TWI838473B - Composition for forming anisotropic pigment film, anisotropic pigment film and optical element - Google Patents

Abstract

The present invention provides a composition for forming an anisotropic dye film that can achieve excellent optical properties, especially can achieve a sufficient dichroic ratio. The anisotropic dye film-forming composition of the present invention comprises a dye and a polymerizable liquid crystal compound, and the above-mentioned dye comprises a compound represented by formula (1). A ¹ -CH=CH-A ² -(N=NA ³ ) _n -X (1) (wherein, A ¹ represents a monovalent group of an aromatic hydrocarbon ring that may have a substituent (but excluding a sulfonic group) or a monovalent group of an aromatic heterocyclic ring that may have a substituent (but excluding a sulfonic group); A ² and A ³ each independently represent a divalent group of an aromatic hydrocarbon ring that may have a substituent (but excluding a sulfonic group) or a divalent group of an aromatic heterocyclic ring that may have a substituent (but excluding a sulfonic group); X represents a monovalent organic group; n represents 1, 2 or 3)

Description

Composition for forming anisotropic pigment film, anisotropic pigment film and optical element

The present invention relates to an anisotropic dye film forming composition, an anisotropic dye film, and an optical element that exhibits higher dichroism, which is useful for an anisotropic dye film formed by coating a liquid crystal composition, especially a polarizing film possessed by a dimming element, a liquid crystal element (LCD), and an organic electroluminescent element (OLED) display element. This case claims priority based on Japanese Patent Application No. 2019-037800 filed in Japan on March 1, 2019, and its contents are cited herein.

In LCD, linear polarizing film and circular polarizing film are used to control the optical rotation or birefringence during display. In OLED, circular polarizing film is used to prevent reflection of external light in bright places.

Previously, as such polarizing films, for example, polarizing films obtained by dyeing polyvinyl alcohol (PVA) with low-concentration iodine (iodine-PVA polarizing films) are known (Patent Document 1). In addition, 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, there is no disclosure of a polarizing film containing a dichroic dye having a maximum absorption in the wavelength range of 380 nm to 520 nm and having a sufficient dichroic ratio. Furthermore, an anisotropic dye film using a non-polymerizable polymer liquid crystal and a stilbene dye as a dichroic dye is also known (Non-Patent Document 1). However, a sufficient dichroic ratio for a polarizing film cannot be obtained by combining with a polymer liquid crystal. [Prior Art Document] [Patent Document]

[Patent document 1] Japanese Patent Publication No. 1-105204 [Patent document 2] Japanese Patent Publication No. 2007-510946 [Non-patent document]

[Non-patent document 1] Jae Bok Chang et al., “Optimized molecular structures of guest-host system for highly efficient coatable polarizer”, Dyes and Pigments (2015), 121, 265-275

[The problem the invention is trying to solve]

However, such low-concentration iodine-PVA polarizing plates have the following problems: depending on the usage environment, iodine sublimates or deteriorates, causing the color tone to change; or the PVA stretching is relaxed, causing warping. In addition, regarding the polarizing film formed by coating the liquid crystal composition containing the pigment, there is a problem that a higher light absorption selectivity performance cannot be obtained.

Under such circumstances, a polarizing film having high light absorption selectivity even in a thin film is desired. In order to improve the dichroism of an anisotropic dye film formed by an anisotropic dye film-forming composition, it is considered to increase the ratio of the major axis to the minor axis of the dichroic dye contained in the anisotropic dye film-forming composition, that is, to expand the π-conjugated system to increase the molecular major-minor axis ratio.

However, if the π-conjugated system of the dichroic pigment molecule is extended to increase the molecular length-short axis ratio, the dichroism is improved, but it becomes a pigment that absorbs in the long-wavelength visible light region. On the other hand, in order to absorb in the short-wavelength visible light region, the π-conjugated system must be shortened. Yellow dichroic pigments that absorb in the short-wavelength visible light region tend to have smaller molecular length-short axes and lower dichroism. Therefore, it is particularly difficult to obtain a polarizing film with high light absorption selectivity in the short-wavelength visible light region of 380 nm to 520 nm. On the other hand, in a polarizing film covering the entire visible light region, since the dichroism in the short-wavelength visible light region is relatively low, light in the blue region cannot be fully shielded and passes through, which is known as "bluish".

Furthermore, it is known that in a polarizing film formed by coating a liquid crystal composition containing a pigment, the combination of liquid crystal molecules and dichroic pigments makes the dichroic ratio different, and it is important to use a dichroic pigment that matches the liquid crystal molecule combination used. Under such circumstances, it is desired to develop a dichroic pigment molecule that can make an anisotropic pigment film show higher dichroism and a composition for forming an anisotropic pigment film containing the dichroic pigment molecule.

The object of the present invention is to provide a composition for forming an anisotropic pigment film capable of achieving excellent optical performance, especially capable of achieving a sufficient dichroic ratio. In addition, the object of the present invention is to provide an anisotropic pigment film capable of achieving excellent optical performance, especially capable of achieving a sufficient dichroic ratio. In addition, the object of the present invention is to provide an optical element including an anisotropic pigment film capable of achieving excellent optical performance, especially capable of achieving a sufficient dichroic ratio. [Technical means for solving the problem]

The inventors of the present invention have found that the above-mentioned problem can be solved by using a compound having a specific structure as a pigment in a composition for forming an anisotropic pigment film containing a pigment and a polymerizable liquid crystal compound. That is, the present invention has the following aspects.

[1] A composition for forming an anisotropic dye film, comprising a dye and a polymerizable liquid crystal compound, wherein the dye comprises a compound represented by formula (1). A ¹ -CH=CH-A ² -(N=NA ³ ) _n -X (1) (wherein, A ¹ represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (but excluding a sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent (but excluding a sulfo group); A ² and A ³ each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent (but excluding a sulfo group) or a divalent group of an aromatic heterocyclic ring which may have a substituent (but excluding a sulfo group); X represents a monovalent organic group; and n represents 1, 2 or 3) [2] The composition for forming an anisotropic dye film as described in [1], wherein A ³ is a phenylene group which may have a substituent (but excluding a sulfo group). [3] The anisotropic dye film-forming composition as described in [1] or [2], wherein ^A2 is a divalent aromatic hydrocarbon group which may have a substituent (but excluding a sulfo group). [4] The anisotropic dye film-forming composition as described in any one of [1] to [3], wherein ^A1 is a monovalent aromatic hydrocarbon group which may have a substituent (but excluding a sulfo group). [5] The anisotropic dye film-forming composition according to any one of [1] to [4], wherein X is -O-( ^Rx ) or -N( ^-Rx ) ^-Ry ; ^Rx and ^Ry each independently represent an alkyl group having 1 to 15 carbon atoms which may have a branch or an aryl group having 5 to 14 atoms constituting a ring; ^Rx and ^Ry may be combined to represent an alkylene group having 2 to 15 carbon atoms which may have a branch; the alkyl group having 1 to 15 carbon atoms which may have a branch and the aryl group having 5 to 14 atoms constituting a ring may each have a substituent; and one or more methylene groups contained in the alkylene group having 2 to 15 carbon atoms which may have a branch may be substituted with an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, or _-CF2 -, -CHCl-, -CCl ₂ -; the amine nitrogen atom is -NH- or -N(R ^z )-; R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms. [6] The anisotropic dye film-forming composition as described in any one of [1] to [5], wherein the ratio (r _n1 /r _n2 ) of the number of ring structures possessed by the polymerizable liquid crystal compound to the number of ring structures possessed by the compound represented by the formula (1) (r _n1 /r _n2 ) is 0.7 to 1.5. [7] The anisotropic dye film-forming composition as described in any one of [1] to [6], wherein the polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond. [8] The anisotropic dye film-forming composition as described in any one of [1] to [7], further comprising a polymerization initiator. [9] A composition for forming an anisotropic pigment film as described in any one of [1] to [8], wherein the pigment further comprises one or more compounds having an absorption curve showing a maximum value in the wavelength region of 380 nm to 780 nm at a wavelength greater than the wavelength at which the compound represented by the above formula (1) shows a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm. [10] An anisotropic pigment film formed using the composition for forming an anisotropic pigment film as described in any one of [1] to [9]. [11] An optical element comprising the anisotropic pigment film as described in [10]. [Effect of the Invention]

The anisotropic pigment film-forming composition of the present invention can achieve excellent optical performance, especially a sufficient dichroic ratio. The anisotropic pigment film of the present invention is formed by using the anisotropic pigment film-forming composition of the present invention, so it can achieve excellent optical performance, especially a sufficient dichroic ratio. The optical element of the present invention can achieve excellent optical performance, especially a sufficient dichroic ratio, because it includes the anisotropic pigment film of the present invention.

Hereinafter, the embodiments of the present invention will be specifically described, but the present invention is not limited to the following embodiments and can be implemented with various modifications within the scope of the gist thereof.

The so-called anisotropic pigment film in the present invention refers to a pigment film having anisotropy in any two directions of the three directions in the three-dimensional coordinate system selected from the thickness direction of the anisotropic pigment film and any two directions in the orthogonal plane. As electromagnetic properties, for example, optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance can be listed. As films having optical anisotropy such as absorption and refraction, for example, polarizing films such as linear polarizing films and circular polarizing films, phase difference films, and conductive anisotropic pigment films can be listed. The anisotropic pigment film of the present invention is preferably used as a polarizing film or a conductive anisotropic pigment film, and is more preferably used for a polarizing film.

