Compound, composition for anisotropic dye film containing said compound, anisotropic dye film and optical element

Abstract

A compound represented by formula (1) or formula (11).　X-A1-(N=N-A2)n-N=N-A3-Y … (1) (In formula (1), -A1- and -A2- each independently represent a divalent group of an optionally substituted aromatic heterocycle including one or more S atoms in which atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent, a divalent group of an optionally substituted benzoisothiazole ring, or a divalent group of an optionally substituted aromatic hydrocarbon ring, -A3- represents a divalent group of an optionally substituted aromatic hydrocarbon ring, -X represents a branched C3 or higher alkyl group, alkoxy group, or alkylsulfanyl group, -Y represents a monovalent organic group, and n represents 1, 2, or 3.　When n is 2 or 3, the multiple -A2- may be the same or different.　However, -A1- and -A2- are not both divalent groups of an optionally substituted aromatic hydrocarbon ring.)　X-A41-(N=N-A42)n-N=N-A43-Y … (11) (In formula (11), at least one -A42- is a divalent group of an optionally substituted aromatic heterocycle including one or more S atoms, -A41- and -A43- each independently represent a divalent group of an optionally substituted aromatic hydrocarbon ring, X represents a branched C3 or higher alkyl group, alkoxy group, or alkylsulfanyl group, -Y represents a monovalent organic group, and n represents 1, 2, or 3.　When n is 2 or 3, the multiple -A42 may be the same or different.)

Description

[Technical Field]

[0001] The present invention relates to a compound useful for polarizing films and the like provided in display devices such as light control devices, liquid crystal devices (LCDs), and organic electroluminescence devices (OLEDs). The present invention also relates to a composition for forming an anisotropic dye film, an anisotropic dye film, and an optical device containing the compound. [Background technology]

[0002] In LCDs, linear and circular polarizing films are used to control the optical rotation and birefringence of the display. OLEDs also use circular polarizing films to prevent reflection of external light in bright places.

[0003] Conventionally, such polarizing films include, for example, polarizing films (iodine-PVA polarizing films) made by dyeing polyvinyl alcohol (PVA) with low concentrations of iodine (Patent Document 1). However, depending on the usage environment, low-concentration iodine-PVA polarizing plates have problems such as color changes due to iodine sublimation or deterioration, and warping due to relaxation of the stretching of the PVA.

[0004] It is also known that an anisotropic dye film formed by coating a liquid crystal composition containing a dye functions as a polarizing film (Patent Document 2). However, no dichroic dye has been disclosed that has a maximum absorption in the wavelength range of 560 nm to 800 nm and that has both a sufficient dichroic ratio and solubility.

[0005] An anisotropic dye film is known that combines a dye having a benzothiazole or thienothiazole skeleton with a polymerizable liquid crystal as a dichroic dye having a maximum absorption in the wavelength range of 550 nm to 800 nm (Patent Document 3). However, the dye having a benzothiazole or thienothiazole skeleton may precipitate in an anisotropic dye film-forming composition that requires solubility.

[0006] [Patent Document 1] Japanese Patent Application Publication No. 1-105204 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-210624 [Patent Document 3] Japanese Patent Application Laid-Open No. 2016-170368

[0007] <Object of the First Invention> Polarizing films formed by coating liquid crystal compositions containing dyes are desired to have high light absorption selectivity even in thin films and to have no light leakage in the wavelength range of 350 nm to 800 nm. Therefore, it is necessary to use multiple dyes with high dichroism to adjust the composition so that it comprehensively absorbs the wavelength range of 350 nm to 800 nm. However, in this case, the dye concentration in the composition is high because multiple dyes are included. When coated under thin-film conditions, the dye concentration becomes high relative to the liquid crystal, which makes the dyes more likely to precipitate, resulting in poor coating performance.

[0008] To prevent dye precipitation, it is necessary to improve the solubility of the dye. One method for achieving this is to introduce a substituent that is highly compatible with the compounds in the composition. However, depending on the type and position of the introduced substituent, there is a risk of a decrease in the dichroic ratio due to an increase in the angle between the transition moment that determines the dye's absorption axis and the molecular long axis. Furthermore, if the substituent is too bulky, there is a risk of a decrease in the dichroic ratio due to the interference with the molecular orientation of the dye.

[0009] It is known that anisotropic dye films formed by coating an anisotropic dye film-forming composition containing a polymerizable liquid crystal compound and a dye have different dichroic ratios and maximum absorption wavelengths due to intermolecular interactions between the dye and the liquid crystal compound. In the combination of a dye and a liquid crystal compound, it is important that the dye has a molecular structure that is compatible with the liquid crystal molecules.

[0010] Under these circumstances, there is a demand for the development of dye molecules and compositions for forming anisotropic dye films that exhibit high dichroism and good coating performance when formed.

[0011] <Problem of the second invention> Iodine-PVA polarizing film dyed with low concentrations of iodine has problems such as the color changing due to the iodine sublimating or deteriorating depending on the usage environment, and warping due to relaxation of the PVA stretching.

[0012] A polarizing film formed by coating a liquid crystal composition containing a dye exhibits high light absorption selectivity even in a thin film. It is desirable for the polarizing film to have no light leakage in the wavelength range of 380 nm to 780 nm. To achieve this, it is necessary to use multiple dyes with high dichroism to adjust the film so that it comprehensively absorbs the wavelength range of 380 nm to 780 nm. However, in this case, the dye concentration in the composition is high because multiple dyes are included. When the composition is coated under thin-film conditions, the dye concentration relative to the liquid crystal becomes high, which makes the dye more likely to precipitate, resulting in poor coating performance.

[0013] One method for designing a dye with a maximum absorption in the wavelength range of 550 nm to 800 nm is to introduce a heterocycle. However, to obtain good dichroism, the introduced heterocycle must be one that can increase the linearity of the dye molecular structure. Among heterocycles, the introduction of a benzothiazole or thienothiazole skeleton tends to improve the linearity of the molecular structure and increase the dichroic ratio. However, the increased bulkiness of the molecular structure reduces solubility, raising concerns about precipitation from the anisotropic dye film-forming composition. Furthermore, depending on the type of heterocycle introduced, differences in electron distribution can cause changes in intermolecular interactions, potentially hindering alignment.

[0014] In a polarizing film formed by applying a composition containing a polymerizable liquid crystal compound and a dichroic dye, it is known that the dichroic ratio and maximum absorption wavelength of the dye vary depending on the intermolecular interaction between the dye and the liquid crystal compound. Therefore, it is important to combine a dichroic dye having a molecular structure compatible with the liquid crystal compound to be used.

[0015] Under these circumstances, there is a demand for the development of a composition for forming an anisotropic dye film, which has high dye solubility, is free from concerns about precipitation of the dye, and therefore has good coating properties, and which allows the resulting anisotropic dye film to exhibit high dichroism. Summary of the Invention

[0016] The first object of the present invention is to provide a compound that has both high dichroism and high solubility. Another object of the present invention is to provide a composition for forming an anisotropic dye film, an anisotropic dye film, and an optical element, each containing the compound.

[0017] The first invention solves the above problems by providing a compound having a specific structure. The first invention has the following aspects.

[0018] [1] A compound represented by the following formula (1) or the following formula (11): XA 1 -(N=NA 2 ) n -N=NA 3 -Y …(1) (In formula (1), -A 1 -and-A 2 each - independently represents a divalent group of an aromatic heterocycle containing one or more S atoms which may have a substituent, wherein atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other; a divalent group of a benzisothiazole ring which may have a substituent; or a divalent group of an aromatic hydrocarbon ring which may have a substituent; -A 3 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, -X is a branched alkyl group having 3 or more carbon atoms; alkoxy group or an alkylsulfanyl group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A 2 - may be the same or different. However, -A 1 -and-A2 Both - and - are not divalent groups of aromatic hydrocarbon rings which may have a substituent. XA 41 -(N=NA 42 ) n -N=NA 43 -Y …(11) (In formula (11), -A 42 at least one of - is a divalent aromatic heterocyclic group containing one or more optionally substituted S atoms, -A 41 -and-A 43 each - independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent; -X is a branched alkyl group having 3 or more carbon atoms; alkoxy group or an alkylsulfanyl group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A 42 - may be the same or different.)

[0019] [2] The compound according to [1], wherein in the formula (1), the aromatic heterocycle containing one or more S atoms, in which atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other, is a thiophene ring, a benzothiophene ring, a thiazole ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, or a benzothiazole ring.

[0020] [3] In the formula (1), -A 3 The compound according to [1] or [2], wherein - is a phenylene group which may have a substituent.

[0021] [4] In the formula (1), -A 2 The compound according to any one of [1] to [3], wherein - is a phenylene group which may have a substituent.

[0022] [5] In the formula (1), -Y is -OR x or -N(-Ry )-R x The compound according to any one of [1] to [4], wherein However, -R x and -R y each independently represents an optionally branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms, -R x and -R y may be joined together to form a ring, The alkyl group having 1 to 15 carbon atoms which may be branched and the aryl group having 5 to 14 ring-constituting atoms each may have a substituent; The alkyl group having 1 to 15 carbon atoms which may be branched, the cycloalkyl group having 5 to 14 ring atoms or -R x and -R y One or more methylene groups contained in the ring formed by combining these may be -O-, -S-, -NH-, -N(R z )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, -CCl2-, an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group, R z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0023] [6] In the formula (11), when n is 2 or 3, -A 42 The compound according to any one of [1] to [5], wherein each - independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, or a divalent group of an aromatic heterocycle which contains one or more S atoms which may have a substituent.

[0024] [7] In the formula (11), -A 42The compound according to any one of [1] to [6], wherein the aromatic heterocycle is a thiophene ring, a benzothiophene ring, a thiazole ring, an isothiazole ring, a 1,3,4-thiadiazole ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisothiazole ring, or a benzothiazole ring.

[0025] [8] In the formula (11), -A 43 The compound according to any one of [1] to [7], wherein - is a phenylene group which may have a substituent.

[0026] [9] In the formula (11), -A 41 The compound according to any one of [1] to [8], wherein - is a phenylene group which may have a substituent.

[0027]

[10] A composition for forming an anisotropic dye film, comprising the compound according to any one of [1] to [9] and a polymerizable liquid crystal compound.

[0028]

[11] A composition for forming an anisotropic dye film, comprising a compound represented by the following formula (21) and a polymerizable liquid crystal compound: XA 21 -(N=NA 22 ) n -N=NA 23 -Y …(21) (In formula (21), -A 21 -and-A 22 each - independently represents a divalent aromatic heterocyclic group containing one or more S atoms which may have a substituent, or a divalent aromatic hydrocarbon ring group which may have a substituent; -A 23 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, -X is a branched alkyl group having 3 or more carbon atoms; alkoxy group or an alkylsulfanyl group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A22 - may be the same or different. However, -A 21 -and-A 22 At least one of the groups is a divalent aromatic heterocyclic group containing one or more optionally substituted S atoms.

[0029] The second invention aims to provide a composition for forming an anisotropic dye film, which has good coating properties due to high dye solubility and no risk of precipitation of the dye or the like in the composition, and which can achieve high dichroism in the resulting anisotropic dye film, and which can achieve a sufficient dichroic ratio, particularly in the wavelength region of 550 to 800 nm. Another object of the second invention is to provide an anisotropic dye film and an optical element having excellent optical performance, particularly a sufficient dichroic ratio.

[0030] The second invention solves the above problems by using a composition for forming an anisotropic dye film, which contains a dye having a specific structure and a polymerizable liquid crystal compound. The second invention has the following aspects.

[0031]

[12] A composition for forming an anisotropic dye film, comprising a compound represented by the following formula (31) and a polymerizable liquid crystal compound: A 31 -(N=NA 32 ) n -N=NA 33 -Y …(31) (In formula (31), -A 31 represents a group represented by any one of the following formulae (a-2) to (a-7), which may have a substituent (in the following formulae (a-2) to (a-7), * represents a bond on the -N side, and S4 to S 14 represents the substitution position when a substituent is present),

[0032] [ka]

[0033] -A 32- represents a divalent group of an aromatic hydrocarbon ring which may have a substituent or a divalent group of an aromatic heterocyclic ring which may have a substituent; -A 33 - represents an optionally substituted phenylene group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A 32 - may be the same or different.)

[0034]

[13] In the formula (31), -A 32 The composition for forming an anisotropic dye film according to

[12] , wherein - is a divalent group of an aromatic hydrocarbon ring which may have a substituent.

[0035]

[14] In the formula (3), -Y is -OR x or -N(-R y )-R x The composition for forming an anisotropic dye film according to

[12] or

[13] , wherein However, -R x and -R y each independently represents an optionally branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms, -R x and -R y may be joined together to form a ring, The alkyl group having 1 to 15 carbon atoms which may be branched and the aryl group having 5 to 14 ring-constituting atoms each may have a substituent; The alkyl group having 1 to 15 carbon atoms which may be branched, the cycloalkyl group having 5 to 14 ring atoms or -R x and -R y One or more methylene groups contained in the ring formed by combining these may be -O-, -S-, -NH-, -N(R z)-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, -CCl2-, an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group, R z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0036] The first and second inventions also have the following common aspects.

[0037]

[15] The number of ring structures (r n1 ) and the number of ring structures (r n2 ) and the ratio (r n1 / r n2 ) is 0.7 to 1.5.

[0038]

[16] The composition for forming an anisotropic dye film according to any one of

[10] to

[15] , wherein the polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond.

[0039]

[17] The anisotropic dye film according to any one of

[10] to

[16] , further comprising a dye having a wavelength showing a maximum value in an absorption curve in a wavelength range of 350 nm to 800 nm that is shorter than the wavelength showing a maximum value in an absorption curve in a wavelength range of 350 nm to 800 nm of the compound represented by formula (1), formula (11), formula (21), or formula (31). formation Composition for use.

[0040]

[18] An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of

[10] to

[17] .

[0041]

[19] An optical element comprising the anisotropic dye film according to

[18] .

[0042]

[20] A method for producing an anisotropic dye film, comprising a step of applying the composition for forming an anisotropic dye film according to any one of

[10] to

[17] to a substrate. [Effects of the Invention]

[0043] The compound of the first invention has a bulky substituent and exhibits both high dichroism and solubility. The anisotropic dye film-forming composition of the first invention contains the compound of the present invention, and therefore can suppress precipitation of the compound, improve coating performance, and achieve a high dichroic ratio. The anisotropic dye film of the first invention is formed using the anisotropic dye film-forming composition of the present invention, and therefore has multiple absorption maxima, and can achieve excellent coating properties and excellent optical performance. The optical element of the first invention contains the anisotropic dye film of the present invention, and therefore has multiple absorption maxima, and can achieve excellent coating properties and excellent optical performance.

[0044] The anisotropic dye film-forming composition of the second invention has high dye solubility and no risk of precipitation of the dye in the composition, resulting in good coating properties and enabling the resulting anisotropic dye film to achieve high dichroism. Therefore, the anisotropic dye film-forming composition of the second invention can provide an anisotropic dye film with excellent optical performance and a sufficient dichroic ratio, particularly in the wavelength region of 550 to 800 nm, with high productivity.

[0045] The anisotropic dye film and optical element of the present invention can achieve excellent optical performance, particularly a sufficient dichroic ratio. DETAILED DESCRIPTION OF THE INVENTION

[0046] The present invention will be described in detail below with reference to the following embodiments. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0047] As described above, the present invention includes the first invention and the second invention. The first invention and the second invention are collectively referred to as "the present invention."

[0048] <Anisotropic dye film> The anisotropic dye film of the present invention is a dye film that has anisotropy in electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system: the thickness direction of the anisotropic dye film and any two orthogonal in-plane directions. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance. Examples of films having optical anisotropy such as absorption or refraction include polarizing films such as linear polarizing films and circular polarizing films, retardation films, and conductive anisotropic dye films. The anisotropic dye film of the present invention is preferably used as a polarizing film or a conductive anisotropic dye film, and more preferably as a polarizing film.

[0049] <Composition for forming anisotropic dye film> The composition for forming an anisotropic dye film of the present invention contains a dye and a polymerizable liquid crystal compound. The anisotropic dye film-forming composition of the present invention may be in the form of a solution, liquid crystal, or dispersion as long as it does not cause phase separation, but the anisotropic dye film-forming composition is preferably in the form of a solution from the viewpoint of ease of application to a substrate. On the other hand, the solid components remaining after removing the solvent from the anisotropic dye film-forming composition are preferably in the form of a liquid crystal phase at any temperature from the viewpoint of alignment on a substrate as described below.

[0050] In the present invention, the liquid crystal phase state specifically refers to a liquid crystal state that exhibits both liquid and crystalline properties or intermediate properties, such as a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase, as described on pages 1 to 16 of "Fundamentals and Applications of Liquid Crystals" (by Shoichi Matsumoto and Ichiro Tsunoda; 1991).

[0051] <Dye> In the present invention, a dye is a substance or compound that absorbs at least part of the wavelengths in the visible light region (350 nm to 800 nm). Examples of dyes that can be used in the present invention include dichroic dyes. A dichroic dye is a dye that has different absorbance in the long axis direction of the molecule and absorbance in the short axis direction. The dye may or may not have liquid crystallinity. Having liquid crystallinity means that the dye exhibits a liquid crystal phase at any temperature.

[0052] [Compound of the First Invention] The compound of the first invention is a novel compound represented by the following formula (1) or (11).

[0053] XA 1 -(N=NA 2 ) n -N=NA 3 -Y …(1) (In formula (1), -A 1 -and-A 2 each - independently represents a divalent group of an aromatic heterocycle containing one or more S atoms which may have a substituent, wherein atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other; a divalent group of a benzisothiazole ring which may have a substituent; or a divalent group of an aromatic hydrocarbon ring which may have a substituent; -A 3 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, -X is a branched alkyl group having 3 or more carbon atoms; alkoxy group or an alkylsulfanyl group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A 2 - may be the same or different. However, -A 1 -and-A 2 Both - and - are not divalent groups of aromatic hydrocarbon rings which may have a substituent.

[0054] XA 41 -(N=NA 42 ) n-N=NA 43 -Y …(11) (In formula (11), -A 42 at least one of - is a divalent aromatic heterocyclic group containing one or more optionally substituted S atoms, -A 41 -and-A 43 each - independently represents a divalent group of an aromatic hydrocarbon ring which may have a substituent; -X is a branched alkyl group having 3 or more carbon atoms; alkoxy group or an alkylsulfanyl group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A 42 - may be the same or different.)

[0055] Furthermore, the composition for forming an anisotropic dye film of the first invention described below contains a polymerizable liquid crystal compound and a compound represented by the following formula (21).

[0056] XA 21 -(N=NA 22 ) n -N=NA 23 -Y …(21) (In formula (21), -A 21 -and-A 22 each - independently represents a divalent aromatic heterocyclic group containing one or more S atoms which may have a substituent, or a divalent aromatic hydrocarbon ring group which may have a substituent; -A 23 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent, -X is a branched alkyl group having 3 or more carbon atoms; alkoxy group or an alkylsulfanyl group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A 22 - may be the same or different. However, -A21 -and-A 22 At least one of the groups is a divalent aromatic heterocyclic group containing one or more optionally substituted S atoms.

[0057] Hereinafter, the compound represented by formula (1) will be referred to as "compound (1)." The compound represented by formula (11) will be referred to as "compound (11)." The compound represented by formula (21) will be referred to as "compound (21)." Compounds (1), (11), and (21) will be collectively referred to as "compounds of the first invention."

[0058] (-X) -X represents a branched alkyl group (-R), an alkoxy group (-O-R), or an alkylsulfanyl group (-SR) having 3 or more carbon atoms. The number of carbon atoms in -X is preferably 3 or more and 15 or less, more preferably 3 or more and 10 or less, from the viewpoint of improving molecular alignment with the polymerizable liquid crystal compound used in the first invention.

[0059] Examples of -R include 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2,2-trimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 1,3,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 2,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 4,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,2-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,4,4-trimethylpentyl group, 2 ... trimethylpentyl group, 1,4,4-trimethylpentyl group, 3,3,4-trimethylpentyl group, 2,3,3-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,2,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 1,2,2-trimethylpentyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1-methylhexyl group, 5,5-dimethylhexyl group, 4,4-dimethylhexyl group, 3,3-dimethylhexyl group, 2,2-dimethylhexyl group, 1,5-dimethylhexyl group, 1,4-dimethylhexyl group, 3,5,5-trimethylhexyl group, 5-methylheptyl group, 6-methyloctyl group, 3-methyloctyl group, 1-methyloctyl group, and 1-methylnonyl group.

[0060] Among the above, from the viewpoint of improving the molecular orientation of the compound of the first invention, a structure having a branch on the -R terminal side is desirable, and examples thereof include 2-methylpropyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2,3,3-trimethylbutyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 4,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, and 2,4,4-trimethylpentyl group. Preferred are ethylpentyl, 3,3,4-trimethylpentyl, 2,3,3-trimethylpentyl, 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 5,5-dimethylhexyl, 4,4-dimethylhexyl, 3,3-dimethylhexyl, 3,5,5-trimethylhexyl, 5-methylheptyl, 6-methyloctyl, 3-methyloctyl, 1-methyloctyl, and 1-methylnonyl groups.

[0061] From the viewpoint of improving molecular alignment with the polymerizable liquid crystal compound used in the first invention, it is preferable that —X does not have a cycloalkyl structure. In addition, from the viewpoint of improving molecular alignment with the polymerizable liquid crystal compound used in the first invention, it is preferable that -X does not contain a polymerizable group, which will be described later. On the other hand, from the viewpoint of improving the mechanical strength of the anisotropic dye film, it is preferable that -X contains a polymerizable group, which will be described later.

