an optical laminate was produced which included a cellulose acylate film 1, a photo-alignment layer PA1, a light absorption anisotropic film P2, and an oxygen-blocking layer B1 adjacent to each other in this order.

[0163] The solubility of the liquid crystal composition P2 was evaluated for the optical laminate prepared in Example 15 using the same method as in Example 1, and the result was rated A. Furthermore, the degree of orientation of the optically absorptive anisotropic film in the optical laminate prepared in Example 15 was calculated using the following method and evaluated according to the following criteria, resulting in an AA rating. First, using an AxoScan OPMF-1 (manufactured by Optoscience), the polar angle relative to the normal direction of the optically absorptive anisotropic film was changed in 1° increments from -70° to 70° during measurement, and the Mueller matrix at 400 nm to 700 nm at each polar angle was measured to determine the minimum transmittance (Tmin). Next, after removing the influence of surface reflection, Tmin at the polar angle at which Tmin is highest was defined as Tm(0), and Tmin in the direction 40° polar angle larger than the polar angle at which Tmin is highest was defined as Tm(40). The absorbance (A) was calculated from the obtained Tm(0) and Tm(40) using the following formula, and A(0) and A(40) were calculated. A = -log(Tm) Here, Tm represents transmittance, and A represents absorbance. From the calculated A(0) and A(40), the degree of orientation S at wavelengths of 400 nm to 700 nm, as defined by the following formula, was calculated. Based on the obtained degree of orientation, the degree of orientation was evaluated according to the following evaluation criteria. S = (4.6 x A(40) - A(0)) / (4.6 x A(40) + 2 x A(0)) AA: degree of orientation is 0.95 or more A: degree of orientation is 0.93 or more and less than 0.95 B: degree of orientation is 0.90 or more and less than 0.83 C: degree of orientation is less than 0.90

Claims

1. A liquid crystal composition comprising a dichroic substance represented by the following formula (1) and a liquid crystal compound: In the formula (1), Y represents an n-valent dye skeleton structure, and n represents an integer of 1 or more. Ｂ represents a divalent aliphatic hydrocarbon group having one or more carbon atoms, and -CH ２ One or more of - may be substituted with -CO-, -O-, -S-, -NH- or -N(Q)-. Q represents a substituent. However, when n represents an integer of 2 or more, multiple L Ｂ may be the same or different. X represents an acid-cleavable group represented by any one of the following formulae (A1) to (A6). However, when n represents an integer of 2 or more, the multiple Xs may be the same or different. In the formulae (A1) to (A6), * represents L Ｂ R represents the bonding position with Ａ１ represents a hydrogen atom or a monovalent hydrocarbon group, and a portion of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom, and a portion of the carbon atoms may be substituted with silicon or oxygen. Ａ１ may be the same or different and may be bonded to each other to form a ring. Ａ２ represents a monovalent hydrocarbon group, in which some of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms, and some of the carbon atoms may be substituted with silicon or oxygen. Ａ２ may be the same or different and may be bonded to each other to form a ring.

2. The liquid crystal composition according to claim 1, wherein X in the formula (1) represents an acid-cleavable group represented by any one of the formulas (A1) to (A5).

3. The liquid crystal composition according to claim 2, wherein X in the formula (1) represents an acid-cleavable group represented by the formula (A2).

4. Two R in the formula (A2) Ａ２ The liquid crystal composition according to claim 3 , wherein each independently represents a linear or branched monovalent aliphatic hydrocarbon group.

5. R in the above formula (A2) Ａ２ The liquid crystal composition according to claim 4 , wherein the molecular weight of the compound is 300 or less.

6. The liquid crystal composition according to claim 1, wherein n in formula (1) represents an integer of 2 or more.

7. The liquid crystal composition according to any one of claims 1 to 6, wherein the dichroic material is represented by the following formula (2): In the formula (2), X and L Ｂ are the same as those in the formula (1). However, the two Xs may be the same or different, and the two Ls may be the same or different. Ｂ may be the same or different. n1 and n2 each independently represent an integer of 0 to 4. k represents an integer of 1 to 4. Ar １ represents an (n1+2)-valent aromatic hydrocarbon group or an (n1+2)-valent heterocyclic group, provided that when k represents an integer of 2 to 4, a plurality of Ar １ may be the same or different. ２ R represents an (n2+2)-valent aromatic hydrocarbon group or an (n2+2)-valent heterocyclic group. １ and R ２ each independently represents a substituent. However, when n1 represents an integer of 2 to 4, multiple R １ may be the same or different, and when n2 represents an integer of 2 to 4, a plurality of R ２ may be the same or different. Ｃ represents -N=N-, -N=CY-, -CY=CY-, -OCO-, -SCO- or -NHCO-, and Y represents a substituent. However, when k represents an integer of 2 or 3, a plurality of L Ｃ may be the same or different.

8. The liquid crystal composition according to any one of claims 1 to 6, wherein the content of the dichroic substance is 4 to 80% by mass based on the total mass of the solid content of the liquid crystal composition.

9. An optically absorptive anisotropic film obtained by fixing the alignment state of the liquid crystal composition according to any one of claims 1 to 6.

10. The optically absorptive anisotropic film according to claim 9, wherein the liquid crystal compound contained in the liquid crystal composition is fixed in a horizontally aligned state.

11. The optically absorptive anisotropic film according to claim 9, wherein the angle θ between the central axis of transmittance of the optically absorptive anisotropic film and the normal direction to the surface of the optically absorptive anisotropic film is from 0° to 45°.

12. A method for producing an optically absorbing anisotropic film according to claim 9, comprising: a coating film formation step of coating a liquid crystal composition according to any one of claims 1 to 6 to form a coating film; a cleavage step of generating an acid in the coating film by light irradiation or heating after the coating film formation step, thereby cleaving the acid cleavable group of the dichroic material represented by formula (1); an alignment step of orienting the dichroic material whose acid cleavable group has been cleaved after the cleavage step; and a curing step of fixing the orientation state of the dichroic material to obtain an optically absorbing anisotropic film after the alignment step.

13. An optical laminate comprising the optically absorptive anisotropic film according to claim 9.

14. An image display device comprising the optically absorptive anisotropic film according to claim 9.

Images