[Anisotropic dye film forming composition] The anisotropic dye film forming composition 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 a solution, a liquid crystal, or a dispersed state as long as it does not cause phase separation. As an anisotropic dye film forming composition, a solution is preferred from the viewpoint of easy coating on a substrate. On the other hand, the solid component obtained by removing the solvent from the anisotropic dye film forming composition is preferably in a liquid crystal phase at any temperature from the viewpoint of being aligned on the substrate as described below. Furthermore, in the present invention, the state of the liquid crystal phase refers specifically to the liquid crystal state showing both liquid and crystal properties or intermediate properties as described in "Fundamentals and Applications of Liquid Crystals" (Matsumoto Masakazu and Kakuda Ichiyoshi; 1991) pages 1 to 16, which is a nematic phase, lamellar phase, cholesteric phase, or discotic phase.

(Pigment) The pigment referred to in the present invention refers to a substance or compound that absorbs at least a portion of the wavelength in the visible light region (380 nm to 780 nm). As a pigment that can be used in the present invention, a dichroic pigment can be cited. Furthermore, the so-called dichroic pigment refers to a pigment having a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. In addition, the pigment may be a pigment with liquid crystal properties or may not have liquid crystal properties. Furthermore, the so-called liquid crystal properties refer to the expression of a liquid crystal phase at any temperature.

The dye contained in the anisotropic dye film-forming composition of the present invention includes at least a compound represented by formula (1).

A ¹ -CH=CH-A ² -(N=NA ³ ) _n -X (1)

In the formula, ^A1 represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent (except a sulfo group); ^A2 and ^A3 each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group) or a divalent group of an aromatic heterocyclic ring which may have a substituent (except a sulfo group); X represents a monovalent organic group; n represents 1, 2 or 3.

The pigment contained in the composition for forming an anisotropic pigment film of the present invention has a molecular length-short axis ratio that is sufficiently large for achieving a good dichroic ratio due to the structure represented by formula (1). At the same time, since the elongation of the π-conjugated system is suppressed, it becomes absorbed in the short-wavelength visible light region. In addition, in the structure represented by formula (1), the combination with the liquid crystal molecules and the intermolecular interaction between the liquid crystal molecules and the pigment molecules are also good, so that a higher dichroic ratio can be displayed without disturbing the molecular orientation of the liquid crystal molecules. In terms of these effects, the pigment having the structure represented by formula (1) can simultaneously achieve a higher dichroic ratio and absorption in the short-wavelength visible region, which is a previous topic.

^A1 represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent.

The aromatic hydrocarbon ring in ^A1 is a monocyclic or condensed aromatic hydrocarbon ring. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 or more. In addition, it is preferably 20 or less, more preferably 16 or less, and further preferably 10 or less. By being within these ranges, there is a tendency for the combination with liquid crystal to become good. For example, the number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 16, and further preferably 6 to 10. The number of rings in the case of a condensed ring is not particularly limited, but in terms of the tendency for the combination with liquid crystal to become good, it is preferably 2 or more and preferably 5 or less. As aromatic hydrocarbon rings, there can be listed: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetraphenylene ring, pyrene ring, benzopyrene ring, Among them, the monovalent group of the aromatic hydrocarbon ring of ^A1 is preferably a monovalent group of a benzene ring (phenyl) or a monovalent group of a naphthyl ring (naphthyl), and more preferably a phenyl group from the viewpoint of improving the linearity of the molecule.

The aromatic heterocyclic ring in ^A1 is a monocyclic or condensed aromatic heterocyclic ring. The number of carbon atoms in the aromatic heterocyclic ring is preferably 2 or more, more preferably 3 or more, and further preferably 4 or more. Also, it is preferably 20 or less, more preferably 13 or less, and further preferably 9 or less. Within these ranges, there is a tendency for the combination with liquid crystal to become good. For example, the number of carbon atoms in the aromatic heterocyclic ring is preferably 2 to 20, more preferably 3 to 13, and further preferably 4 to 9. The number of rings in the case of a condensed ring is not particularly limited, but in terms of the tendency for the combination with liquid crystal to become good, it is preferably 2 or more and preferably 5 or less.

Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofurano The ring may include a pyridine ring, a pyridine ring, a pyridine ring, a pyridine ring, a pyridine ring, a pyridine ring, a pyridine ring, a pyridine ring, a pyrimidine ring, a pyrimidine ring, a triazole ring, a quinoline ring, an isoquinoline ring, a pyridine ring, a quinoline ring, a phenanthridine ring, a quinazoline ring, a phenanthridine ring, a quinazoline ring, and a quinazolinone ring. Among them, the aromatic heterocyclic ring for ^A1 is preferably a furan ring, a thiophene ring, a thienothiazole ring, a benzoxazole ring, a benzothiazole ring, or a benzimidazole ring from the viewpoint of improving the linearity of the molecule, and particularly preferably a thienothiazole ring, a benzoxazole ring, a benzothiazole ring, or a benzimidazole ring.

Permissible substituents other than sulfo in the monovalent aromatic hydrocarbon ring or the monovalent aromatic heterocyclic ring in ^A1 include ^-RA , -OH, ^-ORA , -OC(=O) ^-RA , _-NH2 , -NH- ^RA , -N(-RB)-RA, -C(=O)-RA ^, -C(=O) ^-ORA , -C(=O) _-NH2 , -C(=O)-NH- ^RA , ^-C (=O)-N(-RB) ^-RA , -SH, ^-SRA , trifluoromethyl, sulfonylamine, carboxyl, ^cyano , nitro, and halogen. Here, ^RA and ^RB each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms. One or more methylene groups contained in the above-mentioned linear or branched alkyl group having 1 to 15 carbon atoms may be substituted with ether oxygen atoms, thioether sulfur atoms, amine nitrogen atoms, carbonyl groups, ester bonds, amide bonds, -CHF-, _-CF2- , -CHCl-, _-CCl2- structures, or may be substituted with polymerizable groups such as acryloxy groups, methacryloxy groups, or glycidyloxy groups. Among them, the substituent other than the sulfo group in the monovalent group of the aromatic hydrocarbon ring or the monovalent group of the aromatic heterocyclic ring in ^A1 is preferably ^-RA or ^-ORA , and examples thereof include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 5,5-dimethyl-3-methylhexyloxy, 11-(acryloyloxy)undecyloxy, etc. The above-mentioned amine nitrogen atom represents -NH- or -N( ^Rz )-, and ^Rz represents a linear or branched alkyl group having 1 to 6 carbon atoms.

^A1 is preferably a monovalent group of an aromatic hydrocarbon ring, more preferably a phenyl group or a naphthyl group, from the viewpoint of showing a higher dichroic ratio. From the viewpoint of improving linearity, a phenyl group is further preferred. ^A1 's substituent is preferably a substituent selected from the group consisting of ^-RA , ^-ORA and -C(=O) ^-ORA , and more preferably a substituent selected from the group consisting of ^-RA and ^-ORA at the 4-position. By having the above substituent, there is a tendency for the combination with liquid crystal to become good.

^A2 and ^A3 each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent (but excluding a sulfo group) or a divalent group of an aromatic heterocyclic ring which may have a substituent.

The aromatic hydrocarbon rings in ^A2 and ^A3 are the same as those in ^A1 . As the divalent group of the aromatic hydrocarbon ring in ^A2 , a divalent group of a benzene ring (phenylene) or a divalent group of a naphthalene ring (naphthylene) is preferred, 1,4-phenylene, 1,4-naphthylene, 2,6-naphthylene is more preferred, and 1,4-phenylene is more preferred. As the divalent group of the aromatic hydrocarbon ring in ^A3 , a phenylene or a naphthylene is preferred, a phenylene is more preferred, and 1,4-phenylene is more preferred. By making ^A2 and/or ^A3 the above groups, the effect of increasing the aspect ratio of the molecule can be obtained, and there is a tendency that the combination with liquid crystal becomes good.

The aromatic heterocyclic ring in ^A2 and ^A3 is the same as the aromatic heterocyclic ring in ^A1 .

The substituents other than sulfo which are permitted on the divalent aromatic hydrocarbon ring or divalent aromatic heterocyclic ring in ^A2 and ^A3 are the same as the substituents other than sulfo which are permitted on the monovalent aromatic hydrocarbon ring or monovalent aromatic heterocyclic ring in ^A1 .

A ² is preferably a divalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group) from the viewpoint of showing a higher dichroic ratio, more preferably a phenylene group or a naphthylene group which may have a substituent (except a sulfo group), and further preferably a 1,4-phenylene group or a 1,4-naphthylene group which may have a substituent (except a sulfo group). From the viewpoint of improving linearity, further preferably a 1,4-phenylene group which does not have a substituent. A ³ is preferably a divalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group) from the viewpoint of showing a higher dichroic ratio. Among these, more preferably a phenylene group or a naphthylene group which may have a substituent (except a sulfo group), and further preferably a 1,4-phenylene group or a 1,4-naphthylene group which may have a substituent (except a sulfo group). In particular, from the viewpoint of improving linearity, 1,4-phenylene group having no substituent is particularly preferred.

In the above ^A1 , ^A2 and ^A3 , a substituent other than a sulfo group is permitted. When the substituent is a sulfo group, the compatibility with liquid crystal and solvent decreases, thereby causing a decrease in the dichroic ratio and further causing precipitation of the pigment, which may significantly deteriorate the performance of the anisotropic pigment film.