[0062] (-A 1 -,-A 2 -,-A 3 -,-A 41 -,-A 42 -,-A 43 -,-A 21 -,-A 22 -,-A 23 -) In formula (1), -A 1 -and-A 2each - independently represents a divalent group of an aromatic heterocycle containing one or more S atoms which may have a substituent, wherein atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other; a divalent group of a benzisothiazole ring which may have a substituent; or a divalent group of an aromatic hydrocarbon ring which may have a substituent; -A 3 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent. However, -A 1 -and-A 2 Both - are not divalent groups of aromatic hydrocarbon rings which may have substituents.

[0063] In formula (11), -A 42 at least one of - is a divalent aromatic heterocyclic group containing one or more optionally substituted S atoms, -A 41 -and-A 43 Each - independently represents a divalent aromatic hydrocarbon ring group which may have a substituent.

[0064] In formula (21), -A 21 -and-A 22 each - independently represents a divalent aromatic heterocyclic group containing one or more S atoms which may have a substituent, or a divalent aromatic hydrocarbon ring group which may have a substituent; -A 23 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent. However, -A 21 -and-A 22 At least one of the - is a divalent aromatic heterocyclic group containing one or more S atoms which may have a substituent.

[0065] A divalent aromatic heterocyclic group containing one or more optionally substituted S atoms: The aromatic heterocyclic group of the divalent aromatic heterocyclic group containing one or more optionally substituted S atoms is a monocyclic or condensed aromatic heterocyclic group. The number of carbon atoms in the aromatic heterocyclic ring is not particularly limited, but is preferably 4 to 20.

[0066] Examples of the aromatic heterocycle include a thiophene ring, a benzothiophene ring, a thiazole ring, an isothiazole ring, a 1,3,4-thiadiazole ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisothiazole ring, and a benzothiazole ring. Among these, from the viewpoint of improving the molecular orientation of the compound of the first invention, a thiophene ring, a benzothiophene ring, a thiazole ring, an isothiazole ring, a 1,3,4-thiadiazole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisothiazole ring, and a benzothiazole ring are preferred. The absorption transition moment of the compound of the first invention tends to coincide with the long axis direction of the dye, thereby increasing the dichroic ratio. The following structures are more preferred. (In the following structures, *1 represents the bond on the -X or -N side in formula (1), and *2 represents the bond on the -N side.)

[0067] [ka]

[0068] Examples of the substituents that may be present on the divalent group of the aromatic heterocyclic ring containing one or more S atoms include those exemplified as the substituents that may be present on the divalent group of the aromatic hydrocarbon ring that may have a substituent, which will be described later. The same applies to preferred substituents. However, it is preferable that the divalent group of the aromatic heterocycle containing one or more S atoms does not have a substituent, in view of exhibiting higher molecular linearity.

[0069] A divalent aromatic hydrocarbon ring group which may have a substituent: Examples of the aromatic hydrocarbon ring of the divalent group of the aromatic hydrocarbon ring which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0070] As the divalent group of the aromatic hydrocarbon ring, a divalent group of a benzene ring (phenylene group) or a divalent group of a naphthalene ring (naphthylene group) is preferred, and a divalent group of a benzene ring (phenylene group) is more preferred, since the absorption transition moment of the compound of the first invention tends to coincide with the long axis direction of the dye, thereby increasing the dichroic ratio. In particular, a 1,4-phenylene group, a 1,4-naphthylene group, or a 2,6-naphthylene group is more preferred, a 1,4-phenylene group is even more preferred, and an unsubstituted 1,4-phenylene group is particularly preferred. This tends to coincide with the absorption transition moment of the compound of the first invention with the long axis direction of the compound, thereby increasing the dichroic ratio.

[0071] The substituents allowed for the divalent group of the aromatic hydrocarbon ring include -R A , -OH, -OR A , -OC(=O)-R A , -NH2, -NH-R A , -N(-R B )-R A , -C(=O)-R A , -C(=O)-OR A , -C(=O)-NH2, -C(=O)-NH-R A , -C(=O)-N(-R B )-R A , -SH, -SR A , trifluoromethyl group, sulfamoyl group, carboxy group, cyano group, nitro group, and halogen. A and -R B each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms. A and -R B The number of carbon atoms in the group is preferably 1 or more and 12 or less, more preferably 1 or more and 9 or less, from the viewpoint of improving molecular alignment with the polymerizable liquid crystal compound used in the first invention.

[0072] One or more methylene groups contained in the linear or branched alkyl group may be substituted with an ethereal oxygen atom, a thioethereal sulfur atom, an amine nitrogen atom (-NH-, -N(R z )-: where R zrepresents a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.) It may have a structure substituted with a carbonyl group, an ester bond, an amide bond, -CHF-, -CF2-, -CHCl- or -CCl2-, and may be substituted with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group or a glycidyloxy group.

[0073] Among these, the substituents allowed for the divalent group of the aromatic hydrocarbon ring are -R A , -OR A , a trifluoromethyl group, or a fluoro group is preferred. A Examples of the substituent include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 5,5-dimethyl-3-methylhexyl, etc. By having the above substituent, the molecular orientation of the dye of the compound of the first invention tends to be improved.

[0074] In formula (1), -A 1 -and-A 2 - each independently represents a divalent group of an aromatic heterocycle containing one or more optionally substituted S atoms, in which atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent, a divalent group of an optionally substituted benzisothiazole ring, or a divalent group of an optionally substituted aromatic hydrocarbon ring (provided that -A 1 -and-A 2 and - are not both divalent groups of an aromatic hydrocarbon ring which may have a substituent.) Here, examples of an aromatic heterocycle containing one or more S atoms which may have a substituent and in which atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other include a thiophene ring, a benzothiophene ring, a thiazole ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, and a benzothiazole ring. In particular, -A 2When - is an aromatic heterocycle containing one or more optionally substituted S atoms and atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, or a thienothiazole ring is preferred from the viewpoint of enhancing molecular linearity.

[0075] -A in formula (1) 2 -,-A 3 Preferably, each - is independently a phenylene group which may have a substituent.

[0076] In formula (11), -A 42 At least one of - is a divalent group of an aromatic heterocycle containing one or more S atoms which may have a substituent. As the aromatic heterocycle, a thiophene ring, a benzothiophene ring, a thiazole ring, an isothiazole ring, a 1,3,4-thiadiazole ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisothiazole ring, or a benzothiazole ring is preferred, a benzothiophene ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, or a benzothiazole ring is more preferred, and a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, or a thienothiazole ring is even more preferred from the viewpoint of enhancing molecular linearity.

[0077] In formula (11), when n is 2 or 3, two or three -A 42 At least one of - is a divalent aromatic heterocyclic group containing one or more optionally substituted S atoms, and the remaining - A 42 Preferably, each - is independently a divalent group of an aromatic hydrocarbon ring which may have a substituent, or a divalent group of an aromatic heterocycle containing one or more S atoms which may have a substituent.

[0078] In formula (11), -A 41 -,-A 43 Preferably, each - is independently a phenylene group which may have a substituent.

[0079] In formula (21), -A 23 - is preferably a phenylene group which may have a substituent.

[0080] In formula (21), -A 21 -,-A 22 At least one of - is a divalent group of an aromatic heterocycle containing one or more S atoms which may have a substituent, and the aromatic heterocycle is more preferably a thiophene ring, a benzothiophene ring, a thiazole ring, an isothiazole ring, a 1,3,4-thiadiazole ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisothiazole ring, or a benzothiazole ring, and further preferably a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, or a thienothiazole ring from the viewpoint of enhancing molecular linearity.

[0081] In formula (21), -A 21 -and-A 22 When - contains a divalent group of an aromatic hydrocarbon ring which may have a substituent, the group is preferably a phenylene group which may have a substituent.

[0082] (-Y) -Y represents a monovalent organic group.

[0083] The monovalent organic group in -Y is a hydrogen atom, a hydroxy group, an amino group, a cyano group, a carbamoyl group, a nitro group, a halogen atom, -R x , -OR x , -NH-R x , -N(-R y )-R x , -C(=O)-R x , -C(=O)-OR x , -C(=O)-NH-R x , -C(=O)-N(-R y )-R x , -OC(=O)-R x , -NH-C(=O)-R x , -N(-R y)-C(=O)-R x -R x and -R y each independently represents an optionally branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms. x and -R y may join together to form a ring having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms. From the viewpoint of improving molecular alignment with the polymerizable liquid crystal compound used in the first invention, it is preferable that the monovalent organic group in -Y does not have a polymerizable group as described below, whereas from the viewpoint of improving the mechanical strength of the anisotropic dye film, it is preferable that the monovalent organic group in -Y has a polymerizable group as described below.

[0084] An optionally branched alkyl group having 1 to 15 carbon atoms preferably has 1 to 6 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms preferably has 5 to 10 ring atoms, and an aryl group having 5 to 14 ring atoms preferably has 5 to 10 ring atoms.

[0085] The alkyl group having 1 to 15 carbon atoms, which may be branched, the cycloalkyl group having 5 to 14 ring atoms, and the aryl group having 5 to 14 ring atoms each may have a substituent. In addition, an alkyl group having 1 to 15 carbon atoms which may be branched, a cycloalkyl group having 5 to 14 atoms constituting a ring, or -R x and -R y One or more methylene groups contained in the ring formed by combining these may be -O-, -S-, -NH-, -N(R z )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, or -CCl2-, or may be a structure in which R is replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0086] -R x and -R y Examples of the substituents permitted for the optionally branched alkyl group having 1 to 15 carbon atoms in the formula (I) include -OH, -OR f , -OC(=O)-R f , -NH2, -NH-R f , -N(-R g )-R f , -C(=O)-R f , -C(=O)-OR f , -C(=O)-NH2, -C(=O)-NH-R f , -C(=O)-N(-R g )-R f , -SH, -SR f , sulfamoyl group, carboxy group, cyano group, nitro group, halogen, etc. f and -R g each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms are selected from the group consisting of -O-, -S-, -NH-, -N(R h )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, or -CCl2-, or may be a structure in which R is replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group. h represents a linear or branched alkyl group having 1 to 6 carbon atoms. Of these, -R x and -R y Examples of the substituents permitted for the optionally branched alkyl group having 1 to 15 carbon atoms in the formula (I) include -OR fare preferred, and examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, acryloyloxy, methacryloyloxy, and glycidyloxy.

[0087] -R x and -R y In the above, examples of the substituents permitted for the cycloalkyl group or aryl group having 5 to 14 ring atoms include -R i , -OH, -OR i , -OC(=O)-R i , -NH2, -NH-R i , -N(-R j )-R i , -C(=O)-R i , -C(=O)-OR i , -C(=O)-NH2, -C(=O)-NH-R i , -C(=O)-N(-R j )-R i , -SH, -SR i , trifluoromethyl group, sulfamoyl group, carboxy group, cyano group, nitro group, and halogen. i and -R j each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

[0088] Of these, -R x and -R y In the above, examples of the substituents permitted for the cycloalkyl group or aryl group having 5 to 14 ring atoms include -R i , -OR i are preferred, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, 2-ethylhexyloxy, 5,5-dimethyl-3-methylhexyloxy, and the like.

[0089] -Rx and -R y Examples of the cycloalkane ring of a cycloalkyl group having 5 to 14 ring-constituting atoms include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetrahydronaphthalene ring, and a bicyclo[2.2.2]octane ring.

[0090] -R x and -R y The aryl group having 5 to 14 atoms constituting the ring is -A in formula (1). 1 -aromatic heterocycle in -A 2 -and-A 3 Examples of the monovalent groups of the rings exemplified as the aromatic hydrocarbon ring in - include:

[0091] -R x and -R y is an alkyl group having 1 to 15 carbon atoms which may be branched, or -R x and -R y and -R preferably combine to form a ring having 2 to 15 carbon atoms which may have a substituent. Furthermore, -R is an alkyl group having 1 to 6 carbon atoms which may have a branch, or -R x and -R y and more preferably form a ring having 2 to 10 carbon atoms; an optionally branched alkyl group having 1 to 3 carbon atoms, or -R x and -R y more preferably, they are taken together to form a ring having 2 to 6 carbon atoms; an unbranched alkyl group having 1 to 3 carbon atoms, or -R x and -R y are particularly preferably united to form a ring having 2 to 6 carbon atoms. This tends to improve the molecular orientation of the compound of the first invention.

[0092] The monovalent organic group in -Y is -R x , -OR x , -OC(=O)-Rx , -C(=O)-OR x , -N(-R y )-R x is preferred, -OR x , -OC(=O)-R x , -N(-R y )-R x is more preferred, -OR x , -N(-R y )-R x is more preferred, and -N(-R y )-R x is particularly preferred. y )-R x Specific examples of the alkyl group include dimethylamino, diethylamino, di-n-propylamino, ethylmethylamino, methylpropylamino, azetidinyl, pyrrolidinyl, piperidinyl, azepanyl, morpholinyl, piperazinyl, and thiomorpholinyl, and more preferably diethylamino, pyrrolidinyl, and piperidinyl. The above arrangement makes the absorption transition moment of the compound of the first invention coincide with the long axis direction of the compound, and therefore the dichroism tends to be good.

[0093] (n) n represents 1, 2, or 3. n is preferably 1 or 2, and more preferably 1. By being as described above, the molecular orientation of the compound of the first invention tends to be good. When n is 2 or 3, each -A 2 -, -A 42 -, -A 22 - may be the same or different.

[0094] In terms of improving the linearity of the compound of the first invention, it is preferable that -N=N- in formula (1), formula (11) and formula (21) is in a trans configuration.

[0095] (Specific Examples of the Compound of the First Invention) Specific examples of the compound of the first invention include, but are not limited to, the following compounds:

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[0100] (Absorption characteristics) In an anisotropic dye film prepared by the method described below, the compound of the first invention may have an absorption maximum (λmax1) in the wavelength range of 350 to 800 nm, preferably in the wavelength range of 50 to 800 nm, more preferably in the wavelength range of 510 to 750 nm, and even more preferably in the wavelength range of 510 to 700 nm. Having an absorption maximum (λmax1) in this wavelength range tends to enable comprehensive absorption over the wavelength range of 350 to 800 nm when combined with a dye having an absorption maximum at a shorter wavelength.

[0101] The compound of the first invention preferably has a longer wavelength absorption maximum (λmax1) in the anisotropic dye film than the absorption maximum (λmax2) measured when dissolved in a solvent. This longer wavelength shift occurs when the compound of the first invention is dispersed in a polymerizable liquid crystal compound and / or a polymer having units based on a polymerizable liquid crystal compound, and indicates strong intermolecular interactions between the compound of the first invention and the polymerizable liquid crystal compound and / or a polymer having units based on a polymerizable liquid crystal compound. The longer wavelength shift means that the difference in absorption maxima (λmax1 - λmax2) is a positive value, and this difference is preferably 10 nm or more, more preferably 20 nm or more.

[0102] (Solubility) The solubility of the compound of the first invention is not particularly limited, but the solubility in toluene is preferably 0.3 mass % or more, more preferably 0.4 mass % or more. When the solubility is above the lower limit, good coating film performance tends to be obtained.

[0103] [Compound of the second invention] The composition for forming an anisotropic dye film of the second invention contains a compound represented by the following formula (31) (hereinafter referred to as "compound (31)" or "compound of the second invention") and a polymerizable liquid crystal compound. A 31 -(N=NA 32 ) n -N=NA 33 -Y …(31)

[0104] (In formula (31), -A 31 represents a group represented by any one of the following formulae (a-2) to (a-7), which may have a substituent (in the following formulae (a-2) to (a-7), * represents a bond on the -N side, and S4 to S 14 represents the substitution position when a substituent is present), [ka] -A 32- represents a divalent group of an aromatic hydrocarbon ring which may have a substituent or a divalent group of an aromatic heterocyclic ring which may have a substituent; -A 33 - represents an optionally substituted phenylene group, -Y represents a monovalent organic group; n represents 1, 2 or 3. If n is 2 or 3, multiple -A 32 - may be the same or different.)

[0105] (-A 31 ) -A 31 is a group represented by any one of the above formulas (a-2) to (a-7), which may have a substituent. From the viewpoint of improving molecular alignment with the polymerizable liquid crystal compound, -A 31 is preferably a group represented by any one of the above formulas (a-2) to (a-3), which may have a substituent.

[0106] -A 31 The substituents that may be present in a , -OH, -OR a , -OC(=O)-R a , -NH2, -NH-R a , -N(-R b )-R a , -C(=O)-R a , -C(=O)-OR a , -C(=O)-NH2, -C(=O)-NH-R a , -C(=O)-N(-R b )-R a , -SH, -SR a , trifluoromethyl group, sulfamoyl group, carboxy group, cyano group, nitro group, halogen, etc. 31 may have only one of these substituents, or may have two or more of one or more types of substituents.

[0107] Above -R a and -R beach independently represents an optionally branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms. a and -R b The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 9. In the aryl group, it is preferably 5 to 12, more preferably 5 to 9. In the cycloalkyl group, it is preferably 5 to 12, more preferably 5 to 9. When the number of carbon atoms is within these ranges, molecular orientation with the polymerizable liquid crystal compound tends to be good.

[0108] One or more methylene groups contained in the optionally branched alkyl group having 1 to 15 carbon atoms or the cycloalkyl group having 5 to 14 ring-constituting atoms are selected from the group consisting of -O-, -S-, -NH-, -N(R c )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, or -CCl2-, or may be a structure in which R is replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group. c represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0109] Of these, -A 31 The substituents that may be present in a , -OR a , -SR a , a trifluoromethyl group, a fluoro group, or a cyano group is preferred. a As the substituent, n-methyl, n-ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and 5,5-dimethyl-3-methylhexyl are more preferable. By having the above substituent, molecular alignment with the polymerizable liquid crystal compound tends to be improved.

[0110] -A 31The substitution position of the substituent is not particularly limited, but in particular, S4 is preferred in formula (a-2). In formula (a-3), S5 or S6 is preferred, and if the substituent is singular, S6 is more preferred. In formula (a-4), S7, S8 or S9 is preferred, and S8 is more preferred. In formula (a-5), S 10 or S 11 In formula (a-6), S 12 or S 13 is preferred, and S 13 In formula (a-7), S 14 These substitution positions tend to make the absorption transition moment of compound (31) coincide with the long axis direction of compound (31), thereby increasing the dichroic ratio.

[0111] (-A 32 -and-A 33 -) -A 32 - represents a divalent group of an aromatic hydrocarbon ring which may have a substituent or a divalent group of an aromatic heterocyclic ring which may have a substituent. Also, -A 33 - represents an optionally substituted phenylene group.

[0112] -A 32 The aromatic hydrocarbon ring in - is a monocyclic or condensed aromatic hydrocarbon ring. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 or more, and is preferably 20 or less, and more preferably 10 or less. When the number of carbon atoms is within this range, the absorption transition moment of compound (31) tends to coincide with the long axis direction of compound (31), thereby increasing the dichroic ratio.

[0113] Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0114] -A 32As the divalent group of the aromatic hydrocarbon ring, a divalent group of a benzene ring (phenylene group) or a divalent group of a naphthalene ring (naphthylene group) is preferred, since the absorption transition moment of compound (31) tends to coincide with the long axis direction of compound (31), thereby increasing the dichroic ratio. A 1,4-phenylene group, a 1,4-naphthylene group, or a 2,6-naphthylene group is more preferred, and a 1,4-phenylene group is even more preferred.

[0115] -A 32 The aromatic heterocycle in - is a monocyclic or condensed aromatic heterocycle. The number of carbon atoms in the aromatic heterocycle is preferably 4 or more, and is preferably 20 or less, and more preferably 10 or less. When the number of carbon atoms is within this range, the absorption transition moment of compound (31) tends to coincide with the long axis direction of compound (31), thereby increasing the dichroic ratio.

[0116] Examples of aromatic heterocycles include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, Examples of such rings include a furopyrrole ring, a furofuran ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, and an azulene ring.

[0117] -A 32 -A is an aromatic hydrocarbon ring or an aromatic heterocyclic ring; 33 Acceptable substituents for the phenylene group of -A include 31 The substituents are the same as those that may be possessed by -.

[0118] -A 32As -, a divalent group of an aromatic hydrocarbon ring which may have a substituent is preferable, a phenylene group which may have a substituent is more preferable, and an unsubstituted 1,4-phenylene group is even more preferable. By being as described above, the absorption transition moment of compound (31) tends to coincide with the direction of the long axis of compound (31), thereby increasing the dichroic ratio.

[0119] -A 33 As for -, a 1,4-phenylene group having no substituent is more preferable. As a result, the absorption transition moment of compound (31) tends to coincide with the long axis direction of compound (31), thereby increasing the dichroic ratio.

[0120] (-Y) -Y represents a monovalent organic group. Examples of the monovalent organic group for -Y include the same as the monovalent organic group for -Y in the above formula (1), and the preferred groups and reasons for their preference are also the same.

[0121] (n) n represents 1, 2, or 3. When n represents 2 or 3, each -A 32 - may be the same or different. n is preferably 1 or 2, and more preferably 1. When n is 1 or 2, the molecular orientation of compound (31) tends to be good.

[0122] In addition, it is preferable that —N═N— in the compound (31) is in a trans form in terms of improving the linearity of the compound (31).

[0123] (Specific example of compound (31)) Specifically, examples of compound (31) include, but are not limited to, the following compounds:

[0124] [ka]

[0125] (Absorption characteristics) The compound (31) of the second invention may have an absorption maximum (λmax1) in the wavelength range of 350 to 800 nm in an anisotropic dye film prepared by the method described below. The absorption maximum is preferably in the wavelength range of 450 to 800 nm, more preferably in the wavelength range of 480 to 750 nm, and even more preferably in the wavelength range of 510 to 700 nm. By having an absorption maximum in this range, when combined with a dye having an absorption maximum at a shorter wavelength, the compound tends to absorb the entire wavelength range of 350 to 800 nm.