X represents a monovalent organic group. Examples of the monovalent organic group in X include a hydrogen atom, a hydroxyl group, an amino group, a cyano group, an aminoformyl group ^, a nitro group, a halogen atom, ^-Rx , ^-ORx , -NH- ^Rx , -N(-Ry ⁾ -Rx, -C(=O)-Rx ^, -C(=O)-ORx ^, -C(=O)-NH- ^Rx , -C(=O)-N(-Ry ^{) -Rx} , -OC(=O) ^-Rx , -NH-C(=O) ^-Rx , -N( ^-Ry )-C(=O) ^-Rx , and the like. Furthermore, ^Rx and ^Ry each independently represent an alkyl group having 1 to 15 carbon atoms which may have a branch or an aryl group having 5 to 14 atoms constituting a ring; ^Rx and ^Ry may be combined to represent an alkylene group having 2 to 15 carbon atoms which may have a branch. The alkyl group having 1 to 15 carbon atoms which may have a branch and the aryl group having 5 to 14 atoms constituting a ring may each have a substituent. One or more methylene groups contained in the alkyl group having 1 to 15 carbon atoms which may have a branch and the alkylene group having 2 to 15 carbon atoms which may have a branch may be substituted (displaced) with an ethereal oxygen atom, a thioethereal sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, _-CF2- , -CHCl-, or _-CCl2- . The above-mentioned amine nitrogen atom represents -NH- or -N( ^Rz )-, and ^Rz represents a linear or branched alkyl group having 1 to 6 carbon atoms.

Permissible substituents for the optionally branched alkyl group having 1 to 15 carbon atoms in ^Rx include -OH, ^-ORA , -OC(=O) ^-RA , _-NH2 , -NH- ^RA , -N ⁽ -RB)-RA, ^-C (=O)-RA, ^-C (=O) ^-ORA , -C(=O)-NH2, -C(=O) _-NH - ^RA , -C(=O)-N( ^-RB ) ^-RA , -SH, ^-SRA , sulfonamide, carboxyl, cyano, nitro, and halogen. Here, ^RA and ^RB each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms. One or more methylene groups contained in the above-mentioned linear or branched alkyl group having 1 to 15 carbon atoms may be substituted with etheric oxygen atoms, thioetheric sulfur atoms, amine nitrogen atoms, carbonyl groups, ester bonds, amide bonds, -CHF-, _-CF2- , -CHCl-, or _-CCl2- . Furthermore, one or more methylene groups contained in the above-mentioned linear or branched alkyl group having 1 to 15 carbon atoms may be substituted with polymerizable groups such as acryloxy, methacryloxy, or glycidyloxy. Among them, the permissible substituents in the alkyl group having 1 to 15 carbon atoms which may have a branch in ^Rx are preferably ^-ORA in terms of the tendency to obtain a pigment which is well combined with a liquid crystal, and examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptyloxy, n-octyloxy, acryloxy, methacryloxy, glycidyloxy, etc. Furthermore, the above-mentioned amine nitrogen atom is -NH- or -N( ^Rz )-, and ^Rz represents a linear or branched alkyl group having 1 to 6 carbon atoms.

Permissible substituents in the aryl group having 5 to 14 atoms constituting the ring in ^Rx include ^-RA , -OH, ^-ORA , ^-OC (=O) ^-RA , _-NH2 , -NH- ^RA , -N ⁽ -RB) ^-RA , -C(=O)-RA, -C(=O)-ORA, -C ⁽ =O) _-NH2 , -C(=O)-NH- ^RA , -C(=O)-N( ^-RB ) ^-RA , -SH, ^-SRA , trifluoromethyl, sulfonylamine, carboxyl, cyano, nitro, and halogen. Here, ^RA and ^RB each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms. Among them, the permissible substituents in the aryl group having 5 to 14 ring atoms in R ^x are preferably ^-RA and ^-ORA . 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-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, and 5,5-dimethyl-3-methylhexyloxy.

As the aryl group having 5 to 14 atoms constituting the ring, there can be mentioned the monovalent groups of the rings exemplified as the aromatic hydrocarbon ring and the aromatic heterocyclic ring in ^A1 of the formula (1). As the monovalent group of the aromatic hydrocarbon ring, a monovalent group of a benzene ring (phenyl) and a monovalent group of a naphthyl ring (naphthyl) are preferred. As the monovalent group of the aromatic heterocyclic ring, a monovalent group of a furan ring, a monovalent group of a thiophene ring, a monovalent group of a thienothiazole ring, a monovalent group of a benzoxazole ring, a monovalent group of a benzothiazole ring, and a monovalent group of a benzimidazole ring are preferred. The monovalent groups of the aromatic hydrocarbon ring and the aromatic heterocyclic ring mentioned above tend to increase the linearity of the molecule. Among them, phenyl is more preferred from the viewpoint of exhibiting a higher dichroic ratio.

As ^Rx and ^Ry , in terms of the tendency to obtain a pigment that is well combined with liquid crystal, preferably an alkyl group having 1 to 15 carbon atoms which may have a branch, or ^Rx and ^Ry are combined to form an alkylene group having 2 to 15 carbon atoms which may have a branch; more preferably, an alkyl group having 1 to 6 carbon atoms which may have a branch, or ^Rx and ^Ry are combined to form an alkylene group having 2 to 10 carbon atoms which may have a branch; further preferably, an alkyl group having 1 to 3 carbon atoms which may have a branch, or ^Rx and ^Ry are combined to form an alkylene group having 2 to 6 carbon atoms which may have a branch.

As the monovalent organic group in X, ^-ORx , -NH- ^Rx , and -N(-Ry)-Rx are preferred, and ^-ORx and -N( ^-Ry ) ^{-Rx are} more preferred, and -N( ^{-Ry ) -Rx} is further preferred, because they tend to combine well with liquid crystals. Specifically, for example, dimethylamino, diethylamino, di-n-propylamino, ethylmethylamino, methylpropylamino, azacyclobutyl, pyrrolidinyl, piperidinyl, azaquinoline, oxathioline, piperazinyl, and thiooxathioline are further preferred, and diethylamino, pyrrolidinyl, and piperidinyl are further preferred.

n represents 1, 2 or 3. With respect to n, in view of the tendency to form a pigment having a sufficiently large molecular aspect ratio and absorption in a short wavelength region, it is preferably 1 or 2, and more preferably 1. When n represents 2 or 3, each A ³ may be the same or different.

From the perspective of increasing the aspect ratio of the molecule, -CH=CH- in formula (1) is preferably in the inverse form. From the perspective of increasing the aspect ratio of the molecule, -N=N- in formula (1) is preferably in the inverse form.

Specifically, the compound represented by formula (1) includes the following compounds, but is not limited thereto.

[Chemistry 1]

[Chemistry 2]

[Chemistry 3]

[Chemistry 4]

[Chemistry 5]

[Chemistry 6]

[Chemistry 7]

[Chemistry 8]

[Chemistry 9]

[Chemistry 10]

The compound represented by formula (1) contained in the anisotropic pigment film-forming composition of the present invention may have a maximum absorption (λ _max1 ) at any wavelength in the anisotropic pigment film produced by the following method, preferably in the range of 350 to 550 nm, more preferably in the range of 410 to 530 nm, and further preferably in the range of 430 to 520 nm. In addition, the compound represented by formula (1) contained in the anisotropic pigment film-forming composition of the present invention preferably has a maximum absorption (the above λ _max1 ) in the anisotropic pigment film at a longer wavelength than the maximum absorption (λ _max2 ) measured when dissolved in a solvent. The long-wavelength shift is a phenomenon that occurs when the compound represented by formula (1) is dispersed in a polymerizable liquid crystal compound and/or a polymer having units based on a polymerizable liquid crystal compound, indicating that the compound represented by formula (1) has a stronger intermolecular interaction with the polymerizable liquid crystal compound and/or a polymer having units based on a polymerizable liquid crystal compound. It is believed that the compound represented by formula (1) can exhibit a higher dichroic ratio due to the stronger intermolecular interaction. The so-called long-wavelength shift means that the difference in absorption maximum (λ _max1 -λ _max2 ) becomes a positive value. From the perspective of exhibiting higher dichroism, the difference is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 15 nm or more. In addition, the upper limit is not particularly limited, and for example, it can be 50 nm or less.

The composition for forming anisotropic pigment film of the present invention may contain other pigments in addition to the compound represented by formula (1). Examples of other pigments include azo pigments, quinone pigments (including naphthoquinone pigments, anthraquinone pigments, etc.), stilbene pigments, cyanine pigments, phthalocyanine pigments, indigo pigments, condensed polycyclic pigments (including perylene pigments, thiazolinium pigments, acridine pigments, etc.). Among these pigments, azo pigments are preferred in terms of being able to form a higher molecular arrangement in the anisotropic pigment film. The so-called azo dye refers to a dye having at least one azo group (-N=N-). The number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and further preferably 3 or less from the viewpoint of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production.

Examples of the azo dye include compounds represented by formula (A).

R ¹¹ -D ¹ -N=N-(D ² -N=N) _p -D ³ -R ¹² (A)

In formula (A), D ¹ , D ² and D ³ each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent; p represents an integer of 0 to 4; when p is an integer greater than 2, a plurality of D ^2's may be the same or different; R ¹¹ and R ¹² each independently represent a monovalent organic group.

D ¹ , D ² and D ³ each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent. As the substitution position of the phenylene group, 1,4-phenylene is preferred in terms of higher linearity of the molecule. As the substitution position of the naphthylene group, 1,4-naphthylene or 2,6-naphthylene is preferred in terms of higher linearity of the molecule.

As a divalent heterocyclic group, the number of carbon atoms forming the ring is preferably 3 or more and 14 or less, and more preferably 10 or less, from the viewpoint of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production. In particular, monocyclic or bicyclic heterocyclic groups are preferred in terms of the tendency for the molecular aspect ratio to increase. As atoms other than carbon constituting the divalent heterocyclic group, at least one selected from nitrogen atoms, sulfur atoms, and oxygen atoms can be listed. When the heterocyclic group has multiple atoms constituting the ring other than carbon, they may be the same or different. Specifically, there can be mentioned 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, an o-phthalimidediyl group, an oxadiazolediyl group, a benzooxadiazolediyl group, and the like.

As the substituents optionally possessed by the phenylene group, naphthylene group, and divalent heterocyclic group in D ¹ , D ² , and D ³ , there can be listed: 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; nitro; hydroxyl; halogen atom; substituted or unsubstituted amino groups such as amino, diethylamino, and pyrrolidinyl. The above-mentioned substituted amino groups refer to amino groups having 1 or 2 alkyl groups having 1 to 4 carbon atoms, or amino groups in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. The unsubstituted amino group is -NH ₂ . As the alkyl groups having 1 to 4 carbon atoms, there can be listed methyl, ethyl, and butyl groups. Examples of the alkanediyl group having 2 to 8 carbon atoms include ethyl, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc. In terms of higher molecular linearity, in the case of unsubstituted or substituted, substituted with methyl, methoxy, hydroxyl, fluorine, chlorine, dimethylamino, pyrrolidinyl, or piperidinyl is preferred.

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

R ¹¹ and R ¹² represent the same or different monovalent organic groups. Examples of the monovalent organic groups in R ¹¹ and R ¹² include: a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a branched chain; an alicyclic alkyl group having 1 to 15 carbon atoms; an alkoxy group having 1 to 15 carbon atoms which may have a branched chain, such as a methoxy group, an ethoxy group, and a butoxy group; a fluorinated alkyl group having 1 to 15 carbon atoms which may have a branched chain, such as a trifluoromethyl group; a cyano group; a nitro group; a hydroxyl group; a halogen atom; an amino group, a diethylamino group, a pyrrolidinyl group, and other substituted or unsubstituted amino groups; a carboxyl group; and an alkoxycarbonyl group having 1 to 15 carbon atoms which may have a branched chain, such as a butoxycarbonyl group. ; alkylphenyl alkenyl groups such as 2-(4-butylphenyl)vinyl; aminoformyl; alkylaminoformyl groups having 1 to 15 carbon atoms and which may have a branched chain such as butylaminoformyl; aminosulfonyl; alkylaminosulfonyl groups having 1 to 15 carbon atoms and which may have a branched chain such as butylaminosulfonyl; acylamino groups having 1 to 15 carbon atoms and which may have a branched chain such as butylcarbonylamino; acyloxy groups having 1 to 15 carbon atoms and which may have a branched chain such as butylcarbonyloxy; butylyl; alkylthio groups having 1 to 15 carbon atoms and which may have a branched chain such as butylthio; Q ¹ -R ¹ - and Q ² -R ² - in the following polymerizable liquid crystal compounds. Furthermore, the substituted amino group means an amino group having one or two alkyl groups having 1 to 15 carbon atoms which may have a branch, 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 -NH ₂ . Furthermore, examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, and butyl. Examples of the alkanediyl group having 2 to 15 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

As R ¹¹ and R ¹² , hydrogen atoms, chain groups, aliphatic organic groups ("aliphatic organic groups" include chain groups and cyclic groups), aliphatic organic groups in which a portion of carbon is replaced by nitrogen and/or oxygen, etc. are listed. In one embodiment, hydrogen atoms and chain groups are preferred. In another embodiment, hydrogen atoms and aliphatic organic groups are preferred. In another embodiment, hydrogen atoms and aliphatic organic groups are preferred. In another embodiment, hydrogen atoms and aliphatic organic groups in which a portion of carbon is replaced by nitrogen and/or oxygen are preferred. Furthermore, the "aliphatic organic group in which a portion of carbon is replaced by nitrogen and/or oxygen" includes chain groups and cyclic groups, and includes aliphatic organic groups in which a portion of methyl groups is replaced by hydroxyl groups, pendoxy groups (=O), amino groups, imino groups, etc.

Examples of the chain group include: the above-mentioned alkyl group having 1 to 15 carbon atoms which may have a branch; the alkoxy group having 1 to 15 carbon atoms which may have a branch; the fluorinated alkyl group having 1 to 15 carbon atoms which may have a branch; a substituted or unsubstituted amino group; a carboxyl group; an alkoxycarbonyl group having 1 to 15 carbon atoms which may have a branch; an aminoformyl group; an alkylaminoformyl group having 1 to 15 carbon atoms which may have a branch; an aminosulfonyl group; an alkylaminosulfonyl group having 1 to 15 carbon atoms which may have a branch; an acylamino group having 1 to 15 carbon atoms which may have a branch; an acyloxy group having 1 to 15 carbon atoms which may have a branch; an alkyl group; an alkylthio group having 1 to 15 carbon atoms, etc. Furthermore, the above-mentioned substituted amino group means an amino group having 1 or 2 alkyl groups having 1 to 15 carbon atoms which may have a branch. Unsubstituted amino groups are -NH ₂ .

Examples of the aliphatic organic group include the above-mentioned alkyl group with 1 to 15 carbon atoms which may have a branched chain, and alicyclic alkyl group with 1 to 15 carbon atoms. Examples of the aliphatic organic group in which a portion of the carbon atoms is substituted with nitrogen and/or oxygen include: the above-mentioned alkoxy group with 1 to 15 carbon atoms which may have a branched chain; a substituted or unsubstituted amino group; a carboxyl group; an alkoxycarbonyl group with 1 to 15 carbon atoms which may have a branched chain; an aminoformyl group; an alkylaminoformyl group with 1 to 15 carbon atoms which may have a branched chain; an acylamino group with 1 to 15 carbon atoms which may have a branched chain; and an acyloxy group with 1 to 15 carbon atoms which may have a branched chain. Furthermore, the above-mentioned substituted amino group means an amino group having 1 or 2 alkyl groups with 1 to 15 carbon atoms which may have a branch, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group with 2 to 15 carbon atoms. An unsubstituted amino group is -NH ₂ . Furthermore, as the alkyl group with 1 to 15 carbon atoms, methyl, ethyl and butyl groups can be listed. As the alkanediyl group with 2 to 15 carbon atoms, ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl and the like can be listed.

In terms of higher molecular linearity, R ¹¹ and R ¹² are preferably independently a hydrogen atom, or substituted by an alkyl group having 1 to 10 carbon atoms such as butyl, pentyl, hexyl, heptyl, octyl, or an alkoxy group having 1 to 10 carbon atoms such as butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, diethylamino, pyrrolidinyl, or piperidinyl. Also preferred are Q ¹ -R ¹ - and Q ² -R ² - in the following polymerizable liquid crystal compound.

Furthermore, the pigment other than the compound represented by formula (1) contained in the anisotropic pigment film-forming composition of the present invention is not particularly limited, and known pigments may be used. As known pigments, for example, the pigments described in the above-mentioned patent document 1, Japanese Patent No. 5982762, Japanese Patent Application Publication No. 2017-025317, and Japanese Patent Application Publication No. 2014-095899 (dichroic pigments, dichroic dyes) can be cited.

Specifically, the pigments described below can be listed, but are not limited to them.

[Chemistry 11]

[Chemistry 12]

[Chemistry 13]

[Chemistry 14]

Furthermore, as the pigment other than the compound represented by formula (1) contained in the anisotropic pigment film-forming composition of the present invention, it is preferred that the wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm is greater than the wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm of the compound represented by formula (1) contained in the anisotropic pigment film-forming composition, more preferably, it is preferred that the wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm is greater than the wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm of the compound represented by formula (1) contained in the anisotropic pigment film-forming composition by 5 nm or more, and further preferably, it is preferred that the wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm of the compound represented by formula (1) contained in the anisotropic pigment film-forming composition The wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm is 10 nm or more larger than the wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm of the compound represented by formula (1) contained in the anisotropic pigment film-forming composition. By making the wavelength showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm of the pigment other than the compound represented by formula (1) fall within the above range, it tends to be easy to adjust the color tone.

The molecular weight of the pigment contained in the anisotropic pigment film-forming composition of the present invention (the molecular weight of each pigment when two or more pigments are used in combination) is preferably 300 or more, more preferably 350 or more, and further preferably 380 or more. Furthermore, it is preferably 1500 or less, more preferably 1200 or less, and further preferably 1000 or less. Specifically, the molecular weight of the pigment contained in the anisotropic pigment film-forming composition of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and further preferably 380 to 1000. By being in the above range, the molecular aspect ratio tends to be large.

The content of the pigment (dichroic pigment) in the anisotropic pigment film-forming composition (the sum of the contents of each pigment when two or more pigments are used in combination) is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 30 parts by mass or less, more preferably 10 parts by mass or less, for example, relative to the solid content (100 parts by mass) of the anisotropic pigment film-forming composition. Specifically, the content of the pigment (dichroic pigment) in the anisotropic pigment film-forming composition 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 anisotropic pigment film-forming composition. As long as the content of the pigment (dichroic pigment) is within the above range, the compound contained in the anisotropic pigment film-forming composition of the present invention tends to be polymerized without disturbing the alignment of the liquid crystal compound contained in the anisotropic pigment film-forming composition of the present invention. In addition, if the content of the pigment (dichroic pigment) is above the above lower limit, sufficient light absorption and sufficient polarization performance tend to be obtained. In addition, if the content of the pigment (dichroic pigment) is below the above upper limit, the alignment obstruction of the liquid crystal molecules tends to be easily suppressed.