[0126] The compound of the second invention preferably has a longer absorption maximum in the anisotropic dye film (λmax1) than the absorption maximum (λmax2) measured after dissolving in a solvent. This longer wavelength shift occurs when the compound of the second invention is dispersed in a polymerizable liquid crystal compound and / or a polymer having units based on a polymerizable liquid crystal compound, and indicates strong intermolecular interactions between the compound of the second invention and the polymerizable liquid crystal compound and / or a polymer having units based on a polymerizable liquid crystal compound. The longer wavelength shift means that the difference in absorption maxima (λmax1 - λmax2) is a positive value, and this difference is preferably 10 nm or more, more preferably 20 nm or more.

[0127] [Anisotropic dye film-forming composition] <Dye> The composition for forming an anisotropic dye film of the present invention contains a dye and a polymerizable liquid crystal compound, and the dye contains at least the compound of the first invention or the compound of the second invention (hereinafter, these are referred to as "the compound of the present invention"). The composition for forming an anisotropic dye film of the present invention may contain only one type of the compound of the present invention, or may contain two or more types.

[0128] <Other dyes> The anisotropic dye film-forming composition of the present invention contains the compound of the present invention as a dye, but may also contain a dye other than the compound of the present invention. Examples of the dye other than the compound of the present invention contained in the anisotropic dye film-forming composition of the present invention include azo dyes, quinone dyes (including naphthoquinone dyes, anthraquinone dyes, etc.), stilbene dyes, cyanine dyes, phthalocyanine dyes, indigo dyes, and condensed polycyclic dyes (including perylene dyes, oxazine dyes, acridine dyes, etc.).

[0129] The composition for anisotropic dye film of the present invention may contain only one type of dye other than the compound of the present invention, or may contain two or more types in any combination and ratio.

[0130] Among the dyes exemplified above, azo dyes are preferred because they can achieve high molecular alignment in the anisotropic dye film.

[0131] The azo dye refers to a dye having at least one azo group (-N=N-), and the number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less, from the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production.

[0132] Examples of azo dyes include compounds represented by the following formula (A). R 11 -E 1 -N=N-(E 2 -N=N) p -E 3 -R 12 …(A) (In formula (A), -E 1 -, -E 2 - and -E 3 each - independently represents an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted divalent heterocyclic group; p represents an integer of 0 to 4; When p is an integer of 2 or more, multiple -E 2 - may be identical or different from each other; R 11 and R 12 each independently represents a monovalent organic group.

[0133] -E 1 -, -E 2 - and -E 3 Each - independently represents an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted divalent heterocyclic group. The substitution position of the phenylene group is preferably a 1,4-phenylene group because the molecule has high linearity. The substitution position of the naphthylene group is preferably a 1,4-naphthylene group or a 2,6-naphthylene group because the molecule has high linearity.

[0134] The divalent heterocyclic group is a heterocyclic group having a ring with preferably 3 to 14 carbon atoms, more preferably 10 or less carbon atoms. Monocyclic or bicyclic heterocyclic groups are particularly preferred.

[0135] The atom other than carbon constituting the divalent heterocyclic group is at least one selected from a nitrogen atom, a sulfur atom, and an oxygen atom. When the heterocyclic group has multiple atoms other than carbon constituting the ring, these atoms may be the same or different. Specific examples of the divalent heterocyclic group include a pyridinediyl group, a quinolinediyl group, an isoquinolinediyl group, a thiazolediyl group, a benzothiazolediyl group, a thienothiazolediyl group, a thienothiophenediyl group, a benzimidazolidinonediyl group, a benzofurandiyl group, a phthalimidodiyl group, an oxazolediyl group, and a benzoxazolediyl group.

[0136] -E 1 -, -E 2 - and -E 3Examples of the substituents that the phenylene group, naphthylene group, and divalent heterocyclic group in - may optionally have include alkyl groups having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, and butoxy; fluorinated alkyl groups having 1 to 4 carbon atoms such as trifluoromethyl; cyano group; nitro group; hydroxyl group; halogen atoms; and substituted or unsubstituted amino groups such as amino, diethylamino, and pyrrolidino groups (a substituted amino group is an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or two substituted alkyl groups mutually bonded to each other). It means an amino group that bonds to form an alkanediyl group having 2 to 8 carbon atoms. An unsubstituted amino group is -NH2. Examples of alkyl groups having 1 to 4 carbon atoms include a methyl group, an ethyl group, and a butyl group. Examples of alkanediyl groups having 2 to 8 carbon atoms include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group.

[0137] Due to its high molecular linearity, -E 1 -, -E 2 - and -E 3 The phenylene group, naphthylene group, and divalent heterocyclic group in - are unsubstituted, or if substituted, are preferably substituted with a methyl group, a methoxy group, a hydroxyl group, a fluorine atom, a chlorine atom, a dimethylamino group, a pyrrolidinyl group, or a piperidinyl group.

[0138] p represents an integer of 0 to 4. From the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production, p is preferably 1 or more and 4 or less, and more preferably 3 or less.

[0139] R 11 and R 12 represent the same or different monovalent organic groups. R 11 and R 12Examples of the monovalent organic group in the formula (I) include a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, which may be branched; an alicyclic alkyl group having 1 to 15 carbon atoms; an alkoxy group having 1 to 15 carbon atoms, which may be branched, such as a methoxy group, an ethoxy group, and a butoxy group; a fluorinated alkyl group having 1 to 15 carbon atoms, which may be branched, such as a trifluoromethyl group; a cyano group; a nitro group; a hydroxyl group; a halogen atom; and substituted or unsubstituted amino groups such as an amino group, a diethylamino group, and a pyrrolidino group (a substituted amino group means an amino group having one or two alkyl groups having 1 to 15 carbon atoms, which may be branched, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 15 carbon atoms. An unsubstituted amino group is -NH2. Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, and a butyl group. Examples of the alkanediyl group having 2 to 15 carbon atoms include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, and a methyl group). ,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc.); carboxy group; optionally branched C alkyloxycarbonyl groups such as butoxycarbonyl group; alkylphenylalkenyl groups such as 2-(4-butylphenyl)ethenyl group; carbamoyl group; optionally branched C alkylphenylalkenyl groups such as butylcarbamoyl group. an alkylcarbamoyl group having 1 to 15 carbon atoms; a sulfamoyl group; an alkylsulfamoyl group having 1 to 15 carbon atoms, which may be branched, such as a butylsulfamoyl group; an acylamino group having 1 to 15 carbon atoms, which may be branched, such as a butylcarbonylamino group; an acyloxy group having 1 to 15 carbon atoms, which may be branched, such as a butylcarbonyloxy group; a sulfanyl group; an alkylsulfanyl group having 1 to 15 carbon atoms, such as a butylsulfanyl group; -R 1 and -R 2 Examples include:

[0140] R 11 and R 12Examples of the alkyl group include a hydrogen atom, a chain group, an aliphatic organic group ("aliphatic organic group" includes chain and cyclic groups), and an aliphatic organic group in which some of the carbon atoms have been replaced with nitrogen atoms and / or oxygen atoms ("aliphatic organic group in which some of the carbon atoms have been replaced with nitrogen atoms and / or oxygen atoms" includes chain and cyclic groups, and includes aliphatic organic groups in which some of the methyl groups have been replaced with hydroxyl groups, oxo groups (=O), amino groups, imino groups, etc.). In one embodiment, a hydrogen atom or a chain group is preferred, in another embodiment, a hydrogen atom or an aliphatic organic group is preferred, and in yet another embodiment, a hydrogen atom or an aliphatic organic group in which some of the carbon atoms have been replaced with nitrogen atoms and / or oxygen atoms is preferred.

[0141] Examples of the chain group include the above-mentioned alkyl group having 1 to 15 carbon atoms, which may be branched; alkoxy group having 1 to 15 carbon atoms, which may be branched; fluorinated alkyl group having 1 to 15 carbon atoms, which may be branched; substituted or unsubstituted amino group (a substituted amino group means an amino group having one or two alkyl groups having 1 to 15 carbon atoms, which may be branched. An unsubstituted amino group is -NH2); carboxy group; alkyloxycarbonyl group having 1 to 15 carbon atoms, which may be branched; carbamoyl group; alkylcarbamoyl group having 1 to 15 carbon atoms, which may be branched; sulfamoyl group; alkylsulfamoyl group having 1 to 15 carbon atoms, which may be branched; acylamino group having 1 to 15 carbon atoms, which may be branched; acyloxy group having 1 to 15 carbon atoms, which may be branched; sulfanyl group; alkylsulfanyl group having 1 to 15 carbon atoms, etc. The chain group and aliphatic organic group partially overlap.

[0142] Examples of the aliphatic organic group include the above-mentioned alkyl groups having 1 to 15 carbon atoms, which may be branched, and alicyclic alkyl groups having 1 to 15 carbon atoms.

[0143] Examples of the aliphatic organic group in which some of the carbon atoms have been replaced with nitrogen atoms and / or oxygen atoms include the above-mentioned alkoxy group having 1 to 15 carbon atoms, which may be branched; substituted or unsubstituted amino group (a substituted amino group means an amino group having one or two alkyl groups having 1 to 15 carbon atoms, which may be branched, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 15 carbon atoms. An unsubstituted amino group is -NH2. Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, and a butyl group. Examples of the diyl group include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group; a carboxy group; an alkyloxycarbonyl group having 1 to 15 carbon atoms, which may be branched; a carbamoyl group; an alkylcarbamoyl group having 1 to 15 carbon atoms, which may be branched; an acylamino group having 1 to 15 carbon atoms, which may be branched; and an acyloxy group having 1 to 15 carbon atoms, which may be branched.

[0144] Due to its high molecular linearity, R 11 and R 12 are each independently substituted with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms such as a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group; an alkoxy group having 1 to 10 carbon atoms such as a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, or an octyloxy group; a diethylamino group, a pyrrolidino group, or a piperidinyl group. 1 and -R 2 is also preferred.

[0145] The azo dye other than the compound of the present invention contained in the anisotropic dye film-forming composition of the present invention is not particularly limited, and known azo dyes can also be used.

[0146] Known azo dyes include, for example, the dyes (dichroic dyes and dichroic dyes) described in the above-mentioned Patent Document 1, Japanese Patent No. 5982762, JP-A No. 2017-025317, and JP-A No. 2014-095899.

[0147] Specific examples include the azo dyes described below, but are not limited to these.

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] The dye other than the compound of the first invention contained in the composition for forming an anisotropic dye film of the first invention is preferably a compound whose wavelength showing a maximum value in the absorption curve in the wavelength range of 350 to 800 nm is at least 5 nm different from the wavelength showing a maximum value in the absorption curve in the wavelength range of 350 to 800 nm of the compound of the first invention contained in the composition for forming an anisotropic dye film, and more preferably a compound whose wavelength showing a maximum value in the absorption curve in the wavelength range of 350 to 800 nm is at least 10 nm different from the wavelength showing a maximum value in the absorption curve in the wavelength range of 350 to 800 nm of the compound of the first invention contained in the composition for forming an anisotropic dye film.This is advantageous in that when the composition for forming an anisotropic dye film of the first invention is used to form a polarizing element such as a display, the anisotropic dye film exhibits polarization properties over a wide range of the visible light region.

[0153] The dye other than the compound of the second invention contained in the composition for forming an anisotropic dye film of the second invention is preferably a dye whose wavelength showing a maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm is shorter than the wavelength showing a maximum value in the absorption curve of the compound of the second invention in the wavelength range of 350 nm to 800 nm. Furthermore, the difference in wavelength is preferably 5 nm or more, and more preferably 10 nm or more. This allows an anisotropic dye film formed using the composition for forming an anisotropic dye film of the second invention to exhibit polarization properties over a wide range of the visible light region when used in a polarizing element such as a display.

[0154] (molecular weight of dye) The molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention (when two or more dyes are used in combination, the molecular weight of each dye) is preferably 300 or more, more preferably 350 or more, and even more preferably 380 or more, and is preferably 1500 or less, more preferably 1200 or less, and even more preferably 1000 or less. Specifically, the molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and even more preferably 380 to 1000. When the molecular weight is within the above range, appropriate molecular length and bulkiness are achieved, which tends to result in good molecular orientation of the dye.

[0155] (Pigment content) The content of the dye such as a dichroic dye in the composition for forming an anisotropic dye film of the present invention (when two or more dyes are used in combination, the total content of each dye) is, for example, preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and preferably 30 parts by mass or less, more preferably 10 parts by mass or less, relative to the solid content (100 parts by mass) of the composition for forming an anisotropic dye film. Specifically, the content of the dye (dichroic dye) in the composition for forming an anisotropic dye film is, for example, 0.01 to 30 parts by mass, preferably 0.05 to 10 parts by mass, relative to the solid content (100 parts by mass) of the composition for forming an anisotropic dye film.

[0156] When the content of the dye is within the above range, the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention tends to be polymerized without disturbing the alignment of the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention. When the content of the dye is equal to or greater than the above lower limit, sufficient light absorption and sufficient polarization performance tend to be obtained. When the content of the dye is equal to or less than the above upper limit, inhibition of the alignment of the liquid crystal molecules tends to be suppressed. Here, the solid content of the composition for anisotropic dye films corresponds to the total of all components other than the solvent in the composition for anisotropic dye films.

[0157] The composition for anisotropic dye film of the present invention may contain the compound of the present invention as a dye as an essential component, and may also contain the above-mentioned other dyes together with the compound of the present invention. When the composition for an anisotropic dye film of the present invention contains other dyes, from the viewpoint of more effectively obtaining the effects of the present invention by using the compound of the present invention, the proportion of the compound of the present invention in 100% by mass of the total amount of dyes in the composition for an anisotropic dye film of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15 to 100% by mass.

[0158] (Manufacturing method of dye) The dyes such as the compounds of the present invention contained in the composition for forming an anisotropic dye film of the present invention can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipso substitution reaction, diazo coupling reaction, and coupling reaction using a metal catalyst.

[0159] For example, the compounds of the present invention can be synthesized according to the methods described in the Examples below, or the methods described in "New Dye Chemistry" (by Yutaka Hosoda, published on December 21, 1973, by Gihodo), "General Overview of Synthetic Dyes" (by Hiroshi Horiguchi, published by Sankyo Publishing in 1968), and "Theoretical Manufacturing of Dye Chemistry" (by Yutaka Hosoda, published by Gihodo in 1957).

[0160] <Polymerizable liquid crystal compound> In the present invention, the liquid crystal compound refers to a substance that exhibits a liquid crystal state, and specifically refers to a compound that does not directly transition from crystal to liquid, but becomes liquid via an intermediate state that exhibits properties of both crystal and liquid, as described on pages 1 to 28 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000).

[0161] The polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is a liquid crystal compound having a polymerizable group, which will be described later.

[0162] In the polymerizable liquid crystal compound, the polymerizable group can be positioned at any position within the liquid crystal compound molecule, but it is preferable that the polymerizable group is substituted at the end of the liquid crystal compound molecule from the viewpoint of ease of polymerization. In a polymerizable liquid crystal compound, one or more polymerizable groups can be present in the liquid crystal compound molecule. When two or more polymerizable groups are present, it is preferable that they are present at both ends of the liquid crystal compound molecule from the viewpoint of ease of polymerization.

[0163] The polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the liquid crystal compound molecule. When the compound has a carbon-carbon triple bond, the carbon-carbon triple bond can rotate and serve as the core of the liquid crystal molecule, resulting in high molecular mobility and strong intermolecular interactions between the liquid crystal molecules and with compounds having a π-conjugated system such as dye molecules, which tends to result in high molecular orientation.

[0164] The polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is not particularly limited, and any liquid crystal compound having a polymerizable group can be used.

[0165] For example, the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention may be a compound represented by the following formula (2) (hereinafter, sometimes referred to as "polymerizable liquid crystal compound (2)").

[0166] Q 1 -R 1 -A 11 -Y1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2)

[0167] (In formula (2), -Q 1 represents a hydrogen atom or a polymerizable group, -Q 2 represents a polymerizable group, -R 1 - and -R 2 - each independently represents a chain organic group; -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (3), a divalent organic group, or a single bond: -A 12 - represents a partial structure represented by the following formula (3) or a divalent organic group: -Y 1 - and -Y 2 each - independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CHCH-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-; -A 11 -and-A 13 - is a partial structure represented by the following formula (3) or a divalent organic group: k is 1 or 2. If k is 2, two -Y 2 -A 13 - may be the same or different.)

[0168] -C y -X 2 -C≡CX 1 - ...(3) (In formula (3), -C y - represents a hydrocarbon ring group or a heterocyclic group; -X1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -C2O-, -OCH2-, -CH2S-, or -SCH2-; -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CHCH-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-.

[0169] In addition, -A 11 When - is a partial structure represented by formula (3), formula (2) may be the following formula (2A) or the following formula (2B). Q 1 -R 1 -C y -X 2 -C≡CX 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2A) Q 1 -R 1 -X 1 -C≡CX 2 -C y -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2B)

[0170] Also, -A 12 When - is a partial structure represented by formula (3), formula (2) may be the following formula (2C) or the following formula (2D). Q 1 -R 1-A 11 -Y 1 -C y -X 2 -C≡CX 1 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2C) Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡CX 2 -C y -(Y 2 -A 13 ) k -R 2 -Q 2 …(2D)

[0171] Also, -A 13 When - is a partial structure represented by formula (3), formula (2) may be the following formula (2E) or the following formula (2F). Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -C y -X 2 -C≡CX 1 ) k -R 2 -Q 2 …(2E) Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡CX 2 -C y ) k -R 2 -Q 2 …(2F)

[0172] Similarly, -A 11 -, -A12 -, and -A 13 - When two or more of the partial structures are the partial structure represented by formula (3), the orientation of each partial structure represented by formula (3) may be inverted.

[0173] As mentioned above, -A 11 -, -A 12 -, and -A 13 - is independently a partial structure represented by formula (3) or a divalent organic group, and -A 11 -and-A 13 - may be a single bond, but -A 11 -and-A 13 -, but neither of them is a single bond.

[0174] (-C y -) -C y The hydrocarbon ring group in - includes aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups. The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

[0175] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked aromatic hydrocarbon ring group more preferably has 6 to 15 carbon atoms. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0176] The linked aromatic hydrocarbon ring group is a divalent group in which multiple monocyclic or fused aromatic hydrocarbon rings are bonded by single bonds and have a bond on an atom constituting the ring. The monocyclic or fused ring preferably has 6 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The monocyclic or fused ring more preferably has 6 to 15 carbon atoms. Examples of the linked aromatic hydrocarbon ring group include a divalent group in which a first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded to a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond, and the divalent group has a first bond on an atom constituting the first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms. Specific examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

[0177] As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction acting between liquid crystal compounds, thereby improving molecular alignment. Of these, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene group). As the phenylene group, a 1,4-phenylene group is preferred. -C y When - is one of these groups, the linearity of the liquid crystal molecules increases, and the effect of improving molecular alignment tends to be obtained.

[0178] The non-aromatic hydrocarbon ring group includes an unlinked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0179] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic hydrocarbon ring group more preferably has 3 to 15 carbon atoms. Examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetrahydronaphthalene ring, and a bicyclo[2.2.2]octane ring.

[0180] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group that has an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred from the viewpoint of productivity.

[0181] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or fused non-aromatic hydrocarbon rings are bonded together with single bonds and which has a bond on an atom constituting the ring; or a divalent group in which one or more rings selected from the group consisting of monocyclic aromatic hydrocarbon rings, fused aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings, and fused non-aromatic hydrocarbon rings are bonded together with a monocyclic or fused non-aromatic hydrocarbon ring with a single bond and which has a bond on an atom constituting the ring. The number of carbon atoms in the single ring or condensed ring is preferably 3 to 20 because an appropriate core size provides good molecular orientation.

[0182] Examples of linked non-aromatic hydrocarbon ring groups include divalent groups in which a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Further examples include divalent groups in which a monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0183] Specific examples of the linking non-aromatic hydrocarbon ring group include a bis(cyclohexane)-4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.

[0184] The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group, because it optimizes the intermolecular interactions acting between liquid crystal compounds, thereby improving molecular alignment.

[0185] The non-linked non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl group), and the cyclohexanediyl group is preferably a cyclohexane-1,4-diyl group. y When - is one of these groups, the linearity of the liquid crystal molecules increases, and the effect of improving molecular alignment tends to be obtained.

[0186] -C y The heterocyclic group in - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0187] The aromatic heterocyclic group includes an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.

[0188] The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0189] Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0190] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0191] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0192] Non-aromatic heterocyclic groups include unlinked non-aromatic heterocyclic groups and linked non-aromatic heterocyclic groups.

[0193] The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0194] Examples of the non-aromatic heterocycle of a divalent group of a monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidine ring, a piperidine ring, a dihydropyridine ring, a piperazine ring, a tetrahydrothiazole ring, a tetrahydrooxazole ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, and a quinuclidine ring.

[0195] The linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0196] Linking non-aromatic heterocyclic group Examples of the divalent group include a divalent group in which a first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and a second bond on an atom constituting the second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0197] -C y The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are respectively represented by -R k , -OH, -OR k , -OC(=O)-Rk , -NH2, -NH-R k , -N(R k’ )-R k , -C(=O)-R k , -C(=O)-OR k , -C(=O)-NH2, -C(=O)-NH-R k , -C(=O)-N(R k’ )-R k , -SH, -SR k -R may be substituted with one or more groups selected from the group consisting of a trifluoromethyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, and a halogen atom. k and -R k’ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0198] -C y The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are each preferably independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and more preferably unsubstituted, in terms of having a highly linear molecular structure, facilitating association of the polymerizable liquid crystal compounds (2) with each other, and facilitating the development of a liquid crystal state.

[0199] -C y The substituents possessed by the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in - may be the same or different, and the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group may be entirely substituted, entirely unsubstituted, or partly substituted and partly unsubstituted.

[0200] -C y As -, a hydrocarbon ring group is preferred, and a phenylene group or a cyclohexanediyl group is more preferred, since it can improve the molecular alignment of the polymerizable liquid crystal compound (2). -C is preferred, since it can improve the linearity of the molecular structure of the polymerizable liquid crystal compound (2). yAs -, a 1,4-phenylene group and a cyclohexane-1,4-diyl group are more preferred, and a 1,4-phenylene group is particularly preferred.

[0201] (-X 1 -) -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CHCH-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-. Among these, -X 1 Preferred examples of - include -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -C2O-, -OCH2-, -CH2S-, and -SCH2-, which have a small π-bonding property. Among these, -C(=O)O-, -OC(=O)-, -CH2CH2-, -C2O-, and -OCH2- are more preferred, and -X 1 - is -C(=O)O- or -OC(=O)-. 1 - is preferably -CH2CH2-, -CH2O-, or -OCH2-.

[0202] (-X 2 -) -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -C2O-, -OCH2-, -CH2S-, or -SCH2-.

[0203] In order to increase the size of the core of the polymerizable liquid crystal compound (2) and the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film, a group with high linearity, -C y It is preferable to link - and -C≡C-. Specifically, -X2 The - is preferably a single bond or -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH=CH-, -C(=O)NH-, or -NHC(=O)-, which has π-bonding properties, and more preferably a single bond due to its higher linearity.

[0204] (-Q 1 and -Q 2 ) -Q 1 and -Q 2 The polymerizable group in (1) is a group having a partial structure that can be polymerized by light, heat, and / or radiation, and is a functional group or atomic group necessary to ensure the polymerization function. From the viewpoint of producing an anisotropic dye film, the polymerizable group is preferably a photopolymerizable group.

[0205] Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a vinyloxy group, an ethynyl group, an ethynyloxy group, a 1,3-butadienyl group, a 1,3-butadienyloxy group, an oxiranyl group, an oxetanyl group, a glycidyl group, a glycidyloxy group, a styryl group, and a styryloxy group. A group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an oxiranyl group, a glycidyl group, or a glycidyloxy group is preferred, an acryloyl group, a methacryloyloxy group, a methacryloylamino group, a methacryloylamino group, a glycidyl group, or a glycidyloxy group is more preferred, and an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group is even more preferred.

[0206] (-R 1 - and -R 2 -) -R 1 - and -R 2The chain organic group in - is a divalent organic group that does not contain a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, or non-aromatic heterocycle. Examples of such a chain organic group include -(alkylene group)-, -O-(alkylene group)-, -S-(alkylene group)-, -NH-(alkylene group)-, -N(alkyl group)-(alkylene group)-, -OC(=O)-(alkylene group)-, and -C(=O)O-(alkylene group)-.

[0207] The alkylene group in these chain organic groups may be a straight-chain or branched alkylene group having 1 to 25 carbon atoms. The carbon-carbon bond of the alkylene group may be partially unsaturated. One or more methylene groups contained in the alkylene group may be -O-, -S-, -NH-, -N(R m )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, or -CCl2- may be substituted. m represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0208] The alkylene group in these chain organic groups is preferably a linear alkylene group having 1 to 25 carbon atoms, in which some of the carbon atoms of the alkylene group may be unsaturated, or in which one or more methylene groups contained in the alkylene group may be replaced by the above-mentioned group, due to high molecular linearity.

[0209] The number of atoms in the main chain (meaning the longest chain portion in the chain organic group) of the chain organic group is preferably 3-25, more preferably 5-20, and even more preferably 6-20.

[0210] The chain organic group is -(CH2) r -CH2-, -O-(CH2) r -CH2-, -(O) r1 -(CH2CH2O) r2 -(CH2)r3 -, -(O) r1 -(CH2) r2 -(CH2CH2O) r3 - is preferred. In these formulas, r represents an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and even more preferably an integer of 5 to 19. In these formulas, r1, r2, and r3 each independently represent an integer, and are appropriately adjusted so that the number of atoms in the main chain of the chain organic group (meaning the longest chain portion in the chain organic group) is preferably 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

[0211] -R 1 - and -R 2 Each - is preferably independently -(alkylene group)- or -O-(alkylene group)-, more preferably -(alkylene group)- or -O-(alkylene group)-. 1 - and -R 2 The chain organic group in - is -(alkylene group)-, and in another embodiment, is -O-(alkylene group)-.

[0212] As in the formula (2B) and formula (2E), -X 1 -and-R 1 -or-X 1 -and-R 2 - is bonded; in the formula (2B), -A 13 - is a single bond, or in the formula (2E), -A 11 - is a single bond, and -R 1 -or-R 2 -ga, -Y 1 -or- Y 2 -X 1 -, -Y 1 -or- Y 2 - and directly bonded to -R 1 -or-R 2 - is preferably -(alkylene group)-.

[0213] Other than the above, -X 1 -, -Y1 -or- Y 2 -R not directly bonded to - 1 -or-R 2 - is preferably -O-(alkylene group)-.

[0214] (-A 11 -, -A 12 -, and -A 13 -(divalent organic group in -A 11 -, -A 12 -, and -A 13 The divalent organic group in - is preferably a group represented by the following formula (4).

[0215] -Q 3 - …(4) (In formula (4), Q 3 represents a hydrocarbon ring group or a heterocyclic group.

[0216] -Q 3 The hydrocarbon ring group in - includes aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups. The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

[0217] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms because the appropriate core size provides good molecular orientation. The non-linked aromatic hydrocarbon ring group more preferably has 6 to 15 carbon atoms. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0218] The linked aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or fused aromatic hydrocarbon rings are bonded by single bonds and which has a bond on an atom constituting the ring. The monocyclic or fused ring preferably has 6 to 20 carbon atoms because the appropriate core size provides good alignment. The linked aromatic hydrocarbon ring group more preferably has 6 to 15 carbon atoms. Examples of the linked aromatic hydrocarbon ring group include a divalent group in which a first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded to a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond, which has a first bond on an atom constituting the first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms. Specific examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

[0219] As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction acting between liquid crystal compounds, thereby improving molecular alignment. Of these, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene group). As the phenylene group, a 1,4-phenylene group is preferred. -Q 3 When - is one of these groups, the linearity of the liquid crystal molecules increases, and the effect of improving molecular alignment tends to be obtained.

[0220] The non-aromatic hydrocarbon ring group includes an unlinked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0221] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic hydrocarbon ring group more preferably has 3 to 15 carbon atoms. Examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetrahydronaphthalene ring, and a bicyclo[2.2.2]octane ring.

[0222] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group that has an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred from the viewpoint of productivity.

[0223] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or fused non-aromatic hydrocarbon rings are bonded together with single bonds and which has a bond on an atom constituting the ring; or a divalent group in which one or more rings selected from the group consisting of monocyclic aromatic hydrocarbon rings, fused aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings, and fused non-aromatic hydrocarbon rings are bonded together with a monocyclic or fused non-aromatic hydrocarbon ring with a single bond and which has a bond on an atom constituting the ring. The number of carbon atoms in the single ring or condensed ring is preferably 3 to 20 because an appropriate core size provides good molecular orientation.

[0224] Examples of linked non-aromatic hydrocarbon ring groups include divalent groups in which a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Further examples include divalent groups in which a monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0225] Specific examples of the linking non-aromatic hydrocarbon ring group include a bis(cyclohexane)-4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.

[0226] The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group, because it optimizes the intermolecular interactions acting between liquid crystal compounds, thereby improving molecular alignment.

[0227] As the unlinked non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl group) is preferred, and as the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferred.

[0228] -Q 3 The heterocyclic group in - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0229] The aromatic heterocyclic group includes an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.

[0230] The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0231] Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0232] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0233] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0234] Non-aromatic heterocyclic groups include unlinked non-aromatic heterocyclic groups and linked non-aromatic heterocyclic groups.

[0235] The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0236] Examples of the non-aromatic heterocycle of a divalent group of a monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidine ring, a piperidine ring, a dihydropyridine ring, a piperazine ring, a tetrahydrothiazole ring, a tetrahydrooxazole ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, and a quinuclidine ring.

[0237] The linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0238] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0239] -Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are respectively represented by -R n , -OH, -OR n , -OC(=O)-R n , -NH2, -NH-Rn , -N(R n’ )-R n , -C(=O)-R n , -C(=O)-OR n , -C(=O)-NH2, -C(=O)-NH-R n , -C(=O)-N(R n’ )-R n , -SH, -SR n -R may be substituted with one or more groups selected from the group consisting of a trifluoromethyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, and a halogen atom. n and -R n’ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0240] -Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are each preferably independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and more preferably unsubstituted, in terms of having a highly linear molecular structure, facilitating association of the polymerizable liquid crystal compounds (2) with each other, and facilitating the development of a liquid crystal state.

[0241] -Q 3 The substituents possessed by the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in - may be the same or different, and the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group may be entirely substituted, entirely unsubstituted, or partly substituted and partly unsubstituted.

[0242] -A 11 -, -A 12 -and-A 13 The substituents of the divalent organic group in -A may be the same or different, 11 -, -A 12 -and-A 13All of the divalent organic groups in - may be substituted, all may be unsubstituted, or some may be substituted and some may be unsubstituted.

[0243] -Q 3 As -, a hydrocarbon ring group is preferable, and a phenylene group or a cyclohexanediyl group is more preferable. Since the linearity of the molecular structure of the polymerizable liquid crystal compound (2) can be increased, -Q 3 As -, a 1,4-phenylene group and a cyclohexane-1,4-diyl group are more preferred.

[0244] -A 11 -, -A 12 -and-A 13 As the divalent organic group of -, -Q 3 Preferably, - is a hydrocarbon ring group, i.e., the divalent organic group is a hydrocarbon ring group. As the divalent organic group, a phenylene group or a cyclohexanediyl group is more preferred, and a 1,4-phenylene group or a cyclohexane-1,4-diyl group is even more preferred because they can increase the linearity of the molecular structure of the polymerizable liquid crystal compound (2).

[0245] The polymerizable liquid crystal compound (2) includes -A 11 -, -A 12 -and-A 13 -, one of which is a partial structure represented by formula (3), and the other two are each independently a divalent organic group; 11 -, -A 12 -and-A 13 -C of the partial structure represented by formula (3) y - is preferably a hydrocarbon ring group, and the divalent organic group is particularly preferably a hydrocarbon ring group. Furthermore, the hydrocarbon ring group is preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group. 11 -and-A 13 Preferably, one of the groups is a cyclohexane-1,4-diyl group.

[0246] -A 11 -and-A13 -, one of which is a partial structure represented by formula (3), and the other one and -A 12 It is more preferable that - is a divalent organic group. 11 -and-A 13 Among -, one of the divalent organic groups is preferably a cyclohexane-1,4-diyl group, and -A 12 It is particularly preferred that - is a 1,4-phenylene group.

[0247] (-Y 1 - and -Y 2 -) -Y 1 - and -Y 2 Each - independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CHCH-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-. Since the polymerizable liquid crystal compound (2) tends to be linear and to easily undergo rotational motion around the molecular minor axis, -Y 1 - and -Y 2 Each of the -'s independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CHCH-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-, which have little π-bonding property, and a single bond, -C(=O)O-, -OC(=O)-, -CHCH-, -CHO-, or -OCH- is more preferable.

[0248] As in the formula (2A), formula (2C), formula (2D), and formula (2F), -X 1 - and -Y 1 -or-X 1 - and -Y 2 If - is bonded, -X 1 - Combines with -Y 1 -or-X 1 - Combines with -Y 2 - is preferably a single bond.1 - and -Y 1 - and -Y 2 The other of - is preferably -C(=O)O- or -OC(=O)-.

[0249] As in the formula (2B) and formula (2E), -X 1 -ga-Y 1 - and -Y 2 If it is not bound to any of -, -X 1 - is preferably -CH2CH2-, -CH2O-, or -OCH2-; -Y 1 - and -Y 2 Each - is preferably -C(=O)O- or -OC(=O)-.

[0250] (k) k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2. When k is 2, each -Y 2 - may be the same or different, and each -A 13 - may be the same or different.

[0251] (Preferred structure) As the polymerizable liquid crystal compound (2), a compound represented by the formula (2A), (2B), (2E) or (2F) is preferred because it optimizes the intermolecular interactions acting between the liquid crystal compounds and provides an appropriate core size, resulting in good molecular orientation.

[0252] (Specific Examples of Polymerizable Liquid Crystal Compounds) Specific examples of the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention include, but are not limited to, the polymerizable liquid crystal compounds shown below. 13 represents an n-hexyl group, 11 means an n-pentyl group.

[0253] [ka]

[0254]

change

[0255]

change

[0256]

change

[0257]

change

[0258]

change

[0259]

change

[0260]

change

[0261]

change

[0262]

change

[0263]

change

[0264] [ka]

[0265] [ka]

[0266] (Liquid crystal compound content) The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention preferably comprises a polymerizable liquid crystal compound (2). The composition for forming an anisotropic dye film of the present invention may contain only one type of polymerizable liquid crystal compound alone, or may contain two or more types in any combination and ratio.

[0267] The content of the liquid crystal compound in the composition for anisotropic dye film of the present invention (when two or more liquid crystal compounds are used in combination, the total content of each compound) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, and preferably 99 parts by mass or less, more preferably 98 parts by mass or less, relative to the solid content (100 parts by mass) of the composition for anisotropic dye film. When the content of the liquid crystal compound in the composition for anisotropic dye film is between the above-mentioned lower limit and the above-mentioned upper limit, the alignment of the liquid crystal molecules tends to be high.

[0268] The composition for anisotropic dye film of the present invention may contain one or more polymerizable or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (2). However, from the viewpoint of more effectively obtaining the effects of the present invention by using the polymerizable liquid crystal compound (2), the proportion of the polymerizable liquid crystal compound (2) in 100% by mass of the total amount of liquid crystal compounds contained in the composition for anisotropic dye film of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15 to 100% by mass.

[0269] (Isotropic phase appearance temperature) From the viewpoint of processing, the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention preferably has an isotropic phase appearance temperature of 160°C or lower, more preferably 140°C or lower, even more preferably 115°C or lower, even more preferably 110°C or lower, and particularly preferably 105°C or lower. Here, the isotropic phase appearance temperature refers to the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid crystal to liquid crystal. In the present invention, it is preferable that at least one of these phase transition temperatures is equal to or lower than the above upper limit, and it is more preferable that both of these phase transition temperatures are equal to or lower than the above upper limit.

[0270] (Method for producing polymerizable liquid crystal compound) The polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipso substitution reaction, and coupling reaction using a metal catalyst. For example, the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be synthesized according to the method described in the examples below or the method described on pages 449 to 468 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000).

[0271] (Relationship between polymerizable liquid crystal compound and compound of the present invention) From the viewpoint of facilitating improvement in the orientation of an anisotropic dye film formed using the composition for forming an anisotropic dye film, it is preferable that the difference between the molecular length of the polymerizable liquid crystal compound and the molecular length of the dye is small, since this results in a stronger intermolecular interaction between the liquid crystal molecules and the dye molecules and makes it less likely that the dye molecules will inhibit the association of the liquid crystal molecules with each other.

[0272] Therefore, in the anisotropic dye film-forming composition of the present invention, the number of ring structures (r n1 ) and the number of ring structures (r n2 ) and the ratio (r n1 / r n2) is preferably 0.7 to 1.5. In addition, a fused ring in which two or more rings are fused is counted as one ring structure.

[0273] Here, the number of ring structures (r n2 ) means A in the formula 1 , A 2 , and A 3 Specifically, when n is 1, r n2 is 3; if n is 2, r n2 is 4; if n is 3, r n2 is 5. Even if -Y is a cyclic functional group such as a pyrrolidinyl group or a piperidinyl group, the number of ring structures contained in -Y is determined based on the number of ring structures (r n2 ) is not included.

[0274] In addition, the number of ring structures (r n2 ) means A in the formula 41 , A 42 , and A 43 Specifically, when n is 1, r n2 is 3; if n is 2, r n2 is 4; if n is 3, r n2 is 5. Even if -Y is a cyclic functional group such as a pyrrolidinyl group or a piperidinyl group, the number of ring structures contained in -Y is determined based on the number of ring structures (r n2 ) is not included.

[0275] In addition, the number of ring structures (r n2 ) means A in the formula 21 , A 22 , and A 23 Specifically, when n is 1, r n2 is 3; if n is 2, r n2 is 4; if n is 3, r n2 is 5. Even if -Y is a cyclic functional group such as a pyrrolidinyl group or a piperidinyl group, the number of ring structures contained in -Y is determined based on the number of ring structures (r n2 ) is not included.

[0276] In addition, the number of ring structures (r n2 ) means -A in formula (31) 31 -, -A 32 -, and -A 33 - is the sum of, specifically, when n is 1, r n2 is 3; if n is 2, r n2 is 4; if n is 3, r n2 is 5. Even if -Y is a cyclic functional group such as a pyrrolidinyl group or a piperidinyl group, the number of ring structures contained in -Y is determined based on the number of ring structures (r n2 ) is not included.

[0277] More specifically, if n is 1, then r n2 is 3, so r n1 is 3 or 4; if n is 2, r n2 is 4, so r n1 is 3, 4, 5, or 6; if n is 3, then r n2 is 5, so r n1 is 4, 5, 6, or 7, the number of ring structures (r n1 ) and the number of ring structures (r n2 ) and the ratio (r n1 / r n2 ) is preferably 0.7 to 1.5.

[0278] The number of ring structures (r n1 ) does not include ring structures (such as oxirane rings and oxetane rings) contained in the polymerizable group in the polymerizable liquid crystal compound.

[0279] <Polymerization initiator> The anisotropic dye film-forming composition of the present invention may contain a polymerization initiator, if necessary.

[0280] The polymerization initiator is a compound capable of initiating the polymerization reaction of the polymerizable liquid crystal compound. As the polymerization initiator, a photopolymerization initiator that generates active radicals by the action of light is preferred.

[0281] Examples of polymerization initiators that can be used include titanocene derivatives; biimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-s-triazine derivatives; alkylphenone derivatives; oxime ester derivatives; benzoins; benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; acetophenone derivatives; thioxanthone derivatives; benzoic acid ester derivatives; acridine derivatives; phenazine derivatives; and anthrone derivatives.

[0282] Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferred.

[0283] Specifically, titanocene derivatives include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyltitanium bis(2,4,6-trifluorophenyl-1-yl), dicyclopentadienyltitanium Examples of the titanium bis(2,6-difluorophenyl-1-yl), dicyclopentadienyltitanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl-1-yl), and dicyclopentadienyltitanium [2,6-difluoro-3-(pyrro-1-yl)-phenyl-1-yl].

[0284] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0285] Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

[0286] Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

[0287] Examples of alkylphenone derivatives include diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0288] Examples of oxime ester derivatives include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, and oxime ester derivatives described in JP-A Nos. 2000-80068, 2006-36750, and WO 2009 / 131189.

[0289] Examples of benzoins include benzoin, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.

[0290] Examples of benzophenone derivatives include benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

[0291] Examples of the acylphosphine oxide derivatives include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0292] Examples of iodonium salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate.

[0293] Sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4,4'-bis[diphenylsulfonio]diphenylsulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluoroantimonate, and 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluorophosphate. -, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)sulfonio-diphenyl sulfide tetrakis(pentafluorophenyl)borate, etc.

[0294] Examples of the anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

[0295] Examples of acetophenone derivatives include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone.

[0296] Examples of thioxanthone derivatives include thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0297] Benzoic acid ester derivatives include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

[0298] Examples of the acridine derivatives include 9-phenylacridine and 9-(p-methoxyphenyl)acridine.

[0299] Examples of phenazine derivatives include 9,10-dimethylbenzphenazine.

[0300] Examples of anthrone derivatives include benzanthrone.

[0301] The polymerization initiator may be used alone or in combination of two or more kinds.

[0302] As the polymerization initiator, commercially available products can also be used. Commercially available products include, for example, IRGACURE (registered trademark, the same applies hereinafter) 250, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE Examples of suitable acrylic resins include 784, OXE-01, and OXE-02 (all manufactured by BASF); Seikuol® BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); Kayacure® BP100 and UVI-6992 (manufactured by The Dow Chemical Company); Adeka Optoma SP-152 and SP-170 (manufactured by ADEKA Corporation); TAZ-A and TAZ-PP (manufactured by Nippon SiberHegner Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); and TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, and TRONLYTR-PBG-314 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.).

[0303] When the composition for forming an anisotropic dye film of the present invention contains a polymerization initiator, the content of the polymerization initiator in the composition for forming an anisotropic dye film of the present invention is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the polymerizable liquid crystal compound, from the viewpoint of preventing the alignment of the polymerizable liquid crystal compound from being disturbed.

[0304] If necessary, a polymerization accelerator may be used in combination with the polymerization initiator. Examples of the polymerization accelerator include N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; mercapto compounds having a heterocycle such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole; and mercapto compounds such as aliphatic polyfunctional mercapto compounds. The polymerization accelerator may also be used alone or in combination of two or more.

[0305] If necessary, a sensitizing dye may be used in combination for the purpose of increasing the sensitivity. An appropriate sensitizing dye is used depending on the wavelength of the exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, etc.; coumarin dyes having a heterocycle described in JP-A-3-239703 and JP-A-5-289335, etc.; 3-ketocoumarin dyes described in JP-A-3-239703 and JP-A-5-289335, etc.; pyrromethene dyes described in JP-A-6-19240, etc.; and JP-A-47-2528 and JP-A-54-155292, etc. and dyes having a dialkylaminobenzene skeleton described in JP-B No. 45-37377, JP-A No. 48-84183, JP-A No. 52-112681, JP-A No. 58-15503, JP-A No. 60-88005, JP-A No. 59-56403, JP-A No. 2-69, JP-A No. 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, and JP-A No. 4-288818. The sensitizing dyes may also be used alone or in combination of two or more.

[0306] <Solvent> The anisotropic dye film-forming composition of the present invention may contain a solvent, if necessary.