The pigment (dichroic pigment) may be a compound represented by formula (1) alone or in combination with a pigment other than the compound represented by formula (1). As described above, as the pigment contained in the anisotropic pigment film-forming composition of the present invention, it is preferred to use a compound represented by formula (1) and at least one compound having a maximum wavelength in the absorption curve in the wavelength range of 380 nm to 780 nm greater than the wavelength in the absorption curve in the wavelength range of 380 nm to 780 nm of the compound represented by formula (1) contained in the anisotropic pigment film-forming composition. In particular, when the anisotropic pigment film is formed using the anisotropic pigment film-forming composition as a polarizing element for a display, it is preferred in terms of exhibiting polarization characteristics in a wider range of the visible light region.

The dye contained in the anisotropic dye film-forming composition 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. For example, the dye contained in the anisotropic dye film-forming composition of the present invention can be synthesized according to the method described in the embodiments, or the method described in "New Dye Chemistry" (written by Toyotaka Hosoda, December 21, 1970, Gihodo), "General Theory of Synthetic Dyes" (written by Hiroshi Horiguchi, 1968, Sankyo Publishing), and "Theoretical Production Dye Chemistry" (written by Toyotaka Hosoda, 1957, Gihodo).

(Polymerizable liquid crystal compound) In the present invention, the so-called liquid crystal compound refers to a substance that exhibits a liquid crystal state, and specifically refers to a compound that does not directly transform from a crystal to a liquid, but becomes a liquid through an intermediate state that exhibits the properties of both a crystal and a liquid, as described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000) on pages 1 to 28.

The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention is a liquid crystal compound having a polymerizable group as described below.

In a polymerizable liquid crystal compound, the polymerizable group can be arranged at any position in the liquid crystal compound molecule. In terms of the tendency of facilitating intermolecular polymerization, it is preferably substituted at the end of the liquid crystal compound molecule. In a polymerizable liquid crystal compound, there can be more than one polymerizable group in the liquid crystal compound molecule. When there are more than two polymerizable groups, they are preferably respectively present at both ends of the liquid crystal compound molecule.

Furthermore, the polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the liquid crystal compound molecule. If the compound has a carbon-carbon triple bond, the carbon-carbon triple bond can perform rotational motion and can become the core of the liquid crystal molecule, the molecular mobility is higher, and the intermolecular interaction between the liquid crystal molecules and the compounds having a π-conjugated system such as the pigment molecules is stronger, and there is a tendency for the molecular orientation to become higher.

The polymerizable liquid crystal compound contained in the anisotropic dye film forming composition of the present invention is not particularly limited, and a liquid crystal compound having a polymerizable group can be used. For example, the polymerizable liquid crystal compound contained in the anisotropic dye film forming composition of the present invention includes the compound represented by formula (2).

Q ¹ -R ¹ -A ¹¹ -Y ¹ -A ¹² -(Y ² -A ¹³ ) _k -R ² -Q ² (2)

(wherein, Q ¹ represents a hydrogen atom or a polymerizable group; Q ² represents a polymerizable group; R ¹ and R ² each independently represent a chain organic group; A ¹¹ and A ¹³ each independently represent 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 represent a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -; One of ^A11 and ^A13 is a partial structure or a divalent organic group represented by the following formula (3); k is 1 or 2)

-Cy-X ² -C≡CX ¹ - (3)

(wherein, Cy represents a cycloalkyl or heterocycloalkyl; -X ¹ - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -; -X ² - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -)

Furthermore, when ^A11 is a partial structure represented by formula (3), formula (2) may be ^{Q1 - R1} -Cy- ^X2 -C≡CX1- ^Y1 - ^A12- ( ^Y2 - ^A13 ) _k -R2- ^Q2 (2A) or Q1 ^{- R1} - ^X1 - ^C≡CX2- Cy- ^Y1 - ^A12- ( ^{Y2 -A13 )} _k - ^R2 - ^Q2 (2B). When ^A12 is a partial structure represented by formula (3), formula (2) may be ^Q1 - ^R1 - ^A11 - ^Y1-Cy - ^{X2 -} C≡CX1-( ^Y2 - ^A13 ) _k - ^R2 - ^Q2 (2C) or ^Q1 - ^R1 - ^A11 -Y1- ^X1 - ^{C≡CX2 -} Cy-( ^Y2 - ^A13 ) _k - ^R2 - ^Q2 (2D). When ^A13 is a partial structure represented by formula (3), formula (2) may be ^Q1 -R1- ^{A11 - Y1} - ^A12- (Y2 ^- Cy- ^X2 -C≡CX1) _k - ^R2 - ^Q2 (2E) or ^Q1 - ^R1 - ^{A11 - Y1} - ^A12- (Y2 ^{-X1 -} C≡CX2 ^- Cy) _k - ^R2 - ^Q2 (2F).

Similarly, when two or more of A ¹¹ , A ¹² , and A ¹³ are partial structures represented by formula (1), the orientation of the partial structures represented by formula (1) can be reversed independently of each other.

As described above, A ¹¹ , A ¹² , and A ¹³ are each independently a partial structure represented by formula (1) or a divalent organic group; and A ¹¹ and A ¹³ may be single bonds, but there is no case where both A ¹¹ and A ¹³ are single bonds.

The cyclic hydrocarbon group in Cy includes an aromatic cyclic hydrocarbon group and a non-aromatic cyclic hydrocarbon group.

The aromatic hydrocarbon ring group includes a non-linked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group. The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the carbon number is preferably 6 to 20. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, a benzopyrene ring, The aromatic hydrocarbon ring is a divalent group in which multiple monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond, and the carbon number of the monocyclic or condensed ring is preferably 6 to 20. For example, a divalent group in which a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded to a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond, and the first bond is on an atom of the first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms, and the second bond is on an atom of the second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. As a linked aromatic hydrocarbon ring group, for example, biphenyl-4,4'-diyl can be cited. As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferred. Among them, the aromatic hydrocarbon 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). The phenylene group is preferably a 1,4-phenylene group. By having the above groups, the molecular orientation of the liquid crystal compound tends to be improved.

The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group. The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the carbon number is preferably 3 to 20. Examples of the non-aromatic hydrocarbon ring include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, northane ring, isocyanate ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring, etc. The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond of the constituent ring of the non-aromatic hydrocarbon ring, and an unsaturated and non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond of the constituent ring of the non-aromatic hydrocarbon ring. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred. The non-aromatic hydrocarbon ring-linked group is a divalent group having a bonding bond on an atom constituting the ring by a plurality of monocyclic or condensed non-aromatic hydrocarbon rings; or one or more rings selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring and a monocyclic or condensed non-aromatic hydrocarbon ring are bonded by a single bond, and a divalent group having a bonding bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, the first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to the second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, the first bond is on an atom of the first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second bond is on an atom of the second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. For example, a divalent group is a monocyclic or condensed aromatic hydrocarbon ring with 3 to 20 carbon atoms and a monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbon atoms bonded by a single bond, and has a first bond on an atom of the constituent ring of the monocyclic or condensed aromatic hydrocarbon ring with 3 to 20 carbon atoms, and a second bond on an atom of the constituent ring of the monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbon atoms. Examples of the non-aromatic hydrocarbon ring-linking group include bis(cyclohexane)-4,4'-diyl and 1-cyclohexylbenzene-4,4'-diyl. As the non-aromatic cyclic group, from the viewpoint of the molecular orientation of the liquid crystal compound, a non-linked non-aromatic cyclic group is preferred. Among them, as the non-aromatic cyclic group, a divalent group of cyclohexane (cyclohexanediyl) is preferred. As the cyclohexanediyl, cyclohexane-1,4-diyl is preferred. By having the above-mentioned groups, the solubility and the molecular orientation of the liquid crystal compound tend to be improved.

The heterocyclic group in Cy includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

Aromatic heterocyclic groups include non-linked aromatic heterocyclic groups and linked aromatic heterocyclic groups. The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic group, and the carbon number is preferably 4 to 20. Examples of the aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanopyrrol ring, furanopyrrol ring, pyropyrrol ring, thiophene ... Furan ring, thienofuran ring, thienothiazole ring, benzoisosazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, tris(III) ring, quinoline ring, isoquinoline ring, oxazolidinone ring, phenanthidine ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring, etc. A linked aromatic heterocyclic group is a divalent group having a bonding bond on the atoms constituting the ring, in which multiple monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a divalent group in which a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, the first bond being on an atom constituting the first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bond being on an atom constituting the second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group. The non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and the carbon number is preferably 4 to 20. The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic ring or a condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. Examples of the non-aromatic heterocyclic ring include a tetrahydrofuran ring, a tetrahydropyran ring, a dihydroalkane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidinyl ring, a piperidine ring, a dihydropyridine ring, a piperidine ring, a tetrahydrothiazolyl ring, a tetrahydroxazolyl ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, The non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond, and the carbon number of the monocyclic or condensed ring is preferably 4 to 20. For example, a divalent group in which a first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, wherein the first bond is on an atom constituting the ring of the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bond is on an atom constituting the ring of the second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

The aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy may be substituted by one or more groups selected from the group consisting of ^Rz , -OH, ^-ORz , -OC(=O) ^-Rz , _-NH2 , -NH- ^{Rz ,} -N(Rz ^' )- ^Rz , -C(=O) ^-Rz , -C(=O)-ORz, -C(=O) ^-NH2 , -C(=O)-NH- ^Rz , _-C (=O)-N(Rz ^' )-Rz, -SH, ^-SRz , trifluoromethyl, sulfonylamine, carboxyl, sulfonyl, cyano, nitro, and halogen. Here, ^Rz and Rz ^' independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. The aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy are preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, respectively, from the viewpoint that the linearity of the molecular structure is high and the molecules represented by formula (2) are easy to aggregate and easily exhibit a liquid crystal state. More preferably, they are unsubstituted. The substituents possessed by the aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different. Furthermore, the aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group may all be substituted, all be unsubstituted, or be partially substituted and partially unsubstituted.