[0307] The solvent that can be used in the anisotropic dye film-forming composition of the present invention is not particularly limited as long as it can disperse or dissolve the dye or other additives sufficiently in the polymerizable liquid crystal compound. Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene. These solvents may be used alone or in combination of two or more.

[0308] The solvent is preferably one that can dissolve the polymerizable liquid crystal compound and the dye, and more preferably one that completely dissolves the polymerizable liquid crystal compound and the dye. The solvent is also preferably one that is inactive to the polymerization reaction of the polymerizable liquid crystal compound. From the viewpoint of coating the anisotropic dye film-forming composition of the present invention described below, the solvent preferably has a boiling point in the range of 50 to 200°C.

[0309] When the anisotropic dye film-forming composition of the present invention contains a solvent, the content of the solvent in the anisotropic dye film-forming composition is preferably 50 to 98 mass % relative to the total amount (100 mass %) of the composition of the present invention. In other words, the solid content in the anisotropic dye film-forming composition of the present invention is preferably 2 to 50 mass %. When the solid content in the anisotropic dye film-forming composition is equal to or less than the upper limit, the viscosity of the anisotropic dye film-forming composition does not become too high, the thickness of the resulting polarizing film tends to be uniform, and unevenness tends to be less likely to occur in the polarizing film.

[0310] The solid content of the anisotropic dye film-forming composition of the present invention can be determined taking into consideration the thickness of the polarizing film to be produced.

[0311] The viscosity of the anisotropic dye film-forming composition of the present invention is not particularly limited as long as a uniform film without uneven thickness can be formed by the coating method described below. From the viewpoints of achieving uniform thickness over a large area, productivity such as coating speed, and in-plane uniformity of optical properties, the viscosity of the anisotropic dye film-forming composition of the present invention is preferably 0.1 mPa·s or more, and preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

[0312] <Other additives> The anisotropic dye film-forming composition of the present invention may further contain, as necessary, other additives other than the dye and polymerizable liquid crystal compound, such as the above-mentioned polymerization initiator, a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersant, an antioxidant, an organic or inorganic filler, an organic or inorganic nanosheet, an organic or inorganic nanofiber, or a metal oxide. The inclusion of these additives may improve the coatability and stability of the anisotropic dye film-forming composition of the present invention, or may improve the stability of the anisotropic dye film formed from the anisotropic dye film-forming composition of the present invention.

[0313] <Method for producing anisotropic dye film-forming composition> The method for producing the composition for anisotropic dye film of the present invention is not particularly limited. For example, a dye containing the compound of the present invention, a polymerizable liquid crystal compound, and optionally a solvent and other additives are mixed, and the mixture is stirred or shaken at 0 to 80° C. to dissolve the dye. If the dye is poorly soluble, a homogenizer, a bead mill disperser, or the like may be used.

[0314] The method for producing the composition for anisotropic dye film of the present invention may include a filtration step for the purpose of removing foreign matter and the like from the composition.

[0315] The anisotropic dye film-forming composition of the present invention, obtained by removing the solvent from the anisotropic dye film-forming composition, may or may not be liquid crystal at any temperature, but preferably exhibits liquid crystallinity at any temperature.

[0316] From the viewpoint of the coating process described below, the composition obtained by removing the solvent from the anisotropic dye film-forming composition of the present invention preferably has an isotropic phase appearance temperature of less than 160°C, more preferably less than 140°C, even more preferably less than 115°C, even more preferably less than 110°C, and particularly preferably less than 105°C.

[0317] [Anisotropic dye film] The anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention, and therefore includes a dye and one or both of a polymerizable liquid crystal compound and a polymer having units based on the polymerizable liquid crystal compound, and the dye includes the compound of the present invention.

[0318] The anisotropic dye film of the present invention may contain, as other components, a non-polymerizable liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, a non-polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersant, an antioxidant, an organic or inorganic filler, an organic or inorganic nanosheet, an organic or inorganic nanofiber, a metal oxide, or the like.

[0319] The anisotropic dye film of the present invention can function as a polarizing film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption. In addition, by selecting the film formation process and the composition containing the substrate and organic compound (dye or transparent material), it can also function as a variety of anisotropic dye films with refractive anisotropy, conductive anisotropy, etc.

[0320] When the anisotropic dye film of the present invention is used as a polarizing element for a liquid crystal display or an anti-reflection film for an OLED, the orientation characteristics of the anisotropic dye film can be expressed using a dichroic ratio. A dichroic ratio of 8 or more will function as a polarizing element, but a dichroic ratio of 15 or more is preferred, a dichroic ratio of 20 or more is more preferred, a dichroic ratio of 25 or more is even more preferred, a dichroic ratio of 30 or more is particularly preferred, and a dichroic ratio of 40 or more is particularly preferred. The higher the dichroic ratio of the anisotropic dye film, the better. When the dichroic ratio is equal to or greater than the lower limit, the film is useful as an optical element, particularly a polarizing element, as described below.

[0321] When used as a polarizing element in an anti-reflection film for OLEDs, even if the performance of peripheral materials such as retardation films is low, the characteristics of the anti-reflection film are improved as long as the performance of the polarizing element is high. Therefore, if the performance of the polarizing element is high, it is easy to simplify the layer structure, and even a thin film structure can easily exhibit sufficient functionality, making it suitable for use in applications where it is used while being deformed, including folding and bending. It also makes it possible to keep costs low.

[0322] The dichroic ratio (D) referred to in the present invention is expressed by the following formula when the dyes are uniformly oriented. D=Az / Ay Here, Az is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye, and Ay is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is perpendicular to the orientation direction of the anisotropic dye.

[0323] The absorbances (Az, Ay) are not particularly limited as long as they are of the same wavelength, and any wavelength may be selected depending on the purpose. When expressing the degree of orientation of an anisotropic dye film, it is preferable to use a value corrected for luminosity in a specific wavelength range of 350 nm to 800 nm of the anisotropic dye film, or a value at the maximum absorption wavelength in the visible range.

[0324] The transmittance of the anisotropic dye film of the present invention is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more, at the wavelength of the intended use. When the anisotropic dye film of the present invention is used as a dye film having anisotropy over the entire visible light wavelength range, the transmittance of the anisotropic dye film in the visible light wavelength range is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. The transmittance of the anisotropic dye film of the present invention may be an upper limit depending on the application. For example, when a high degree of polarization is required, the transmittance is preferably 50% or less. A transmittance within the above range makes the film useful as an optical element, as described below, particularly useful as an optical element for liquid crystal displays used for color display or as an antireflection film combining an anisotropic dye film with a retardation film.

[0325] The anisotropic dye film has a dry thickness of preferably 10 nm or more, more preferably 100 nm or more, and even more preferably 500 nm or more. The anisotropic dye film has a dry thickness of preferably 30 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, and particularly preferably 3 μm or less. When the anisotropic dye film has a thickness within the above range, uniform orientation of the dye within the film and a uniform film thickness tend to be obtained.

[0326] [Method for manufacturing anisotropic dye film] The anisotropic dye film of the present invention is preferably produced by a wet film-forming method using the anisotropic dye film-forming composition of the present invention.

[0327] The wet film-forming method referred to in the present invention is a method of applying and aligning a composition for an anisotropic dye film onto a substrate by some method. Therefore, the composition for an anisotropic dye film only needs to have fluidity, and may or may not contain a solvent. From the viewpoint of viscosity during application and film uniformity, it is more preferable that the composition contains a solvent.

[0328] The liquid crystals and dyes in anisotropic dye films can be aligned by shear during the coating process or by the drying process of the solvent. Alternatively, the liquid crystals and dyes can be aligned and laminated on a substrate through a process of heating after coating and drying to realign them. In wet film-forming methods, when an anisotropic dye film composition is applied to a substrate, the dyes and liquid crystal compounds self-associate (in a molecular association state such as a liquid crystal state) within the anisotropic dye film composition, or during the drying process of the solvent, or after the solvent is completely removed, resulting in alignment over a small area. Applying an external field to this state can induce a uniform orientation in a macroscopic region, resulting in an anisotropic dye film with the desired performance. In this respect, this method differs from methods that rely on dyeing polyvinyl alcohol (PVA) films or the like with a dye-containing solution and stretching them to align the dyes solely through the stretching process. The external field here refers to the influence of an alignment treatment layer previously applied to the substrate, shear force, magnetic field, electric field, heat, etc., and can be used alone or in combination. If necessary, a heating step may be carried out.

[0329] The process of applying the composition for anisotropic dye film onto a substrate to form a film, the process of orienting by applying an external field, and the process of drying the solvent may be carried out sequentially or simultaneously.

[0330] In the wet film-forming method, the composition for forming an anisotropic dye film can be applied to a substrate by, for example, a coating method, a dip coating method, an LB film formation method, a known printing method, etc. There is also a method in which the anisotropic dye film thus obtained is transferred to another substrate.

[0331] Among these, it is preferable to apply the anisotropic dye film-forming composition onto the substrate by using a coating method.

[0332] The orientation direction of the anisotropic dye film may be different from the coating direction. In the present invention, the orientation direction of the anisotropic dye film refers to, for example, the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, or the fast axis or slow axis in the case of a retardation film.

[0333] The method for applying the composition for anisotropic dye film to obtain an anisotropic dye film is not particularly limited, and examples thereof include the method described in "Coating Engineering" by Harasaki Yuji (Asakura Shoten Co., Ltd., published March 20, 1971), pages 253-277, and the method described in "Creation and Application of Molecular Cooperative Materials" edited by Ichimura Kunihiro (CMC Publishing Co., Ltd., published March 3, 1998), pages 118-149, as well as coating a substrate having a stepped structure (which may have been previously subjected to an orientation treatment) by slot die coating, spin coating, spray coating, bar coating, roll coating, blade coating, curtain coating, fountain coating, dipping, etc. Among these, slot die coating and bar coating are preferred because they can produce highly uniform anisotropic dye films.

[0334] The die coater used in the slot die coating method is generally equipped with a coating machine that ejects the coating liquid, a so-called slit die. Slit dies are disclosed, for example, in Japanese Patent Application Laid-Open Nos. 2-164480, 6-154687, and 9-131559, "Fundamentals and Applications of Dispersion, Coating, and Drying" (2014, Techno System Co., Ltd., ISBN 9784924728707 C 305), "Wet Coating Technology for Displays and Optical Components" (2007, Information Organization, ISBN 9784901677752), and "Precision Coating and Drying Technology in the Electronics Field" (2007, Technical Information Association, ISBN 9784861041389). These known slit dies can be used to coat flexible materials such as films and tapes, as well as hard materials such as glass substrates.

[0335] Examples of substrates that can be used for forming the anisotropic dye film of the present invention include glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyether ether ketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl cellulose, and urethane-based films.

[0336] To control the orientation direction of the dye, the substrate surface may be subjected to an alignment treatment (alignment film) using a known method, such as rubbing, forming grooves (fine groove structures) on the alignment film surface, using polarized ultraviolet light or polarized laser (photoalignment), forming an LB film, or oblique deposition of inorganic materials, as described on pages 226 to 239 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000). The preferred alignment treatments are rubbing and photoalignment. Materials used in rubbing include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, and acrylic resin. Materials used in photoalignment include polycinnamate, polyamic acid / polyimide, and azobenzene. When an alignment layer is provided, the liquid crystal compound and dye are thought to be aligned due to the effects of the alignment treatment layer and the shear force applied to the anisotropic dye film composition during application.

[0337] The method and interval for supplying the composition for anisotropic dye film when coating the composition for anisotropic dye film are not particularly limited. Since the operation of supplying the coating liquid may become complicated and the thickness of the coating film may vary when the coating liquid is started and stopped, when the thickness of the anisotropic dye film is thin, it is desirable to apply the composition for anisotropic dye film while continuously supplying it.

[0338] The coating speed of the composition for an anisotropic dye film is usually 0.001 m / min or more, preferably 0.01 m / min or more, more preferably 0.1 m / min or more, even more preferably 1.0 m / min or more, and particularly preferably 5.0 m / min or more. The coating speed of the composition for an anisotropic dye film is usually 400 m / min or less, preferably 200 m / min or less, more preferably 100 m / min or less, and even more preferably 50 m / min or less. When the coating speed is within the above range, the anisotropy of the anisotropic dye film is obtained and the coating tends to be uniform.

[0339] The coating temperature of the composition for anisotropic dye film is usually 0° C. or higher and 100° C. or lower, preferably 80° C. or lower, and more preferably 60° C. or lower.

[0340] The humidity during application of the composition for anisotropic dye film is preferably 10% RH or higher and preferably 80% RH or lower.

[0341] The anisotropic dye film may be subjected to an insolubilization treatment. Insolubilization refers to a treatment that reduces the solubility of the compound in the anisotropic dye film, thereby controlling the elution of the compound from the anisotropic dye film and increasing the stability of the film. Specifically, film polymerization and overcoating are preferred in terms of ease of post-processing and durability of the anisotropic dye film.

[0342] When polymerizing the film, the film in which the liquid crystal molecules and dye molecules are oriented is polymerized using light, heat, and / or radiation.

[0343] When polymerization is carried out using light or radiation, it is preferable to irradiate with active energy rays having a wavelength in the range of 190 to 450 nm. The light source of the actinic energy rays with a wavelength of 190 to 450 nm is not particularly limited, but examples thereof include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. When using light with a specific wavelength, an optical filter can also be used. The exposure dose of the actinic energy rays is 10 to 10,000 J / m 2 is preferred.

[0344] When polymerization is carried out using heat, it is preferably carried out in the range of 50 to 200°C, more preferably in the range of 60 to 150°C.

[0345] Polymerization may be carried out using light, heat, and / or radiation, but photopolymerization or a combination of photopolymerization and thermal polymerization is preferred because it shortens the film formation process time and requires simple equipment.

[0346] [Optical elements] The optical element of the present invention includes the anisotropic dye film of the present invention.

[0347] The optical element in the present invention refers to a polarizing element that utilizes the anisotropy of light absorption to obtain linearly polarized light, circularly polarized light, elliptically polarized light, etc., a phase difference element, an element having functions such as refractive anisotropy and conductive anisotropy, etc. These functions can be appropriately adjusted by selecting the anisotropic dye film formation process and the composition containing the substrate and organic compound (dye or transparent material).

[0348] The optical element of the present invention is most preferably used as a polarizing element. The optical element of the present invention can be suitably used in applications such as flexible displays, since a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating or the like.

[0349] The optical element may be provided with other layers to maintain or improve the functionality of the anisotropic dye film. Examples of such other layers include layers that block specific wavelengths or specific substances (e.g., barrier films such as oxygen barrier films and water vapor barrier films) and are used to improve durability such as light resistance, heat resistance, and water resistance; wavelength cut filters or layers containing materials that absorb specific wavelengths and are used to change the color gamut or improve optical properties; and the like.

[0350] [Polarizing element] A polarizing element (hereinafter sometimes referred to as "the polarizing element of the present invention") can be produced using the anisotropic dye film of the present invention.

[0351] The polarizing element of the present invention may have any other film (layer) as long as it has the anisotropic dye film of the present invention. For example, it can be produced by providing an alignment film on a substrate and then forming the anisotropic dye film of the present invention on the surface of the alignment film.

[0352] The polarizing element is not limited to an anisotropic dye film, and may be used in combination with an overcoat layer having the function of improving polarization performance, improving mechanical strength, etc., an adhesive layer or anti-reflection layer, an alignment film, a layer having optical functions such as a function as a retardation film, a function as a brightness-enhancing film, a function as a reflective or anti-reflection film, a function as a semi-transmissive reflective film, a function as a diffusion film, etc. Specifically, the layers having the various functions described above may be laminated by coating, lamination, etc., and used as a laminate.

[0353] These layers can be provided as appropriate depending on the manufacturing process, properties, and functions, and the position and order of lamination are not particularly limited. For example, each layer may be formed on the anisotropic dye film or on the opposite side of the substrate on which the anisotropic dye film is provided. Furthermore, the order in which each layer is formed may be either before or after the anisotropic dye film is formed.

[0354] These layers having optical functions can be formed by the following methods.

[0355] A layer having a function as a retardation film can be formed by applying or pasting a retardation film onto other layers constituting a polarizing element, etc. The retardation film can be formed, for example, by performing a stretching treatment described in JP-A Nos. 2-59703 and 4-230704, or by performing a treatment described in JP-A No. 7-230007.

[0356] A layer functioning as a brightness enhancement film can be formed by coating or laminating a brightness enhancement film onto other layers constituting a polarizing element, etc. The brightness enhancement film can be formed, for example, by forming micropores using the methods described in JP-A Nos. 2002-169025 and 2003-29030, or by superposing two or more cholesteric liquid crystal layers having different central wavelengths of selective reflection.

[0357] A layer that functions as a reflective film or a semi-transparent reflective film can be formed, for example, by applying or laminating a metal thin film obtained by vapor deposition or sputtering to other layers that constitute the polarizing element.

[0358] The layer functioning as a diffusion film can be formed, for example, by coating another layer constituting the polarizing element with a resin solution containing fine particles.

[0359] A layer functioning as a retardation film or an optical compensation film can be formed by applying a liquid crystal compound such as a discotic liquid crystal compound, a nematic liquid crystal compound, a smectic liquid crystal compound, or a cholesteric liquid crystal compound to another layer constituting a polarizing element and orienting the compound. In this case, an alignment film may be provided on a substrate, and the retardation film or the optical compensation film may be formed on the surface of the alignment film.

[0360] When the anisotropic dye film of the present invention is used as an anisotropic dye film or the like in various display elements such as liquid crystal elements (LCDs) and organic electroluminescence elements (OLEDs), the anisotropic dye film of the present invention may be formed directly on the surface of an electrode substrate or the like constituting these display elements, or a substrate on which the anisotropic dye film of the present invention is formed may be used as a constituent member of these display elements. [Example]

[0361] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. In the following description, "parts" means "parts by mass."

[0362] [Method for identifying liquid crystal phases] The liquid crystallinity of the obtained anisotropic dye film-forming composition was examined by differential scanning calorimetry (Seiko Instruments Inc., "DSC220CU"), X-ray structural analysis (Rigaku Corporation, "NANO-Viewer"), and observation using a polarizing microscope (Nikon Instech Corporation, "ECLIPSE LV100N POL") equipped with a hot stage (Toyo Corporation, "HCS302-LN190"), and the composition was identified as being liquid crystal according to the method described on pages 9-50 and 117-176 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000).

[0363] [Measurement of transmittance and dichroic ratio for polarized light along the absorption axis / polarization axis of anisotropic dye films] The transmittance of the obtained anisotropic dye film for polarized light in the absorption axis / polarization axis direction was measured using a spectrophotometer equipped with a Glan-Thompson polarizer (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100"). Linearly polarized measurement light was incident on the anisotropic dye film, and the transmittance for polarized light in the absorption axis direction of the anisotropic dye film and the transmittance for polarized light in the polarization axis direction of the anisotropic dye film were measured, and the dichroic ratio (D) was calculated using the following formula. D=Az / Ay (In the formula, Ay = -log(Ty); Az = -log(Tz); Tz is the transmittance of the anisotropic dye film for light polarized along the absorption axis; Ty is the transmittance of the anisotropic dye film for polarized light in the direction of the polarization axis.

[0364] Specifically, the anisotropic dye film composition was injected in its isotropic phase into a sandwich cell (cell gap: 8.0 μm, 10.0 μm; pre-formed polyimide film was rubbed with a cloth) consisting of a glass substrate and a polyimide alignment film (LX1400, Hitachi Chemical DuPont Microsystems). The anisotropic dye film was obtained by cooling the cell to 80°C at a rate of 5°C / min. The dichroic ratio was measured at each temperature while the cell was further cooled to 0°C at a rate of 5°C / min. The dichroic ratio at the temperature and wavelength at which the maximum dichroic ratio was obtained was determined as the dichroic ratio of the anisotropic dye film. The dichroic ratio at the wavelength at which the absorbance in the orthogonal direction (the absorption axis direction) of the anisotropic dye film reached its maximum value was also measured at that temperature.

[0365] [Synthesis of Liquid Crystal Compounds] <Liquid Crystal Compound (I-1)> A liquid crystal compound (I-1) was synthesized according to the synthesis method described below.

[0366] [ka]

[0367] Synthesis of (I-1-a): Ethyl propiolate (9.7 g, 99 mmol) and copper(I) oxide (7.5 g, 94 mmol) were added to a solution of p-iodophenol (11.0 g, 50 mmol) in N,N-dimethylformamide (150 mL), and the mixture was stirred at 110°C for 9 hours and allowed to cool to room temperature. The precipitate was filtered off, and then ethyl acetate was added. The mixture was washed with water and then saturated brine. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 7.3 g of brown crystals (I-1-a).

[0368] Synthesis of (I-1-b): (I-1-a) (4.20 g, 22.1 mmol), 11-bromo-1-undecanol (5.55 g, 22.1 mmol), potassium carbonate (6.10 g, 44.2 mmol), and N,N-dimethylformamide (30 mL) were mixed and stirred at 80 °C for 4 hours. The precipitate was filtered off, and then diethyl ether was added. The mixture was washed with water and then saturated brine. Purification was performed by silica gel column chromatography (hexane / ethyl acetate) to obtain 5.5 g of an orange solid (I-1-b).

[0369] Synthesis of (I-1-c): (I-1-b) (3.6 g, 10 mmol), potassium hydroxide (1.7 g, 30 mmol), and water (20 mL) were mixed and stirred at 100°C for 2 hours. Water (20 mL) was added, and the mixture was acidified with concentrated hydrochloric acid. The precipitate was then filtered off. The resulting precipitate was washed by suspending in acetonitrile to obtain 3.2 g of a milky white solid (I-1-c).

[0370] Synthesis of (I-1-d): (I-1-c) (2.33 g, 7.0 mmol) and tetrahydrofuran (20 mL) were mixed, followed by the addition of N,N-dimethylaniline (1.02 g, 8.4 mmol) and 2,5-di-t-butylphenol (54 mg). After cooling in an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was slowly added. After stirring for 6 hours in an ice bath, methylene chloride was added and the mixture was washed sequentially with 1 mol / L hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine. The product was purified by silica gel column chromatography (chloroform / methanol) to obtain 2.0 g of a white solid (I-1-d).