As Cy, from the viewpoint of solubility and molecular orientation of the liquid crystal compound, a cycloalkyl group is preferred, and a phenylene group or a cyclohexanediyl group is more preferred. Furthermore, from the viewpoint of improving the linearity of the molecular structure of the liquid crystal compound, as Cy, a 1,4-phenylene group or a cyclohexane-1,4-diyl group is further preferred, and a 1,4-phenylene group is particularly preferred.

In terms of the linearity of the liquid crystal compound or the tendency of easy rotational motion around the short axis of the molecule, ^-X1- is preferably -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH2O-, -OCH2- _{, -CH2S-} , _-SCH2- , which _have a _{smaller π} bonding property, and more preferably -C(=O)O-, -OC(=O)-, _{-CH2CH2- , -CH2O-} , _-OCH2- . In one embodiment, -X ¹ - is -C(=O)O- or -OC(=O)-. In another embodiment, -X ¹ - is -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -.

From the viewpoint of enlarging the core of the liquid crystal compound and increasing the dichroism of the anisotropic dye film formed from the anisotropic dye film-forming composition, it is preferred to link -Cy- and -C≡C- with a group having a higher linearity. Specifically, ^-X2- 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-, -NHC(=O)- having a π bond. A single bond is further preferred from the viewpoint of higher linearity.

The polymerizable group in the present invention is a group having a partial structure capable of being polymerized by light, heat, and/or radiation, and is a functional group or atomic group required to ensure the polymerization function. It is preferable that the polymerizable group is a photopolymerizable group from the viewpoint of manufacturing anisotropic pigment film. As the polymerizable group, specifically, for example, there can be listed: acryl, methacryl, acryloxy, methacryloxy, acrylamino, methacrylamino, vinyl, vinyloxy, ethynyl, ethynyloxy, 1,3-butadienyl, 1,3-butadienyloxy, ethylene oxide, cyclobutylene oxide, glyceryl, glyceryloxy, styryl, styryloxy, etc. Among them, preferred are acryl, methacryl, acryloxy, methacryloxy, acrylamino, methacrylamino, ethylene oxide, glycidyl, and glycidyloxy groups; more preferred are acryl, methacryl, acryloxy, methacryloxy, acrylamino, methacrylamino, glycidyl, and glycidyloxy groups; and further preferred are acryloxy, methacryloxy, and glycidyloxy groups. The presence of the above-mentioned polymerizable groups makes it easy to control polymerization.

The chain organic group in ^R1 and ^R2 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 heterocyclic ring, non-aromatic heterocyclic ring, etc. Examples of such a chain organic group include -(alkylene)-, -O-(alkylene)-, -S-(alkylene)-, -NH-(alkylene)-, -N(alkyl)-(alkylene)-, -OC(=O)-(alkylene)-, and -C(=O)O-(alkylene)-. As the chain organic group in ^R1 and ^R2 , -(alkylene)- and -O-(alkylene)- are preferred. In one embodiment, the chain organic group in ^R1 and ^R2 is -(alkylene)-. In another embodiment, the chain organic group is -O-(alkylene)-.

Examples of the alkylene group in the chain organic group include linear or branched alkylene groups having 1 to 25 carbon atoms. A portion of the carbon-carbon bonds of the alkylene group may be unsaturated bonds, and one or more methylene groups contained in the alkylene group may be substituted (displaced) with ether oxygen atoms, thioether sulfur atoms, amine nitrogen atoms, carbonyl groups, ester bonds, amide bonds, -CHF-, _-CF2- , -CHCl-, or _-CCl2- . Examples of the amine nitrogen atom include -NH- and -N( ^Rz ), where ^Rz represents a linear or branched alkylene group having 1 to 6 carbon atoms. As the alkylene group in the chain organic group, in terms of higher molecular linearity, a portion of the carbon atoms of the alkylene group may be unsaturated bonds, and one or more methylene groups in the alkylene group may be substituted (displaced) to the above structure, preferably a linear alkylene group having 1 to 25 carbon atoms. The number of atoms in the main chain (meaning the longest chain part in the chain organic group) in the chain organic group is preferably 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

As the chain organic group, -(CH ₂ ) _n -CH ₂ -, -O-(CH ₂ ) _n -CH ₂ -, -(O) _n1 -(CH ₂ CH ₂ O) _n2 -(CH ₂ ) _n3 -, and -(O) _n1 -(CH ₂ ) _n2 -(CH ₂ CH ₂ O) _n3 - are preferred from the viewpoint of improving the molecular alignment of the liquid crystal compound. In addition, n in the formula is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and further preferably an integer of 5 to 19. In the formula, n1, n2, and n3 each independently represent an integer, and the number of atoms in the main chain (meaning the longest chain part in the chain organic group) in the chain organic group is appropriately adjusted so as to preferably be 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

^R1 and ^R2 are independently preferably -(alkylene)-, -O-(alkylene)-, and more preferably -(alkylene)-, -O-(alkylene)-. The above molecular structure has a tendency to improve the molecular orientation of the liquid crystal compound. In the case where ^X1 and ^R1 or ^X1 and ^R2 are bonded as shown in formula (2B) and formula (2E), or in the case where ^A13 is a single bond in formula (2B) or ^A11 is a single bond in formula (2E) and ^R1 or ^R2 is bonded to ^Y1 or ^Y2 , ^R1 or ^R2 bonded to ^X1 or ^Y1 or ^Y2 is preferably -(alkylene)- from the viewpoint of improving the molecular orientation of the liquid crystal compound. In addition, in cases other than the above, R ¹ or R ² not bonding to X ¹ , Y ¹ or Y ² is preferably -O-(alkylene)- from the viewpoint of improving the molecular alignment of the liquid crystal compound.

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

-Q ³ - (4)

In formula (4), Q ³ represents a cycloalkyl group or a heterocycloalkyl group.

The alkyl group in Q ³ includes an aromatic alkyl group and a non-aromatic alkyl group.

The aromatic hydrocarbon ring group includes a non-linked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group. The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the carbon number is preferably 6 to 20. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, a benzopyrene ring, The aromatic hydrocarbon ring is a divalent group in which multiple monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond, and the carbon number of the monocyclic or condensed ring is preferably 6 to 20. For example, a divalent group in which a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded to a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond, and the first bond is on an atom of the first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms, and the second bond is on an atom of the second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. As a linked aromatic hydrocarbon ring group, for example, biphenyl-4,4'-diyl can be cited. As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferred. Among them, the aromatic hydrocarbon 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). The phenylene group is preferably a 1,4-phenylene group. By having the above groups, the molecular orientation of the liquid crystal compound tends to be improved.

The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group. The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the carbon number is preferably 3 to 20. 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 norethane ring, a nitroethane ring, adamantane ring, a tetrahydronaphthalene ring, a bicyclo[2.2.2]octane ring, and the like. The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond of the constituent ring of the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond of the constituent ring of the non-aromatic hydrocarbon ring. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred. The non-aromatic hydrocarbon ring-linked group is a divalent group having a bonding bond on an atom constituting the ring by a plurality of monocyclic or condensed non-aromatic hydrocarbon rings; or a divalent group having a bonding bond on an atom constituting the ring by a single bond to a monocyclic or condensed non-aromatic hydrocarbon ring by one or more rings selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, a divalent group in which a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, wherein the first bond is on an atom constituting the ring of the first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second bond is on an atom constituting the ring of the second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. In addition, for example, a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, and the first bond is on an atom of the constituent ring of the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second bond is on an atom of the constituent ring of the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. As a linking non-aromatic hydrocarbon ring group, for example, bis(cyclohexane)-4,4'-diyl and 1-cyclohexylbenzene-4,4'-diyl can be cited. As the non-aromatic cyclic hydrocarbon group, a non-linked non-aromatic cyclic hydrocarbon group is preferred. Among them, as the non-aromatic cyclic hydrocarbon group, a divalent group of cyclohexane (cyclohexanediyl) is preferred. As the cyclohexanediyl group, from the viewpoint of solubility and molecular orientation of the liquid crystal compound, cyclohexane-1,4-diyl is preferred.

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

Aromatic heterocyclic groups include non-linked aromatic heterocyclic groups and linked aromatic heterocyclic groups. The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic group, and the carbon number is preferably 4 to 20. Examples of the aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanopyrrole ring, furanopyrrol ring, furanopyrrol ring, pyropyrrol ring, thiophene ... Furan ring, thienofuran ring, thienothiazole ring, benzoisosazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyrimidine ring, pyrimidine ring, tris(III) ring, quinoline ring, isoquinoline ring, oxazolidinone ring, phenanthidine ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring, etc. A linked aromatic heterocyclic group is a divalent group having a bonding bond on the atoms constituting the ring, in which multiple monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a divalent group in which a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, the first bond being on an atom constituting the first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bond being on an atom constituting the second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group. The non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and the carbon number is preferably 4 to 20. The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic ring or a condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. Examples of the non-aromatic heterocyclic ring include a tetrahydrofuran ring, a tetrahydropyran ring, a dihydroalkane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidinyl ring, a piperidine ring, a dihydropyridine ring, a piperidine ring, a tetrahydrothiazolyl ring, a tetrahydroxazolyl ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, The non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond, and the carbon number of the monocyclic or condensed ring is preferably 4 to 20. For example, a divalent group in which a first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, the first bond having a first atom in a constituent ring of the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bond having a second atom in a constituent ring of the second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

The aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q3 may be substituted by one or more groups selected from the group consisting of ^Rz , -OH, ^-ORz , -OC(=O) ^-Rz , _-NH2 , -NH- ^{Rz ,} -N(Rz ^' )- ^Rz , -C(=O) ^-Rz , -C(=O)-ORz, -C(=O) ^-NH2 , -C(=O)-NH- ^Rz , _-C (=O)-N(Rz ^' )-Rz, -SH, ^-SRz , trifluoromethyl, sulfonylamine, carboxyl, sulfonyl, cyano, nitro, and halogen. Here, ^Rz and Rz ^' independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. The aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group in ^Q3 are preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, respectively, from the viewpoint that the linearity of the molecular structure is high and the molecules represented by formula (2) are easy to aggregate and easily exhibit a liquid crystal state. It is more preferable that they are unsubstituted. The substituents possessed by the aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different. Furthermore, the aromatic alkyl group, non-aromatic alkyl group, aromatic heterocyclic group, and non-aromatic heterocyclic group may all be substituted, all be unsubstituted, or be partially substituted and partially unsubstituted. Furthermore, the substituents possessed by the divalent organic groups in A ¹¹ , A ¹² , and A ¹³ may be the same or different, and the divalent organic groups in A ¹¹ , A ¹² , and A ¹³ may all be substituted, all be unsubstituted, or be partially substituted and partially unsubstituted.