[0371] Synthesis of (I-1-e): (I-1-e) was synthesized by the synthesis method described in JP 2014-262884 A.

[0372] Synthesis of (I-1-f): (I-1-d) (2.00 g, 5.17 mmol), (I-1-e) (1.01 g, 5.17 mmol), N,N-dimethylamino-4-pyridine (0.13 g, 1.03 mmol), 2,5-di-t-butylphenol (58 mg), and methylene chloride (30 mL) were mixed and cooled in an ice bath. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1.09 g, 5.69 mmol) was added. After standing overnight, the mixture was washed with saturated aqueous ammonium chloride and then saturated brine. Purification by silica gel column chromatography (hexane / ethyl acetate) afforded 1.9 g of a white solid (I-1-f).

[0373] Synthesis of (I-1-g): (I-1-f) (2.6 g, 4.62 mmol), p-toluenesulfonic acid pyridinium salt (0.23 g, 0.92 mmol), 2,5-di-t-butylphenol (44 mg), and ethanol (20 mL) were mixed and stirred for 2 hours at 50° C. The reaction solution was poured into water, and the resulting precipitate was filtered and dried to obtain 2.0 g of a white solid (I-1-g).

[0374] Synthesis of (I-1-h): Compound (I-1-h) was synthesized according to the synthesis method described below.

[0375] [ka]

[0376] (I-1-i) was synthesized according to the method described in Lub et al., Recl. Trav. ChIm. Pays-Bas, 115, 321-328 (1996). Next, (I-1-i) (trans isomer only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed and stirred at 78 °C for 2 hours. The solvent was distilled off, and the residue was dissolved in ethyl acetate (150 mL), and hexane (750 mL) was added and cooled. The precipitate was filtered, washed with hexane, and then dried to obtain 29.2 g of a white solid (I-1-j).

[0377] (I-1-j) (37.2 g, 118.3 mmol), N,N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-t-butylphenol (0.24 g), and tetrahydrofuran (350 mL) were mixed. After cooling in an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was slowly added. After the dropwise addition, the mixture was stirred at 50°C for 2 hours, and then the solvent was distilled off until the liquid volume was 190 mL. The mixture was then poured into 1 mol / L hydrochloric acid under ice cooling. The precipitate was filtered and washed with water and hexane. The mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 39.4 g of a white solid (I-1-h).

[0378] Synthesis of (I-1): (I-1-g) (494 mg, 1.03 mmol), (I-1-h) (400 mg, 1.09 mmol), N,N-dimethylamino-4-pyridine (27 mg, 0.22 mmol), 2,5-di-t-butylphenol (2 mg), and methylene chloride (10 mL) were mixed and cooled in an ice bath. 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (230 mg, 1.19 mmol) was then added. After stirring for 4 hours in an ice bath, the mixture was washed with saturated aqueous ammonium chloride and then saturated brine. The mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 530 mg of liquid crystal compound (I-1) as a white solid.

[0379] The results of liquid chromatography-mass spectrometry of this liquid crystal compound (I-1) are shown below. LC-MS (APCI) m / z 851.5 (M+Na + ) The structure was also confirmed by NMR, and the results are shown below. 1H NMR(CDCl3,400MHz)δ1.20-1.70(m,38H),1.74-1.85(m,2H),2.05-2.25(m,4H),2.49-2. 57(m,1H),3.21-3.29(m,1H),3.46(t,2H,J=6.8Hz),3.99(t,2H,J=6.8Hz),4.15(t,4H,J =6.8Hz),5.80(d,2H,J=10.4Hz),6.12(dd,2H,J=17.2,10.4Hz),6.39(d,2H,J=17.2Hz), 6.89(d,2H,J=6.8Hz),7.10(d,2H,J=6.8Hz),7.19(d,2H,J=6.8Hz),7.55(d,2H,J=6.8Hz)

[0380] The isotropic phase appearance temperature (liquid crystal to liquid phase transition temperature and liquid crystal to liquid crystal phase transition temperature) of the liquid crystal compound (I-1) was determined by differential scanning calorimetry. For the differential scanning calorimetry, 100 parts by mass of the liquid crystal compound (I-1) was used in which 0.2 parts by mass of 4-methoxyphenol was added as a polymerization inhibitor. The liquid crystal compound (I-1) had a liquid crystal to liquid phase transition temperature of 111.0°C and a liquid to liquid crystal phase transition temperature of 109.4°C. This temperature was confirmed by polarizing microscope observation and X-ray structural analysis to be the temperature at which the isotropic phase appears.

[0381] [Synthesis Examples, Examples, and Comparative Examples of the First Invention] [Synthesis of dyes] <Dye (II-1)> Dye (II-1) was synthesized according to the synthesis method described below.

[0382] [ka]

[0383] Synthesis of (II-1-a): Triphenylphosphine (72.7 g, 277.3 mmol), 3,5,5-trimethylhexanol (40.0 g, 277.3 mmol), and dichloromethane (220 mL) were mixed under a nitrogen stream and cooled to 0°C. N-bromosuccinimide (49.4 g, 277.3 mmol) was added and the mixture was stirred at 0°C for 2 hours. The reaction mixture was concentrated, diisopropyl ether (200 mL) was added, and the mixture was sonicated for 10 minutes. The precipitate was then collected by filtration. This procedure was repeated twice and purified by silica gel chromatography (hexane), yielding 43.4 g of (II-1-a).

[0384] Synthesis of (II-1-b): Under a nitrogen stream, tetrahydrofuran (290 mL) and hexane (195 mL) were mixed and cooled to -20°C. A 1.6 M n-butyllithium hexane solution (121 mL) was added dropwise via syringe, and the mixture was heated to 5°C. Thiophene (12.5 g, 154.5 mmol) was added over 10 minutes, and the mixture was heated to 25°C. (II-1-a) (32.0 g, 154.5 mmol) was added all at once, and the mixture was stirred at 50°C for 30 minutes. Cold water (500 mL) was added, and the mixture was extracted with diisopropyl ether. The oil layer was concentrated. The mixture was purified by silica gel chromatography (hexane) to obtain 27.3 g of (II-1-b).

[0385] Synthesis of (II-1-c): Fuming nitric acid (10.6 g, 168.7 mmol) and acetic anhydride (60 mL) were mixed and cooled to -30 °C. Then, a solution of (II-1-b) (27.3 g, 129.8 mmol) and acetic anhydride (60 mL) was added dropwise over 2 hours and stirred at -30 °C for 1.5 hours. After leaving it at room temperature overnight, crushed ice (200 g) was added, and the pH of the reaction solution was adjusted to 4 with 25% aqueous sodium hydroxide. Extraction with dichloromethane and concentration of the oil layer yielded 27.1 g of (II-1-c).

[0386] Synthesis of (II-1-d): (II-1-c) (27.1 g, 106.0 mmol) and 35% hydrochloric acid (75 mL) were mixed and heated to 50 °C, after which tin chloride dihydrate (47.9 g, 212.1 mmol) was added in portions and stirred for 1 hour while cooling. The reaction solution was cooled to 5 °C, and the precipitate was collected by filtration and washed with 35% hydrochloric acid and diisopropyl ether to obtain 8.8 g of (II-1-d) in a wet state.

[0387] Synthesis of (II-1-e): Undried (II-1-d) (8.8 g), sodium thiocyanate (2.7 g, 33.5 mmol), and N-bromosuccinimide (6.0 g, 33.5 mmol) were mixed and stirred at 25°C for 2 hours. The precipitate was then filtered and purified by silica gel chromatography (hexane / ethyl acetate) to obtain 7.4 g of (II-1-e).

[0388] Synthesis of (II-1-f): (II-1-e) (7.4 g, 26.2 mmol), acetic acid (46 mL), and propionic acid (31 mL) were mixed and cooled to 2° C. 40% nitrosylsulfuric acid (10.0 g, 31.4 mmol) was added, and the mixture was stirred at 2° C. for 1 hour. After that, amidosulfuric acid (7.9 g, 8.1 mmol) was added to prepare a diazonium solution. Aniline (10.0 g, 107.3 mmol), formaldehyde sodium bisulfite (14.4 g, 107.3 mmol), and water (300 mL) were mixed and stirred at 70 °C for 2 hours. After cooling to 3 °C, the above diazonium solution was added dropwise over 1 hour, and the mixture was stirred at 3 °C for 1 hour. The precipitated solid was collected by filtration, dispersed in 25% aqueous sodium hydroxide solution (40 mL) and water (200 mL), and stirred at 90 °C for 1.5 hours. After cooling, the precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel chromatography (hexane / ethyl acetate) to obtain 2.6 g of (II-1-f).

[0389] Synthesis of (II-1): (II-1-f) (2.6 g, 6.7 mmol), dimethylformamide (85 mL), and acetic acid (22 mL) were mixed and cooled to 2° C. To this was added 35% hydrochloric acid (2 mL), followed by the addition of sodium nitrite (0.5 g, 7.3 mmol) dissolved in water (5 mL). The mixture was stirred at 2° C. for 2 hours to prepare a diazonium solution. Diethylaniline (1.0 g, 6.7 mmol), methanol (32 mL), and dimethylformamide (3 mL) were mixed and cooled to 2° C., and then the above diazonium solution was added dropwise over 30 minutes while adjusting the pH to 5 with 25% aqueous sodium hydroxide solution, followed by stirring for 3 hours at 2° C. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel chromatography (hexane / dichloromethane) to obtain 0.5 g of dye (II-1).

[0390] The maximum absorption wavelength (λmax) of dye (II-1) in a 10 ppm chloroform solution is 551 nm, and the gram absorption coefficient is 100.7 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (CDCl3, 400MHz) δ0.91(s,9H),δ1.01(d,3H,J=6.3Hz),δ1.24-1.31(m,8H),δ1.59-1.67(m,2H),δ1.73-1.81(m,1H),δ2.91-2.97(m, 2H), δ3.48(q,4H,J=7.1Hz),δ6.74(d,2H,J=9.2Hz),δ6.98(s,1H),δ7.90(d,2H,J=9.2Hz),δ7.97(d,2H,J=8.8Hz),δ8.10(d,2H,J=8.8Hz),

[0391] The solubility of the dye (II-1) in toluene was measured. 3 mg of dye (II-1) was added to 101 mg of toluene and stirred at 80°C for 5 minutes. The mixture was then left to stand at room temperature for 1 hour. The resulting mixture was filtered using a syringe equipped with a syringe filter (Membrane Solutions, PTFE13045, 0.45 μm diameter) to obtain a saturated toluene solution of dye (II-1). This solution was diluted with 767 mg of tetrahydrofuran, and the concentration was determined using HPLC (Hitachi High-Technologies L-2300 series). A 0.1% by mass solution of dye (II-1) was prepared in tetrahydrofuran, and a calibration curve was created at an absorption wavelength of 254 nm. The concentration of the saturated toluene solution was measured using this calibration curve, and the results are shown in Table 1.

[0392] The concentrations of the comparative dyes (III-1) and (III-3) shown below were also measured in a saturated toluene solution in the same manner.

[0393] <Dye (II-2)> Dye (II-2) was synthesized according to the synthesis method described below.

[0394] [ka]

[0395] Synthesis of (II-2-a): Thiophene (12.7 g, 150.9 mmol) and tetrahydrofuran (130 mL) were mixed under a nitrogen stream and cooled to -50°C. A 1.6 M n-butyllithium hexane solution (107 mL) was then added dropwise via syringe and stirred for 1 hour. At -50°C, 1-bromo-3-methylbutane (25.0 g, 165.5 mmol) was added, and the mixture was stirred for 30 minutes, followed by stirring at room temperature for 1 hour. Water (300 mL) was added to the mixture, followed by extraction with hexane. The oil layer was washed with water and saturated brine and concentrated under reduced pressure. The mixture was purified by silica gel chromatography (hexane / ethyl acetate) and then purified ( II-2-a ) was obtained in an amount of 17.0 g.

[0396] Synthesis of (II-2-b): Under a nitrogen stream, ( II-2-a) (17.0 g, 110.2 mmol) and acetic anhydride (170 mL) were mixed and cooled to -30°C, after which nitric acid (8.7 mL, 121.2 mmol) was added and the mixture was stirred at -30°C for 1 hour and at 0°C for 2 hours. Water (500 mL) was added to the mixture, followed by extraction with dichloromethane. The oil layer was washed with water and brine and concentrated under reduced pressure. The mixture was purified by silica gel chromatography (hexane / ethyl acetate) and purified to give the desired product ( II-2-b ) was obtained in an amount of 7.0 g.

[0397] Synthesis of (II-2-c): ( II-2-b ) (3.2 g, 16.1 mmol) and 35% hydrochloric acid (15 mL) were mixed, and tin chloride dihydrate (10.9 g, 48.3 mmol) was added at 2°C. The mixture was stirred vigorously, and then stirred at 25°C for 4 hours. The supernatant was decanted, and the residue was dissolved in ethyl acetate (50 mL). The filtrate was filtered and concentrated under reduced pressure to obtain 6.1 g of (II-2-c) in a wet state.

[0398] Synthesis of (II-2-d): Wet (II-2-c) (6.1 g), acetic acid (30 mL), and sodium thiocyanate (5.2 g, 64.5 mmol) were mixed and cooled to 2 °C. A solution of bromine (1.7 mL, 33.9 mmol) and acetic acid (10 mL) was added, and the mixture was stirred at 25 °C for 1 hour. Sodium sulfite was added, followed by 25% aqueous sodium hydroxide (30 mL), and the mixture was extracted with ethyl acetate. The oil layer was washed with water and saturated brine and concentrated under reduced pressure. 0.5 g of (II-2-d) was obtained by purification using silica gel chromatography (hexane / ethyl acetate).

[0399] Synthesis of (II-2-e): (II-2-d) (7.4 g, 32.7 mmol), acetic acid (46 mL), and propionic acid (31 mL) were mixed and cooled to 2° C. To this was added 40% nitrosylsulfuric acid (12.5 g, 39.2 mmol), and the mixture was stirred at 2° C. for 1 hour to prepare a diazonium solution. Aniline (12.5 g, 133.9 mmol), formaldehyde sodium bisulfite (18.0 g, 133.9 mmol), and water (440 mL) were mixed and stirred at 70 °C for 2 hours. After cooling to 3 °C, the above diazonium solution was added dropwise over 1 hour, and the mixture was stirred at 3 °C for 1 hour. The precipitated solid was collected by filtration, dispersed in 25% aqueous sodium hydroxide solution (40 mL) and water (200 mL), and stirred at 90 °C for 1.5 hours. After cooling, the precipitated solid was collected by filtration to obtain 11.2 g of crude (II-2-e).

[0400] Synthesis of (II-2): (II-2-e) (2.6 g, 6.7 mmol), dimethylformamide (81 mL), and acetic acid (23 mL) were mixed and cooled to 2° C. After adding 35% hydrochloric acid (3 mL), sodium nitrite (0.6 g, 8.6 mmol) dissolved in water (6 mL) was added, and the mixture was stirred at 2° C. for 2 hours to prepare a diazonium solution. Diethylaniline (1.2 g, 7.8 mmol), methanol (33 mL), and dimethylformamide (3 mL) were mixed and cooled to 2° C., and then the above diazonium solution was added dropwise over 30 minutes while adjusting the pH to 5 with 25% aqueous sodium hydroxide solution, followed by stirring for 3 hours at 2° C. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel chromatography (hexane / dichloromethane) to obtain 0.5 g of dye (II-2).

[0401] The maximum absorption wavelength (λmax) of dye (II-2) in a 10 ppm chloroform solution is 550 nm, and the gram absorption coefficient is 110.5 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1H-NMR (CDCl3, 400MHz) δ0.97(d,6H,J=7.7Hz),δ1.25(t,6H,J=7.1Hz),δ1.65-1.69(m,3H),δ2.96(t,2H,J=7.1Hz),δ3.48(q, 4H,J=7.1Hz),δ6.74(d,2H,J=9.3Hz),δ6.98(s,1H),δ7.90(d,2H,J=9.2Hz),δ7.97(d,2H,J=8.9Hz),δ8.10(d,2H,J=8.8Hz), The solubility of dye (II-2) in toluene was measured in the same manner as for dye (II-1) (detection absorption wavelength: 254 nm) and was found to be 0.7%.

[0402] <Dye (II-3)> Dye (II-3) was synthesized according to the synthesis method described below.

[0403] [ka]

[0404] Synthesis of (II-3-a): 3,5,5-Triethyl-1-hexanol (38.4 g, 266 mmol), 47% HBr aqueous solution (50.4 g, 293 mmol), and concentrated sulfuric acid (8.3 g, 82.5 mmol) were mixed and stirred at 120 °C for 5 hours. After cooling to 25 °C, the mixture was added to hexane (600 mL) and washed with water (1200 mL × 3). The organic layer was concentrated and purified by silica gel chromatography (hexane) to obtain 35.5 g of (II-3-a).

[0405] Synthesis of (II-3-b): Under a nitrogen stream, 4-nitrophenol (65.0 g, 467 mmol), (II-3-a) (116.2 g, 560 mmol), dimethylformamide (520 mL), and potassium carbonate (129.1 g, 934 mmol) were mixed and stirred at 90°C for 6 hours. Water (1000 mL) was added, and the mixture was extracted with a 1 / 4 mixture of ethyl acetate and hexane. The oil layer was concentrated. Purification by silica gel chromatography (ethyl acetate / hexane) yielded 113.5 g of (II-3-b).

[0406] Synthesis of (II-3-c): Under an argon stream, (II-3-b) (113.5 g, 427.7 mmol) and ethyl acetate (1100 ml) were mixed, and then palladium-carbon (5% Pd-C, water content 55 wt%, 11.4 g) was added and stirred under a hydrogen atmosphere at 25°C for 60 hours. After replacing the atmosphere in the vessel with argon, the catalyst was filtered off. The catalyst was extracted with dichloromethane, and the organic layers were combined and concentrated. After purification by silica gel chromatography (dichloromethane), 99.5 g of (II-3-c) was obtained.

[0407] [ka]

[0408] Synthesis of (II-3-d): 2-Thiophenecarboxylic acid (2.00 g, 15.6 mmol), diphenylphosphoric azide (4.30 g, 15.6 mmol), triethylamine (2.2 mL, 15.6 mmol), and tert-butyl alcohol (20 mL) were mixed and heated under reflux with stirring for 5 hours. After cooling to 25 °C, water (300 mL) was added and the mixture was extracted with diethyl ether. The organic layer was concentrated and purified by silica gel chromatography (hexane / dichloromethane) to obtain 1.9 g of (II-3-d).

[0409] Synthesis of (II-3-e): (II-3-d) (2.00 g, 10.0 mmol), 12N hydrochloric acid (36 mL), and diethyl ether (85 mL) were mixed and stirred at 25° C. for 30 minutes, and then the solvent was distilled off to obtain 1.36 g of (II-3-e).

[0410] Synthesis of (II-3-f): Under a nitrogen stream, (II-3-c) (47.3 g, 201 mmol) and 12 N hydrochloric acid (375 mL) were mixed, cooled to 0 °C, and stirred for 1 hour. To this was added an aqueous solution of sodium nitrite (17.3 g, 251 mmol) and water (130 mL), and the mixture was stirred at 5 °C for 1 hour to prepare a diazonium solution. (II-3-e) (37.2 g, 241 mmol) and MeOH were mixed and cooled to 0°C, and the above diazonium solution was added dropwise over 40 minutes. The mixture was heated to 25°C and stirred for 3 hours. The precipitated solid was collected by filtration, and the resulting crude product was washed with hexane to obtain 48.1 g of (II-3-f).

[0411] Synthesis of (II-3-g): Under a nitrogen stream, (II-3-f) (48.1 g, 125.7 mmol), sodium thiocyanate (20.4 g, 251.4 mmol), and acetic acid (720 mL) were mixed, and then N-bromosuccinimide (24.6 g, 138.3 mmol) was added dropwise and stirred at 25 °C for 3 hours. Water (600 mL) was added and mixed, and the mixture was filtered. The resulting solid was dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel chromatography (dichloromethane / methanol) to obtain 31.4 g of (II-3-g).

[0412] Synthesis of (II-3): (II-3-g) (0.75 g, 1.86 mmol), acetic acid (3.8 mL), and hydrochloric acid (3.8 mL) were mixed and cooled to 3° C. Sodium nitrite (0.17 g, 2.42 mmol) was added, and the mixture was stirred at 3° C. for 1 hour to prepare a diazonium solution. Diethylaniline (0.56 g, 3.73 mmol), tetrahydrofuran (15 mL), and sodium acetate (7.4 g) were mixed and cooled to 3°C. The diazonium solution was added dropwise over 1 hour and stirred at 3°C ​​for 3 hours. The mixture was heated to 25°C and stirred for 12 hours. Water (7.5 mL) and methanol (15 mL) were then added and stirred. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel chromatography (hexane / dichloromethane) to obtain 0.14 g of dye (II-3).

[0413] The maximum absorption wavelength (λmax) of dye (II-3) in a 10 ppm chloroform solution is 563 nm, and the gram absorption coefficient is 134.8 Lg -1 cm -1 It was.

[0414] The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR(CDCl3,400MHz)δ0.93(s,9H),δ1.03(d,3H,J=6.7Hz),δ1.13-1.18(m,1H),δ1.28-1.37(m,7H),δ1.65-1.72(m,1H),δ1.76-1.91(m,2H),δ3 .53(q,4H,J=7.2Hz),δ4.09(t,2H,J=6.7Hz),δ6.76(d,2H,9.4Hz),δ7.00(d,2H,9.1Hz),δ7.85(s,1H),δ7.88(d,2H,9.1Hz),δ7.95(d,2H,9.4Hz) The solubility of dye (II-3) in cyclopentanone was measured in the same manner as in the measurement of the solubility of dye (IV-1) in cyclopentanone described below (detection absorption wavelength: 254 nm) and was found to be 0.3%.

[0415] The concentration of a cyclopentanone saturated solution of the comparative dye (III-4) described below was also measured in the same manner.

[0416] <Dye (III-2)> Dye (III-2) was synthesized according to the synthesis method described below.

[0417] [ka]

[0418] Synthesis of (III-2-a): Tetrahydrofuran (100 mL) and sodium hydride (60% purity, 6.7 g, 168.0 mmol) were added to an ice-cooled reactor, and a mixture of diethyl (4-nitrobenzyl)phosphonate (18.0 g, 65.9 mmol), 4-butylbenzaldehyde (9.1 g, 56.1 mmol), and tetrahydrofuran (50 mL) was added dropwise over 10 minutes. The mixture was washed with tetrahydrofuran (30 mL) and stirred at 50 °C for 0.5 hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was evaporated. The resulting crude product was dissolved in ethyl acetate (20 mL) with heating, added with hexane (50 mL), and cooled. The precipitate was filtered, washed with hexane, and dried under reduced pressure to obtain 15.0 g of (III-2-a).

[0419] Synthesis of (III-2-b): (III-2-a) (15.0 g, 53.3 mmol), tetrahydrofuran (150 mL), and iron powder (13.9 g, 248.9 mmol) were mixed, and ammonium chloride (13.3 g, 248.6 mmol) dissolved in water (30 mL) was added dropwise, followed by stirring at 50 °C for 3 hours. The mixture was filtered through Celite, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The resulting crude product was suspended in hexane, and the precipitate was filtered off, washed with hexane, and dried to obtain 10.9 g of (III-2-b).

[0420] Synthesis of (III-2): (III-2-b) (2.51 g, 10.0 mmol), N-methylpyrrolidone (40 mL), concentrated hydrochloric acid (2.2 mL), and water (20 mL) were mixed and cooled to 3°C. Then, sodium nitrite (789 mg, 11.4 mmol) was added and the mixture was stirred at 15°C for 3.5 hours. 1-Phenylpyrrolidine (1.47 g, 10.0 mmol), methanol (60 mL), and water (30 mL) were mixed, and the pH was adjusted to 3.5 with concentrated hydrochloric acid. While maintaining the pH at 3 to 5 with aqueous sodium hydroxide, the solution containing the diazonium salt was added dropwise, and the mixture was stirred at 15°C for 3 hours. The resulting precipitate was filtered, washed with water, and dried under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / methylene chloride) to obtain 3.06 g of dye (III-2) as a red solid.

[0421] The maximum absorption wavelength (λmax) of this dye (III-2) in a 10 ppm chloroform solution is 459 nm, and the gram absorption coefficient is 107.6 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (CDCl3, 400MHz) δ0.94(t,3H,J=7.2Hz),1.32-1.43(m,2H),1.55-1.68 (m,2H),2.00-2.12(m,4H),2.62(t,2H,J=7.6Hz),3.41(t,4H,J=6.4Hz),6.6 3(d,2H,J=8.8Hz),7.14(d,2H,J=8.8Hz),7.19(d,2H,J=8.0Hz),7.45(d,2H, J=8.0Hz),7.60(d,2H,J=8.4Hz),7.84(d,2H,J=8.4Hz),7.88(d,2H,J=9.2Hz)

[0422] The chemical structures of the polymerizable liquid crystal compound (I-1) and the dyes (II-1), (III-2), (II-2), and (II-3) synthesized above are shown below. 11 H 22 means that 11 methylene chains are bonded in a linear fashion.

[0423] [ka]

[0424] The chemical structures of the dyes (III-1), (III-3), and (III-4) used in the examples and comparative examples are shown below.

[0425] [ka]

[0426] [Example I-1] 20.00 parts of polymerizable liquid crystal compound (I-1) and 0.30 parts of dye (II-1) were added to 2959.1 parts of chloroform, and the mixture was stirred to dissolve the compound. The solvent was then removed to obtain anisotropic dye film-forming composition I-1. n1 / r n2 is 1. Composition for forming anisotropic dye film I-1 The liquid crystallinity of the compound was confirmed by observing birefringence at 40°C using a polarizing microscope equipped with a hot stage. In order to determine the dichroic ratio by the above-mentioned method using the obtained anisotropic dye film-forming composition I-1, an anisotropic dye film I-1 was produced using a sandwich cell with a cell gap of 8.0 μm, and the dichroic ratio of the anisotropic dye film I-1 was determined. The results are shown in Table 1.

[0427] [Comparative example I-1] Anisotropic dye film-forming composition I-2 and anisotropic dye film I-2 were obtained in the same manner as in Example I-1, except that 0.30 parts of dye (II-1) were replaced with 0.27 parts of dye (III-1) (manufactured by Showa Kako Co., Ltd.). n1 / r n2 is 1. The fact that the anisotropic dye film-forming composition I-2 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film I-2 was also determined. The results are shown in Table 1.

[0428] [Table 1]

[0429] As shown in Table 1, the dye (II-1) used in Example I-1 was highly soluble in toluene and the resulting anisotropic dye film exhibited a high dichroic ratio, whereas Comparative Example I-1 failed to achieve both high solubility in toluene and a high dichroic ratio.

[0430] [Example I-2] To 19.65 parts of polymerizable liquid crystal compound (I-1), 0.09 parts of dye (III-2) dissolved in 885.3 parts of chloroform, 0.10 parts of dye (III-3) (Hayashibara Co., Ltd.) dissolved in 1039.9 parts of chloroform, and 0.23 parts of dye (II-1) dissolved in 2305.2 parts of chloroform were added, stirred to dissolve, and then the solvent was removed to obtain anisotropic dye film-forming composition I-3. n1 / r n2 is 1 for all combinations of liquid crystals and dyes. It was confirmed that the anisotropic dye film-forming composition I-3 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. Using the obtained anisotropic dye film-forming composition I-3, an anisotropic dye film I-3 was prepared in the same manner as in Example I-1, and the dichroic ratio of the anisotropic dye film I-3 was determined. The maximum dichroic ratio of this anisotropic dye film I-3 was 40.5 at 40° C. and a wavelength of 620 nm. The maximum absorption wavelengths of dyes (III-2) and (III-3) in the polymerizable liquid crystal compound (I-1) were 495 nm and 530 nm, respectively.

[0431] [Example I-3] To 718.2 parts of cyclopentanone, 243.6 parts of polymerizable liquid crystal compound (I-1), 4.07 parts of dye (II-1), 5.58 parts of IRGACURE (registered trademark) 369 (BASF product), and 3.62 parts of BYK-361N (BYK-Chemie) were added, and the mixture was heated and stirred at 80°C, and then filtered using a syringe equipped with a syringe filter (Membrane Solutions, PTFE13045, 0.45 μm diameter) to obtain anisotropic dye film composition I-4. n1 / r n2 is 1. Composition I-4 for anisotropic dye films was spin-coated onto a glass substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, alignment film formed by rubbing) had been formed. The film was then dried by heating at 120°C for 2 minutes, cooled to the liquid crystal phase, and exposed to an exposure dose of 500 mJ / cm. 2 Polymerization was performed at 365 nm to obtain an anisotropic dye film I-4. When the obtained anisotropic dye film I-4 was held over a commercially available polarizing plate and rotated, it became bright and dark, confirming that it exhibited good performance suitable for use as a polarizing film.

[0432] [Example I-4] Anisotropic dye film-forming composition I-5 and anisotropic dye film I-5 were obtained in the same manner as in Example I-1, except that 0.28 parts of dye (II-2) was used instead of 0.30 parts of dye (II-1). n1 / r n2 is 1. It was confirmed that the anisotropic dye film-forming composition I-5 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film I-5 was also determined. The results are shown in Table 2.

[0433] [Table 2]

[0434] As can be seen from Table 2, the dye (II-2) used in Example I-4 was highly soluble in toluene, and the resulting anisotropic dye film exhibited a high dichroic ratio.

[0435] [Example I-5] Anisotropic dye film-forming composition I-6 and anisotropic dye film I-6 were obtained in the same manner as in Example I-1, except that 0.27 parts of dye (II-3) was used instead of 0.30 parts of dye (II-1). n1 / r n2 is 1. It was confirmed that the anisotropic dye film-forming composition I-6 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film I-6 was also determined. The results are shown in Table 3.

[0436] [Comparative example I-2] Anisotropic dye film-forming composition I-7 and anisotropic dye film I-7 were obtained in the same manner as in Example I-1, except that 0.20 parts of dye (III-4) was used instead of 0.30 parts of dye (II-1). n1 / r n2 is 1. It was confirmed that the anisotropic dye film-forming composition I-7 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film I-7 was also determined. The results are shown in Table 3.

[0437] [Table 3]

[0438] As shown in Table 3, the dye (II-3) used in Example I-5 exhibited a high dichroic ratio in the resulting anisotropic dye film, and had better solubility in cyclopentanone than the dye (III-4) used in Comparative Example I-2.

[0439] [Synthesis Examples, Examples, and Comparative Examples of the Second Invention] [Synthesis of dyes] <Dye (IV-1)> Dye (IV-1) was synthesized according to the synthesis method described below.

[0440] [ka]

[0441] Synthesis of (IV-1-a): (IV-1-a) was synthesized by the method described in WO 2015 / 048281.

[0442] Synthesis of (IV-1-b): (IV-1-a) (0.5 g, 3.3 mmol), acetic acid (5 mL), and propionic acid (3 mL) were mixed and cooled to 0°C. A solution of concentrated sulfuric acid (2 mL) in water (2 mL) was added, and 40% nitrosylsulfuric acid (1.1 g, 3.4 mmol) was added and stirred at 0°C for 1 hour. A 10% amidosulfuric acid solution (0.3 g, 0.3 mmol) was added to this mixture to prepare a diazonium solution. Aniline (1.3 g, 13.4 mmol), sodium formaldehyde bisulfite (1.8 g, 13.4 mmol), and water (50 mL) were mixed and stirred at 70°C for 2 hours. The mixture was cooled to 0°C, and the above diazonium solution was added dropwise over 30 minutes, followed by stirring at 0°C for 2 hours. The precipitated solid was collected by filtration, dispersed in 1 M aqueous sodium hydroxide solution (3 mL) and water (14 mL), and stirred at 90°C for 2 hours. After cooling, the precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 40°C to obtain 0.6 g of (IV-1-b).

[0443] Synthesis of (IV-1): (IV-1-b) (0.6 g, 2.4 mmol), dimethylformamide (20 mL), and acetic acid (5 mL) were mixed, and 35% hydrochloric acid (1 mL) was added, followed by cooling to 3°C. Sodium nitrite (0.2 g, 2.7 mmol) dissolved in water (2 mL) was added, and the mixture was stirred at 3°C ​​for 1 hour. To this was added 10% amidosulfuric acid solution (0.2 g, 0.2 mmol) to prepare a diazonium solution. Diethylaniline (0.4 g, 2.4 mmol), methanol (8 mL), and dimethylformamide (1 mL) were mixed and cooled to 3° C. The diazonium solution was added dropwise over 30 minutes while adjusting the pH to 3-4 with 25% aqueous sodium hydroxide solution, and then the mixture was stirred at 3° C. for 2 hours. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain 0.2 g of dye (IV-1).

[0444] The maximum absorption wavelength (λmax) of dye (IV-1) in a 10 ppm chloroform solution is 581 nm, and the gram absorption coefficient is 95.1 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (CDCl3, 400MHz) δ1.26(t,6H,J=7.1Hz),δ1.44(t,3H,J=7.5Hz),δ3.04(q,2H,J=7.6Hz),δ3.49(q,4H ,J=7.2Hz),δ6.75(d,2H,J=9.3Hz),δ7.91(d,2H,J=9.2Hz),δ7.97(d,2H,J=8.8Hz),δ8.12(d,2H,J=8.8Hz)

[0445] The solubility of dye (IV-1) in cyclopentanone was measured. 3 mg of dye (IV-1) was added to 103 mg of cyclopentanone and stirred at 80°C for 5 minutes. The mixture was then allowed to stand at room temperature for 1 hour. The resulting mixture was filtered using a syringe equipped with a syringe filter (Membrane Solutions, PTFE13045, 0.45 μm diameter) to obtain a saturated solution of dye (IV-1) in cyclopentanone. This solution was diluted with 746 mg of tetrahydrofuran, and the concentration was determined using HPLC (Hitachi High-Technologies L-2300 series). A 0.1% by mass solution of dye (IV-1) was prepared in tetrahydrofuran, and a calibration curve was prepared at an absorption wavelength of 254 nm. The concentration of the saturated cyclopentanone solution was measured using this calibration curve. The results are shown in Table 4.

[0446] <Dye (IV-2)> Dye (IV-2) was synthesized according to the synthesis method described below.

[0447] [ka]

[0448] Synthesis of (IV-2-a): Concentrated sulfuric acid (1 mL) and sodium nitrite (0.2 g, 2.8 mmol) were mixed and stirred at 60°C for 30 minutes, then cooled to 3°C. Acetic acid (5 mL) and propionic acid (2 mL) were added, and 5-butylthio-1,3,4-thiadiazol-2-amine (0.5 g, 2.6 mmol) was added, followed by stirring at 3°C ​​for 1 hour. To this was added 10% amidosulfuric acid solution (0.3 g, 0.3 mmol) to prepare a diazonium solution. Aniline (1.0 g, 10.8 mmol), formaldehyde sodium bisulfite (1.5 g, 10.8 mmol), and water (50 mL) were mixed and stirred at 70°C for 2 hours. The mixture was cooled to 3°C, and the above diazonium solution was added dropwise over 30 minutes, followed by stirring at 3°C ​​for 2 hours. The precipitated solid was collected by filtration, dispersed in 25% aqueous sodium hydroxide solution (1 mL) and water (16 mL), and stirred at 90°C for 2 hours. After cooling, the precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 40°C to obtain 0.4 g of (IV-2-a).

[0449] Synthesis of (IV-2): (IV-2-a) (0.4 g, 1.5 mmol), dimethylformamide (14 mL), and acetic acid (4 mL) were mixed, and 35% hydrochloric acid (1 mL) was added, followed by cooling to 3°C. Sodium nitrite (0.1 g, 1.6 mmol) dissolved in water (1 mL) was added, and the mixture was stirred at 3°C ​​for 3 hours. 10% amidosulfuric acid solution (0.1 g, 0.1 mmol) was added to the mixture to prepare a diazonium solution. Diethylaniline (0.2 g, 1.5 mmol), methanol (5 mL), and dimethylformamide (1 mL) were mixed and cooled to 3° C. The diazonium solution was added dropwise over 30 minutes while adjusting the pH to 3-4 with 25% aqueous sodium hydroxide solution, and then the mixture was stirred at 3° C. for 2 hours. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.1 g of dye (IV-2).

[0450] The maximum absorption wavelength (λmax) of dye (IV-2) in a 10 ppm chloroform solution is 551 nm, and the gram absorption coefficient is 83.9 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (CDCl3, 400MHz) δ0.99(t,3H,J=7.4Hz),δ1.26(t,6H,J=7.1Hz),δ1.48-1.58(m,2H),δ1.81-1.89(m,2H),δ 3.42-3.52(m,6H),δ6.74(d,2H,J=9.2Hz),δ7.90(d,2H,J=9.2Hz),δ7.96(d,2H,J=8.8Hz),δ8.10(d,2H,J=8.8Hz)

[0451] The solubility of dye (IV-2) in cyclopentanone was measured in the same manner as for dye (IV-1) (detection absorption wavelength: 254 nm). The results are shown in Table 4.

[0452] <Dye (IV-3)> Dye (IV-3) was synthesized according to the synthesis method described below.

[0453] [ka]

[0454] Synthesis of (IV-3-a): 2-Amino-5-methyl-3-thiophenecarbonitrile (0.5 g, 3.6 mmol), acetic acid (5 mL), and propionic acid (3 mL) were mixed and cooled to 3°C. A solution of concentrated sulfuric acid (2 mL) in water (2 mL) was added, and 40% nitrosylsulfuric acid (1.2 g, 3.8 mmol) was added and stirred at 3°C ​​for 1 hour. To this was added 10% amidosulfuric acid solution (0.4 g, 0.4 mmol) to prepare a diazonium solution. Aniline (1.4 g, 14.8 mmol), formaldehyde sodium bisulfite (2.0 g, 14.8 mmol), and water (50 mL) were mixed and stirred at 70°C for 2.5 hours. The mixture was cooled to 3°C, and the above diazonium solution was added dropwise over 30 minutes, followed by stirring at 3°C ​​for 2 hours. The precipitated solid was collected by filtration, dispersed in 25% aqueous sodium hydroxide solution (1 mL) and water (16 mL), and stirred at 90°C for 2 hours. After cooling, the precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 40°C to obtain 0.6 g of (IV-3-a).

[0455] Synthesis of (IV-3): (IV-3-a) (0.6 g, 2.5 mmol), dimethylformamide (20 mL), and acetic acid (5 mL) were mixed, and 35% hydrochloric acid (1 mL) was added, followed by cooling to 3°C. Sodium nitrite (0.2 g, 2.8 mmol) dissolved in water (2 mL) was added, and the mixture was stirred at 3°C ​​for 1 hour. To this was added 10% amidosulfuric acid solution (0.2 g, 0.2 mmol) to prepare a diazonium solution. Diethylaniline (0.4 g, 2.5 mmol), methanol (7 mL), and dimethylformamide (1 mL) were mixed and cooled to 3° C. The diazonium solution was added dropwise over 30 minutes while adjusting the pH to 3-4 with 25% aqueous sodium hydroxide solution, and then the mixture was stirred at 3° C. for 1.5 hours. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.2 g of dye (IV-3).

[0456] The maximum absorption wavelength (λmax) of dye (IV-3) in a 10 ppm chloroform solution is 541 nm, and the gram absorption coefficient is 100.0 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (CDCl3, 400MHz) δ1.25(t,6H,J=7.1Hz),δ2.55(s,3H),δ3.48(q,4H,J=7.1Hz),δ6.74(d,2H ,J=9.3Hz),δ7.05(s,1H),δ7.90(d,2H,J=9.2Hz),δ7.94(d,2H,J=8.9Hz),δ8.05(d,2H,J=8.9Hz)

[0457] The solubility of dye (IV-3) in cyclopentanone was measured in the same manner as for dye (IV-1) (detection absorption wavelength: 254 nm). The results are shown in Table 4.

[0458] <Dye (IV-4)> Dye (IV-4) was synthesized according to the synthesis method described below.

[0459] [ka]

[0460] Synthesis of (IV-4-a): 5-Amino-3-methylisothiazole (0.5 g, 4.4 mmol), acetic acid (5 mL), and propionic acid (3 mL) were mixed and cooled to 0°C. A solution of concentrated sulfuric acid (2 mL) in water (2 mL) was added, and 40% nitrosylsulfuric acid (1.5 g, 4.6 mmol) was added and stirred at 0°C for 1 hour. To this was added 10% amidosulfuric acid solution (0.4 g, 0.4 mmol) to prepare a diazonium solution. Aniline (1.7 g, 18.0 mmol), formaldehyde sodium bisulfite (2.4 g, 18.0 mmol), and water (50 mL) were mixed and stirred at 70°C for 2.5 hours. The mixture was cooled to 0°C, and the above diazonium solution was added dropwise over 1 hour, followed by stirring at 0°C for 2 hours. The precipitated solid was collected by filtration, dispersed in 25% aqueous sodium hydroxide solution (1 mL) and water (16 mL), and stirred at 60°C for 3 hours. After cooling, the precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 40°C to obtain 0.6 g of (IV-4-a).

[0461] Synthesis of (IV-4): (IV-4-a) (0.6 g, 2.9 mmol), dimethylformamide (21 mL), and acetic acid (5 mL) were mixed, and 35% hydrochloric acid (1 mL) was added, followed by cooling to -3°C. Sodium nitrite (0.2 g, 3.2 mmol) dissolved in water (2 mL) was added, and the mixture was stirred at -3°C for 1 hour. To this was added 10% amidosulfuric acid solution (0.3 g, 0.3 mmol) to prepare a diazonium solution. Diethylaniline (0.4 g, 2.9 mmol), methanol (8 mL), and dimethylformamide (1 mL) were mixed and cooled to -3°C. While adjusting the pH to 3-4 with 25% aqueous sodium hydroxide, the above diazonium solution was added dropwise over 30 minutes, and then the mixture was stirred at 0°C for 1 hour. The precipitated solid was collected by filtration, and the resulting crude product was washed with water and hexane to obtain 0.5 g of dye (IV-4).

[0462] The maximum absorption wavelength (λmax) of dye (IV-4) in a 10 ppm chloroform solution is 528 nm, and the gram absorption coefficient is 104.9 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (CDCl3, 400MHz) δ1.25(t,6H,J=7.0Hz),δ2.54(s,3H),δ3.47(q,4H,J=7.1Hz),δ6.74(d,2H,J =9.2Hz),δ7.72-7.75(m,1H),δ7.88(d,2H,J=9.2Hz),δ7.96(d,2H,J=8.9Hz),δ8.09(d,2H,J=8.9Hz)

[0463] The solubility of dye (IV-4) in cyclopentanone was measured in the same manner as for dye (IV-1) (detection absorption wavelength: 254 nm). The results are shown in Table 4.

[0464] <Dye (V-1)> Dye (V-1) was synthesized according to the synthesis method described below.

[0465] [ka]

[0466] Synthesis of (V-1-a): (V-1-a) was synthesized by the method described in WO 2010 / 126163.