Q ³ is preferably a alkyl cyclic group, more preferably a phenylene group or a cyclohexanediyl group. In order to improve the linearity of the molecular structure of the liquid crystal compound, Q ³ is more preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group.

As the divalent organic group, ^Q3 is preferably a cycloalkyl group, i.e., the divalent organic group is a cycloalkyl group. Further, as the divalent organic group, phenylene and cyclohexanediyl are more preferred, and 1,4-phenylene and cyclohexane-1,4-diyl are further preferred in terms of improving the linearity of the molecular structure of the liquid crystal compound.

In formula (2), it is preferred that one of A ¹¹ , A ¹² , and A ¹³ is a partial structure represented by formula (3), and the other two are each independently a divalent organic group. It is preferred that Cy of the partial structure represented by formula (3) among A ¹¹ , A ¹² , and A ¹³ is a cycloalkyl group, and it is particularly preferred that the divalent organic group is a cycloalkyl group. It is further preferred that the cycloalkyl group is 1,4-phenylene or cyclohexane-1,4-diyl. It is further preferred that one of A ¹¹ and A ¹³ is a cyclohexane-1,4-diyl. It is further preferred that one of A ¹¹ and A ¹³ is a partial structure represented by formula (3), and the other one and A ¹² are divalent organic groups. In this case, it is preferred that one of the divalent organic groups of ^A11 and ^A13 is cyclohexane-1,4-diyl, and it is particularly preferred that ^A12 is 1,4-phenylene. With the above structure, the molecular alignment of the liquid crystal compound tends to be improved.

In terms of the linearity of the liquid crystal compound or the tendency of easy rotational motion around the short axis of the molecule, ^-Y1- and ^-Y2- are preferably single bonds having relatively small π bonding properties, -C(=O)O-, -OC(=O)-, -C(=S) _O- , -OC(=S)-, -C(=O)S- _, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O ₎ NH-, -NHC(=O)-, _-CH2O- , -OCH2-, _-CH2S- , or _-SCH2- , and more preferably single bonds, -C(=O)O-, -OC(=O)- _, -CH2CH2- _{, -CH2O-} , or _-OCH2- .

When ^X1 and ^Y1 or X1 and Y2 are bonded as in formula (2A), formula (2C), formula (2D) and formula (2F), ^Y1 bonded to ^{X1 or Y2 bonded} to ^X1 is preferably a ^single bond; ^-X1- and the other of ^-Y1- and -Y2- are preferably -C(=O)O- or -OC(=O) ^- . Moreover, when ^X1 and neither ^Y1 nor ^Y2 are bonded as in formula (2B) and formula ( _2E ), ^-X1- is preferably _-CH2CH2- , _-CH2O- or _-OCH2- ; ^-Y1- and ^-Y2- are preferably both -C(=O)O- or -OC(=O)-. With the above structure, the molecular alignment of the liquid crystal compound tends to be improved.

As formula (2), the above formula (2A), the above formula (2B), the above formula (2E), and the above formula (2F) are preferred. In another embodiment, as formula (2), it is preferred that one of A ¹¹ , A ¹² , and A ¹³ is 1,4-phenylene, and the other two are independently divalent organic groups, and it is particularly preferred that the divalent organic group is a cycloalkyl group. It is further preferred that the cycloalkyl group is 1,4-phenylene or cyclohexane-1,4-diyl. With the above structure, the linearity of the molecule tends to be high.

k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2. By becoming the above value, there is a tendency that the molecular orientation of the liquid crystal compound becomes good. When k is 2, each Y ² may be the same or different, and each A ¹³ may be the same or different.

The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention may specifically include the following polymerizable liquid crystal compounds, but is not limited thereto. In the formula, C ₅ H ₁₁ means n-pentyl, and C ₆ H ₁₃ means n-hexyl.

[Chemistry 15]

[Chemistry 16]

[Chemistry 17]

[Chemistry 18]

[Chemistry 19]

[Chemistry 20]

[Chemistry 21]

[Chemistry 22]

[Chemistry 23]

[Chemistry 24]

[Chemistry 25]

[Chemistry 26]

[Chemistry 27]

[Chemistry 28]

The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention may be used alone or in combination of two or more.

Regarding the polymerizable liquid crystal compound contained in the composition for forming anisotropic dye film of the present invention, from the viewpoint of the process, the isotropic phase appearance temperature is preferably below 160°C, more preferably below 140°C, further preferably below 115°C, further preferably below 110°C, and particularly preferably below 105°C. Furthermore, the isotropic phase appearance temperature here means the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid to liquid crystal. In the present invention, it is preferred that at least one of the phase transition temperatures is within the above range, and it is more preferred that both of the phase transition temperatures are within the above range.

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

(Relationship between polymerizable liquid crystal compounds and compounds represented by formula (1)) From the perspective of easily improving the orientation of an anisotropic dye film formed using an anisotropic dye film-forming composition, in the anisotropic dye film-forming composition, when the difference between the molecular length of the liquid crystal compound and the molecular length of the dye is smaller, the intermolecular interaction between the liquid crystal molecules and the dye molecules is stronger, and the dye molecules are less likely to hinder the aggregation of the liquid crystal molecules, which is better.

Therefore, in the anisotropic dye film-forming composition of the present invention, the ratio (r n1 / r n2 ) of the number of ring structures possessed by the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition (r _n1 ) to the number of ring structures possessed by the compound represented by formula (1) contained in the anisotropic dye film-forming composition (r _n2 ) is preferably _0.7 to _1.5 . In addition, a condensed ring formed by condensing two or more rings is counted as one ring structure.

Here, the number of ring structures (r _n2 ) possessed by the compound represented by formula (1) refers to the total of A ¹ , A ² , and A ³ in the formula. Specifically, when n is 1, r _n2 is 3; when n is 2, r _n2 is 4; when n is 3, r _n2 is 5. Furthermore, even if X is a cyclic functional group such as pyrrolidinyl or piperidinyl, the ring structure contained in X is not included in the number of ring structures (r _n2 ) possessed by the compound represented by formula (1).

More specifically, when n is 1, r _n2 is 3, and thus r _n1 is 3 or 4; when n is 2, r _n2 is 4, and thus r _n1 is 3, 4, 5, or 6; when n is 3, r _n2 is 5, and thus r _n1 is 4, 5, 6, or 7. In this way, the ratio (r _{n1 /r n2} ) of the number of ring structures possessed by the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition (r _n1 ) to the number of ring structures possessed by the compound represented by formula (1) contained in the anisotropic dye film-forming composition (r _n2 ) is preferably _0.7 to 1.5.

The number (r _n1 ) of the ring structures of the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition does not include the ring structures (such as oxirane rings or cyclohexane rings) contained in the polymerizable groups in the polymerizable liquid crystal compound.

(Polymerization initiator) The anisotropic pigment film-forming composition of the present invention may contain a polymerization initiator as needed. The polymerization initiator is a compound that can initiate the polymerization reaction of the polymerizable liquid crystal compound. As the polymerization initiator, a photopolymerization initiator that generates active free radicals by the action of light is preferred.

As polymerization initiators that can be used, for example, there can be listed: titanium bis(cyclopentadienyl) derivatives; bisimidazole derivatives; halogenated oxadiazole derivatives; halogenated methyl-s-triazole derivatives; alkyl phenone derivatives; oxime ester derivatives; benzoin; benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; coronium salts; anthraquinone derivatives; acetophenone derivatives; 9-oxosulfuronium; Derivatives; benzoate derivatives; acridine derivatives; phenanthrone derivatives; anthrone derivatives, etc. Among the photopolymerization initiators, more preferred are alkylphenone derivatives, oxime ester derivatives, bisimidazole derivatives, acetophenone derivatives, and 9-oxosulfuron derivatives. derivatives.

Specifically, the titanium cyclopentadienyl derivatives include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyl titanium, dicyclopentadienyl bis(2,3,4,5,6-pentafluorophenyl-1-yl) titanium, dicyclopentadienyl bis(2,3,5,6-tetrafluorophenyl-1-yl) titanium, dicyclopentadienyl bis(2,4,6-trifluorophenyl-1-yl) titanium, dicyclopentadienyl bis( 2,6-difluorophenyl-1-yl) titanium, dicyclopentadienylbis(2,4-difluorophenyl-1-yl) titanium, bis(methylcyclopentenyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl) titanium, bis(methylcyclopentenyl)bis(2,6-difluorophenyl-1-yl) titanium, dicyclopentadienyl[2,6-di-fluoro-3-(pyrrol-1-yl)-phenyl-1-yl]titanium, etc.