[0467] Synthesis of (V-1-b): 4-Nitroaniline (0.5 g, 3.6 mmol), N-methylpyrrolidone (10 mL), and water (8 mL) were mixed, to which 35% hydrochloric acid (1 mL) was added, and the mixture was cooled to 3°C. Sodium nitrite (0.3 g, 4.0 mmol) dissolved in water (3 mL) was added, and the mixture was stirred at 3°C ​​for 1 hour. To this mixture was added 10% amidosulfuric acid solution (0.4 g, 0.4 mmol) to prepare a diazonium solution. (V-1-a) (0.6 g, 3.6 mmol), methanol (6 mL), and water (1 mL) were mixed and cooled to 3°C. The above diazonium solution was added dropwise over 30 minutes, and then the mixture was stirred at 3°C ​​for 2 hours. The precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 40°C to obtain 1.1 g of (V-1-b).

[0468] Synthesis of (V-1-c): (V-1-b) (1.1 g, 3.5 mmol) and ethanol (70 mL) were mixed and heated to 80°C. Sodium sulfide nonahydrate (3.3 g, 13.9 mmol) dissolved in water (20 mL) was added, and the mixture was stirred at 60°C for 5 hours. The reaction solution was allowed to cool, concentrated, washed with water, and then dried under reduced pressure at 40°C to obtain 0.4 g of (V-1-c).

[0469] Synthesis of (V-1): (V-1-c) (0.4 g, 1.4 mmol), dimethylformamide (13 mL), and acetic acid (3 mL) were mixed, and 35% hydrochloric acid (1 mL) was added, followed by cooling to 3°C. Sodium nitrite (0.1 g, 1.5 mmol) dissolved in water (1 mL) was added, and the mixture was stirred at 3°C ​​for 1 hour. To this was added 10% amidosulfuric acid solution (0.3 g, 0.3 mmol) to prepare a diazonium solution. Diethylaniline (0.5 g, 3.6 mmol), methanol (6 mL), and dimethylformamide (1 mL) were mixed and cooled to 3° C. The diazonium solution was added dropwise over 30 minutes while adjusting the pH to 3-4 with 25% aqueous sodium hydroxide solution, and then the mixture was stirred at 3° C. for 2 hours. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.2 g of dye (V-1).

[0470] The maximum absorption wavelength (λmax) of dye (V-1) in a 10 ppm chloroform solution is 502 nm, and the gram absorption coefficient is 114.0 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (CDCl3, 400MHz) δ1.24(t,6H,J=7.1Hz),δ1.32(t,3H,J=7.6Hz),δ1.53(s,9H),δ2.67(q,2H,J=7.6Hz),δ3.4 5(q,4H,J=7.1Hz),δ6.72(d,2H,J=9.2Hz),δ7.44(d,2H,J=8.9Hz),δ7.84(d,2H,J=9.2Hz),δ7.88(d,2H,J=8.9Hz)

[0471] The solubility of dye (V-1) in cyclopentanone was measured in the same manner as for dye (IV-1) (detection absorption wavelength: 254 nm). The results are shown in Table 4.

[0472] <Dye (V-2)> Dye (V-2) was synthesized according to the synthesis method described below.

[0473] [ka]

[0474] Synthesis of (V-2-a): 2-Amino-4,5-dicyano-1H-imidazole (2.0 g, 8.4 mmol) and water (60 mL) were mixed, 35% hydrochloric acid (2 mL) was added, and the mixture was cooled to 3°C. Sodium nitrite (0.6 g, 9.3 mmol) dissolved in water (3 mL) was added, and the mixture was stirred at 3°C ​​for 1 hour. To this was added 10% amidosulfuric acid solution (0.8 g, 0.8 mmol) to prepare a diazonium solution. Aniline (5.7 g, 18.0 mmol), formaldehyde sodium bisulfite (2.4 g, 18.0 mmol), and water (50 mL) were mixed and stirred at 70°C for 2 hours. The mixture was cooled to 3°C, and the above diazonium solution was added dropwise over 1 hour, followed by stirring at 3°C ​​for 2 hours. The precipitated solid was collected by filtration, dispersed in 25% aqueous sodium hydroxide solution (1 mL) and water (14 mL), and stirred at 90°C for 3 hours. After cooling, the precipitated solid was collected by filtration, washed with water, and dried under reduced pressure at 40°C to obtain 0.3 g of (V-2-a).

[0475] Synthesis of (V-2): (V-2-a) (0.3 g, 1.1 mmol), dimethylformamide (9 mL), and acetic acid (2 mL) were mixed, and 35% hydrochloric acid (1 mL) was added, followed by cooling to 3°C. Sodium nitrite (0.1 g, 1.3 mmol) dissolved in water (1 mL) was added, and the mixture was stirred at 3°C ​​for 2 hours. 10% sulfamic acid amido solution (0.2 g, 0.2 mmol) was added to the mixture to prepare a diazonium solution. Diethylaniline (0.2 g, 1.1 mmol), methanol (8 mL), and water (1 mL) were mixed and cooled to 3° C. The diazonium solution was added dropwise over 30 minutes while adjusting the pH to 3-4 with 25% aqueous sodium hydroxide solution, and then the mixture was stirred at 3° C. for 2 hours. The precipitated solid was collected by filtration, and the resulting crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 0.1 g of dye (V-2).

[0476] The maximum absorption wavelength (λmax) of dye (V-2) in a 10 ppm chloroform solution is 545 nm, and the gram absorption coefficient is 80.5 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1 H-NMR (DMSO-d6, 400MHz) δ1.17(t,6H,J=7.0Hz),δ3.49(q,4H,J=7.0Hz),δ6.85(d,2 H,J=9.3Hz),δ7.84(d,2H,J=9.2Hz),δ7.97(d,2H,J=8.7Hz),δ8.06(d,2H,J=8.7Hz)

[0477] The solubility of this dye (V-2) in cyclopentanone was measured in the same manner as for dye (IV-1) (detection absorption wavelength: 254 nm). The results are shown in Table 4.

[0478] <Dye (V-3)> Dye (V-3) was synthesized according to the synthesis method described below.

[0479] [ka]

[0480] Synthesis of (V-3-a): 2-Amino-5,6-dimethylbenzothiazole (2.5 g, 14.0 mmol) and 85% phosphoric acid (38 mL) were mixed and heated to 80°C for dispersion. This was cooled to 5-10°C, and 40% nitrosylsulfuric acid (5.6 g, 17.6 mmol) was added. The mixture was stirred at 5-10°C for 1 hour to prepare a diazonium solution. Aniline (4.3 g, 46.3 mmol), formaldehyde sodium bisulfite (6.2 g, 46.3 mmol), and water (431 mL) were mixed and stirred at 70°C for 2 hours. The mixture was cooled to 5-10°C, and amidosulfuric acid (0.3 g, 2.8 mmol) was added. The above diazonium solution was added dropwise over 1 hour, and the mixture was stirred at 5-10°C for 30 minutes. Sodium chloride (30 g) was added and the mixture was stirred for 10 minutes. The precipitated solid was collected by filtration and dissolved in 1 M aqueous sodium hydroxide solution ( 250mL) and stirred at 90°C for 2 hours. After cooling, the precipitated solid was collected by filtration and washed with methanol. The solid was then dissolved in chloroform and filtered through Celite to remove insoluble components. The filtrate was concentrated, and the resulting crude product was purified by silica gel column chromatography (chloroform). Reprecipitation was performed with dimethylformamide (10 mL) / water (15 mL), and the collected solid was washed with methanol and dried under reduced pressure at 40°C to obtain 2.0 g of (V-3-a).

[0481] Synthesis of (V-3): (V-3-a) (2.0 g, 7.1 mmol) and N-methylpyrrolidone (24 mL) were mixed and cooled to 5-10°C. 35% hydrochloric acid (2 mL) and water (14 mL) were added, followed by the addition of sodium nitrite (0.5 g, 7.8 mmol) dissolved in water (31 mL), and the mixture was stirred at 5-10°C for 1 hour. 10% sulfamic acid amido solution (0.1 g, 0.1 mmol) was added to the mixture to prepare a diazonium solution. Diethylaniline (1.1 g, 7.1 mmol), methanol (30 mL), and water (30 mL) were mixed and adjusted to pH 3.5 with 35% hydrochloric acid. The mixture was cooled to 5-10°C, and the diazonium solution was added dropwise over 45 minutes while adjusting the pH to 5-6 with 25% aqueous sodium hydroxide. The mixture was then stirred at 5-10°C for 1 hour. Water (350 mL) was added, and the precipitated solid was collected by filtration and washed with water and methanol. The resulting solid was suspended and washed in methanol (80 mL) and then reprecipitated with dichloromethane (50 mL) / methanol (150 mL). The resulting crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain 0.6 g of dye (V-3).

[0482] The maximum absorption wavelength (λmax) of dye (V-3) in a 10 ppm chloroform solution is 546 nm, and the gram absorption coefficient is 106.0 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1H-NMR (CDCl3, 400MHz) δ1.26(t,6H,J=7.1Hz),δ2.43(s,6H),δ3.49(q,4H,J=7.1Hz ), δ6.74(d,2H,J=8.9Hz),δ7.66(s,1H),δ7.90-8.00(m,5H),δ8.17(d,2H,J=8.6Hz)

[0483] The solubility of dye (V-3) in cyclopentanone was measured in the same manner as for dye (IV-1) (detection absorption wavelength: 254 nm). The results are shown in Table 4.

[0484] <Dye (V-4)> Dye (V-4) was synthesized according to the synthesis method described below.

[0485] [ka]

[0486] Synthesis of (V-4-a): Tetrahydrofuran (100 mL) and sodium hydride (60% purity, 6.7 g, 168.0 mmol) were added to an ice-cooled reactor, and a mixture of diethyl (4-nitrobenzyl)phosphonate (18.0 g, 65.9 mmol), 4-butylbenzaldehyde (9.1 g, 56.1 mmol), and tetrahydrofuran (50 mL) was added dropwise over 10 minutes. The mixture was washed with tetrahydrofuran (30 mL) and then stirred at 50 °C for 0.5 hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was evaporated. The resulting crude product was dissolved in ethyl acetate (20 mL) with heating, added with hexane (50 mL), and cooled. The precipitate was filtered, washed with hexane, and dried under reduced pressure to obtain 15.0 g of (V-4-a).

[0487] Synthesis of (V-4-b): (V-4-a) (15.0 g, 53.3 mmol), tetrahydrofuran (150 mL), and iron powder (13.9 g, 248.9 mmol) were mixed, and ammonium chloride (13.3 g, 248.6 mmol) dissolved in water (30 mL) was added dropwise, followed by stirring at 50 °C for 3 hours. The mixture was filtered through Celite, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The resulting crude product was suspended in hexane, and the precipitate was filtered off, washed with hexane, and dried to obtain 10.9 g of (V-4-b).

[0488] Synthesis of (V-4): (V-4-b) (2.51 g, 10.0 mmol), N-methylpyrrolidone (40 mL), concentrated hydrochloric acid (2.2 mL), and water (20 mL) were mixed and cooled to 3°C. Then, sodium nitrite (789 mg, 11.4 mmol) was added and the mixture was stirred at 15°C for 3.5 hours. 1-Phenylpyrrolidine (1.47 g, 10.0 mmol), methanol (60 mL), and water (30 mL) were mixed, and the pH was adjusted to 3.5 with concentrated hydrochloric acid. While maintaining the pH at 3 to 5 with aqueous sodium hydroxide, the solution containing the diazonium salt was added dropwise, and the mixture was stirred at 15°C for 3 hours. The resulting precipitate was filtered, washed with water, and dried under reduced pressure. The resulting crude product was purified by silica gel column chromatography (hexane / methylene chloride) to obtain 3.06 g of a red solid dye (V-4).

[0489] The maximum absorption wavelength (λmax) of dye (V-4) in a 10 ppm chloroform solution is 459 nm, and the gram absorption coefficient is 107.6 Lg -1 cm -1 It was. The structure was also confirmed by NMR, and the results are shown below. 1H-NMR (CDCl3, 400MHz) δ0.94(t,3H,J=7.2Hz),1.32-1.43(m,2H),1.55-1.68 (m,2H),2.00-2.12(m,4H),2.62(t,2H,J=7.6Hz),3.41(t,4H,J=6.4Hz),6.6 3(d,2H,J=8.8Hz),7.14(d,2H,J=8.8Hz),7.19(d,2H,J=8.0Hz),7.45(d,2H, J=8.0Hz),7.60(d,2H,J=8.4Hz),7.84(d,2H,J=8.4Hz),7.88(d,2H,J=9.2Hz)

[0490] The chemical structures of the polymerizable liquid crystal compound and dye synthesized above are shown below. 11 H 22 means that 11 methylene chains are bonded in a linear fashion.

[0491] [ka]

[0492] The chemical structure of the dye (V-5) used in the examples is shown below.

[0493] [ka]

[0494] [Example II-1] 20.00 parts of polymerizable liquid crystal compound (I-1) and 0.32 parts of dye (IV-1) were added to 3154.6 parts of chloroform, and the mixture was stirred to dissolve the compound. The solvent was then removed to obtain an anisotropic dye film-forming composition II-1. n1 / r n2 is 1. The fact that the anisotropic dye film-forming composition II-1 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. In order to determine the dichroic ratio using the obtained anisotropic dye film-forming composition II-1 by the method described above, an anisotropic dye film II-1 was produced using a sandwich cell with a cell gap of 8.0 μm, and the dichroic ratio of the anisotropic dye film II-1 was determined. The results are shown in Table 4.

[0495] [Example II-2] Anisotropic dye film-forming composition II-2 and anisotropic dye film II-2 were obtained in the same manner as in Example II-1, except that 0.36 parts of dye (IV-2) was used instead of 0.32 parts of dye (IV-1). n1 / r n2 is 1. The fact that the anisotropic dye film-forming composition II-2 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film II-2 was also determined. The results are shown in Table 4.

[0496] [Example II-3] Anisotropic dye film-forming composition II-3 and anisotropic dye film II-3 were obtained in the same manner as in Example II-1, except that 0.28 parts of dye (IV-3) was used instead of 0.32 parts of dye (IV-1). n1 / r n2 is 1. The fact that the anisotropic dye film-forming composition II-3 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film II-3 was also determined. The results are shown in Table 4.

[0497] [Example II-4] Anisotropic dye film-forming composition II-4 and anisotropic dye film II-4 were obtained in the same manner as in Example II-1, except that 0.29 parts of dye (IV-4) was used instead of 0.32 parts of dye (IV-1). n1 / r n2is 1. The fact that the anisotropic dye film-forming composition II-4 exhibited liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. The dichroic ratio of the anisotropic dye film II-4 was also determined. The results are shown in Table 4.

[0498] [Comparative Example II-1] Anisotropic dye film-forming composition II-5 and anisotropic dye film II-5 were obtained in the same manner as in Example II-1, except that 0.26 parts of dye (V-1) was used instead of 0.32 parts of dye (IV-1). n1 / r n2 is 1. The dichroic ratio of the anisotropic dye film II-5 was also determined. The results are shown in Table 4.

[0499] [Comparative Example II-2] Anisotropic dye film-forming composition II-6 and anisotropic dye film II-6 were obtained in the same manner as in Example II-1, except that 0.37 parts of dye (V-2) were used instead of 0.32 parts of dye (IV-1). n1 / r n2 is 1. The dichroic ratio of the anisotropic dye film II-6 was also determined. The results are shown in Table 4.

[0500] [Comparative Example II-3] Anisotropic dye film-forming composition II-7 and anisotropic dye film II-7 were obtained in the same manner as in Example II-1, except that 0.28 parts of dye (V-3) was used instead of 0.32 parts of dye (IV-1). n1 / r n2 is 1. The dichroic ratio of the anisotropic dye film II-7 was also determined. The results are shown in Table 4.

[0501] [Table 4]

[0502] As shown in Table 4, the dyes (IV-1) to (IV-4) used in Examples II-1 to II-4 were highly soluble in cyclopentanone and exhibited high dichroic ratios in the resulting anisotropic dye films. On the other hand, Comparative Examples II-1 to II-3 did not achieve both high solubility in cyclopentanone and a high dichroic ratio.

[0503] [Example II-5] To 19.65 parts of polymerizable liquid crystal compound (I-1), 0.09 parts of dye (V-4) dissolved in 885.3 parts of chloroform, 0.10 parts of dye (V-5) (manufactured by Hayashibara Co., Ltd.) dissolved in 1039.9 parts of chloroform, and 0.22 parts of dye (IV-2) dissolved in 2237.2 parts of chloroform were added, stirred to dissolve, and then the solvent was removed to obtain composition II-8 for forming an anisotropic dye film. It was confirmed that the anisotropic dye film-forming composition II-8 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage. Using the obtained anisotropic dye film-forming composition II-8, an anisotropic dye film II-8 was produced by the above-mentioned method in order to determine the dichroic ratio, and the dichroic ratio of the anisotropic dye film II-8 was determined. The maximum dichroic ratio of the anisotropic dye film II-8 was 38.0 at 40°C and a wavelength of 645 nm. The maximum absorption wavelengths of the dyes (V-4) and (V-5) in the polymerizable liquid crystal compound (I-1) were 495 nm and 530 nm, respectively.

[0504] [Example II-6] To 718.2 parts of cyclopentanone, 243.6 parts of polymerizable liquid crystal compound (I-1), 3.95 parts of dye (IV-2), 5.58 parts of IRGACURE (registered trademark) 369 (a product of BASF), and 3.62 parts of BYK-361N (manufactured by BYK-Chemie) were added, and the mixture was heated and stirred at 80°C, and then filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm), thereby obtaining composition II-9 for anisotropic dye films. Composition II-9 for anisotropic dye films was spin-coated onto a glass substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, alignment film formed by rubbing) had been formed. The film was then dried by heating at 120°C for 2 minutes, cooled to the liquid crystal phase, and exposed to an exposure dose of 500 mJ / cm. 2 The anisotropic dye film II-9 was obtained by polymerization at 365 nm. When the obtained anisotropic dye film II-9 was held over a commercially available polarizing plate and rotated, it became bright and dark, confirming its excellent performance as a polarizing film.

[0505] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2020-131810 filed on August 3, 2020, and Japanese Patent Application No. 2020-131811 filed on August 3, 2020, which are incorporated by reference in their entirety. [Industrial Applicability]

[0506] According to the anisotropic dye film-forming composition of the present invention, by using a specific dye and a polymerizable liquid crystal compound, it is possible to achieve excellent film-coating properties and excellent optical performance due to high dichroism. The anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention, and therefore can achieve excellent optical performance. The optical element of the present invention includes the anisotropic dye film of the present invention, and therefore can achieve excellent optical performance.

Claims

1. A compound represented by the following formula (1): X-A １ -(N=N-A ２ ) ｎ -N=N-A ３ -Y …(1) (In formula (1), -A １ - and - A ２ each - independently represents a divalent group of an aromatic heterocycle containing one or more S atoms which may have a substituent, wherein atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other; a divalent group of a benzisothiazole ring which may have a substituent; or a divalent group of an aromatic hydrocarbon ring which may have a substituent; -A ３ - represents a divalent aromatic hydrocarbon ring group which may have a substituent; -X represents an alkyl group (-R), an alkoxy group (-O-R), or an alkylsulfanyl group (-S-R) having 3 or more carbon atoms, which does not have a cycloalkyl structure, has a branch at the -R terminal, and the branch is a dimethyl group or a trimethyl group; -Y represents a monovalent organic group; n represents 1, 2 or 3. When n is 2 or 3, multiple -A ２ - may be the same or different. However, -A １ - and - A ２ Both - and - are not divalent groups of aromatic hydrocarbon rings which may have a substituent.)

2. The compound according to claim 1, wherein in the formula (1), the aromatic heterocycle containing one or more S atoms and in which atoms other than carbon atoms constituting the aromatic heterocycle are not adjacent to each other is a thiophene ring, a benzothiophene ring, a thiazole ring, a thienopyrrole ring, a thienothiophene ring, a furothiazole ring, a thienofuran ring, a thienothiazole ring, or a benzothiazole ring.

3. In the formula (1), -A ３ The compound according to claim 1 or 2, wherein - is a phenylene group which may have a substituent.

4. In the formula (1), -A ２ The compound according to any one of claims 1 to 3, wherein - is a phenylene group which may have a substituent.

5. In the formula (1), -Y is -O-R ｘ or -N(-R ｙ )-R ｘ The compound according to any one of claims 1 to 4, However, -R ｘ and -R ｙ each independently represents an optionally branched alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms, -R ｘ and -R ｙ may be joined together to form a ring, The alkyl group having 1 to 15 carbon atoms which may be branched and the aryl group having 5 to 14 ring atoms each may have a substituent; The alkyl group having 1 to 15 carbon atoms, which may be branched, the cycloalkyl group having 5 to 14 ring atoms, or -R ｘ and -R ｙ and one or more methylene groups contained in the ring formed by combining them may be —O—, —S—, —NH—, —N(R ｚ )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF ２ -, -CHCl-, -CCl ２ -, an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group, R ｚ represents a linear or branched alkyl group having 1 to 6 carbon atoms.

6. A composition for forming an anisotropic dye film, comprising the compound according to any one of claims 1 to 5 and a polymerizable liquid crystal compound.

7. The number of ring structures (r ｎ１ ) and the number of ring structures (r ｎ２ ) and the ratio (r ｎ１ / r ｎ２ 7. The anisotropic dye film-forming composition according to claim 6, wherein the value of (a) is 0.7 to 1.

5.

8. 8. The composition for forming an anisotropic dye film according to claim 6, wherein the polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond.

9. 9. The composition for forming an anisotropic dye film according to claim 6, further comprising a dye having a wavelength showing a maximum value in an absorption curve in a wavelength range of 350 nm to 800 nm that is shorter than the wavelength showing a maximum value in an absorption curve in a wavelength range of 350 nm to 800 nm of the compound represented by formula (1).

10. An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of claims 6 to 9.

11. An optical element comprising the anisotropic dye film according to claim 10.

12. A method for producing an anisotropic dye film, comprising a step of applying the composition for forming an anisotropic dye film according to any one of claims 6 to 9 to a substrate.

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