Examples of the bisimidazole 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.

Examples of halogenated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl)]-1,3,4-oxadiazole, and 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole.

Moreover, as halogenmethyl-s-triazine derivatives, 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, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, and the like can be cited.

Examples of the alkylphenone derivatives include diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-thiazolidine propane-1-one, 2-benzyl-2-dimethylamino-1-(4-thiazolidine phenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-thiazolidine phenyl) butan-1-one, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzyl)coumarin, and 4-(diethylamino)chalcone.

In addition, examples of oxime ester derivatives include 2-(benzyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl-1-[6-(2-methylbenzyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, and oxime ester derivatives described in Japanese Patent Laid-Open No. 2000-80068, Japanese Patent Laid-Open No. 2006-36750, International Publication No. WO2009/131189, and the like.

Furthermore, examples of benzoins include benzoin, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, and the like.

Furthermore, 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'-tetrakis(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone.

Examples of acylphosphine oxide derivatives include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4,6-trimethylbenzyl)phenylphosphine oxide.

Examples of iodine salts include diphenyliodine tetrakis(pentafluorophenyl)borate, diphenyliodine hexafluorophosphate, diphenyliodine hexafluoroantimonate, and di(4-nonylphenyl)iodine hexafluorophosphate.

Examples of coronium salts include triphenylcoronium hexafluorophosphate, triphenylcoronium hexafluoroantimonate, triphenylcoronium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]coronium hexafluorophosphate, 4,4'-bis[diphenylcoronium]diphenyl sulfide bis(hexafluorophosphate), 4,4'-bis[di(β-hydroxyethoxy)phenylcoronium]diphenyl sulfide bis(hexafluoroantimonate), 4,4'-bis[di(β-hydroxyethoxy)phenylcoronium]diphenyl sulfide bis(hexafluorophosphate), 7-[di(p-toluyl)coronium]-2-isopropyl 9-oxysulfonate -Hexafluoroantimony salt, 7-[di(p-toluyl)copperyl]-2-isopropyl 9-oxysulfonate -tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylcorbyl-diphenyl sulfide-hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylcorbyl-diphenyl sulfide-hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluoyl)corbyl-diphenyl sulfide-tetrakis(pentafluorophenyl)borate, and the like.

Examples of anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone.

Moreover, 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-isopropyl-1-propanone, and 1,1,1-trichloromethyl-(p-butylphenyl)ketone.

Also, as 9-oxosulfuron Derivatives, for example: 9-oxosulfuron , 2-ethyl 9-oxosulfuron , 2-isopropyl 9-oxysulfide , 2-chloro-9-oxysulfuron , 2,4-dimethyl 9-oxosulfuron , 2,4-diethyl 9-oxysulfide 、2,4-Diisopropyl 9-oxysulfide wait.

Moreover, examples of benzoic acid ester derivatives include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

Examples of acridine derivatives include 9-phenylacridine and 9-(p-methoxyphenyl)acridine.

In addition, examples of the phenanthrene derivatives include 9,10-dimethylbenzophenanthrene and the like.

In addition, examples of anthrone derivatives include benzanthrone and the like.

The polymerization initiator may be used alone or in combination of two or more.

As the polymerization initiator, a commercial product may be used. As commercial products, for example, IRGACURE (registered trademark, hereinafter the same) 250, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 784, OXE-01, OXE-02 (all manufactured by BASF); Seikuol (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); kayacure (registered trademark) BP100 and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); Adeka Optomer SP-152, and SP-170 (manufactured by ADEKA Co., Ltd.); TAZ-A and TAZ-PP (manufactured by Nihon SiberHegner Co., Ltd.); and TAZ-104 (manufactured by Sanhe Chemical Co., Ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (manufactured by Changzhou TRONLY NEW ELECTRONIC MATERIALS CO., LTD.).

When the composition of the present invention contains a polymerization initiator, from the viewpoint of not easily disturbing the alignment of the polymerizable liquid crystal compound, the content of the polymerization initiator in the composition of the present invention is generally 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.

A polymerization accelerator may be used in combination with the polymerization initiator as needed. Examples of the polymerization accelerator include: N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; heterocyclic alkyl compounds such as 2-alkylbenzothiazole, 2-alkylbenzoxazole, and 2-alkylbenzimidazole; and alkyl compounds such as aliphatic multifunctional alkyl compounds.

Furthermore, a sensitizing dye may be used in combination to improve the sensitivity as needed. The sensitizing dye may be used appropriately according to the wavelength of the exposure light source, for example, the sensitizing dye described in Japanese Patent Laid-Open No. 4-221958, Japanese Patent Laid-Open No. 4-219756, etc. Pigments; coumarin pigments with a heterocyclic ring described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, etc.; 3-ketocoumarin pigments described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, etc.; pyrromethene pigments described in Japanese Patent Laid-Open No. 6-19240, etc.; Japanese Patent Laid-Open No. 47-2528, Japanese Patent Laid-Open No. 54-155292, Japanese Patent Laid-Open No. 45-37377, Japanese Patent Laid-Open No. The pigments having a dialkylaminobenzene skeleton described in Japanese Patent Laid-Open No. 48-84183, Japanese Patent Laid-Open No. 52-112681, Japanese Patent Laid-Open No. 58-15503, Japanese Patent Laid-Open No. 60-88005, Japanese Patent Laid-Open No. 59-56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, Japanese Patent Laid-Open No. 4-288818, etc., etc. The sensitizing pigment may be used alone or in combination of two or more.

(Solvent) The composition for forming anisotropic pigment film of the present invention may also contain a solvent as needed. The solvent that can be used is not particularly limited as long as it can fully disperse or dissolve the pigment or other additives in the liquid crystal compound. For example, alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, 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; acetone, methyl ethyl ketone, cyclopentane ... Ketone solvents such as pentanone, 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, perfluorodecahydronaphthalene, 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.

The solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound and the pigment, and more preferably a solvent that can completely dissolve the polymerizable liquid crystal compound and the pigment. Also, it is preferably a solvent that is inert to the polymerization reaction. Moreover, from the viewpoint of applying the anisotropic pigment film-forming composition of the present invention described below, it is preferably a solvent with a boiling point in the range of 50 to 200°C.

When the anisotropic pigment film forming composition of the present invention contains a solvent, the content ratio of the solvent in the anisotropic pigment film forming composition relative to the total amount of the composition of the present invention (100 mass%) is preferably 50 to 98 mass%. In other words, the solid content in the anisotropic pigment film forming composition of the present invention is preferably 2 to 50 mass%. If the solid content in the anisotropic pigment film forming composition is below the above upper limit, the viscosity of the anisotropic pigment film forming composition will not be too high, the thickness of the obtained polarizing film will become uniform, and the polarizing film will not easily have a tendency to be uneven. The solid content can be determined in consideration of the thickness of the polarizing film to be manufactured. The viscosity of the anisotropic dye film composition of the present invention is not particularly limited as long as a uniform film without uneven thickness can be produced by the coating method described below. From the viewpoint of obtaining uniform thickness over a large area, productivity such as coating speed, and in-plane uniformity of optical properties, the viscosity is preferably 0.1 mPa·s or more, preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

(Other additives) The anisotropic pigment film-forming composition of the present invention may further contain polymerization inhibitors, polymerization aids, polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, metal oxides and other additives as needed. By containing additives, the coating properties or stability of the anisotropic pigment film-forming composition may be improved, or the stability of the anisotropic pigment film formed by the anisotropic pigment film-forming composition may be improved.

[Method for producing anisotropic pigment film-forming composition] The method for producing the anisotropic pigment film-forming composition of the present invention is not particularly limited. For example, the pigment, polymerizable liquid crystal compound, solvent as required, other additives, etc. are mixed, and stirred and shaken at 0 to 80°C to dissolve the pigment. In the case of poor solubility, a homogenizer, a bead mill disperser, etc. can also be used. As a method for producing the anisotropic pigment film-forming composition of the present invention, a filtering step can also be included for the purpose of removing foreign matter in the composition.

Regarding the anisotropic pigment film-forming composition of the present invention, the composition obtained by removing the solvent from the anisotropic pigment film-forming composition may be liquid crystal at any temperature or may not be liquid crystal at any temperature, but preferably exhibits liquid crystal properties at any temperature. From the viewpoint of the coating process described below, the composition obtained by removing the solvent from the anisotropic pigment film-forming composition preferably has an isotropic phase appearance temperature of less than 160°C, more preferably less than 140°C, further preferably less than 115°C, further preferably less than 110°C, and particularly preferably less than 105°C.

[Anisotropic pigment film] The anisotropic pigment film of the present invention is formed using the anisotropic pigment film forming composition of the present invention. Therefore, the anisotropic pigment film of the present invention includes a pigment, and one or both of a polymerizable liquid crystal compound and a polymer having a unit based on the polymerizable liquid crystal compound, and the pigment includes a compound represented by formula (1). The anisotropic pigment film of the present invention may also include 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/inorganic filler, an organic/inorganic nanosheet, an organic/inorganic nanofiber, a metal oxide, etc.

The anisotropic pigment film of the present invention can be formed using the anisotropic pigment film-forming composition of the present invention.

The anisotropic pigment film of the present invention can function as a polarizing film that utilizes the anisotropy of light absorption to obtain linear polarization, circular polarization, elliptical polarization, etc., and can also be functionalized as various anisotropic pigment films such as refractive anisotropy or conductive anisotropy by selecting a film formation process and a substrate or a composition containing an organic compound (pigment or transparent material).

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 OLED, the orientation characteristics of the anisotropic dye film can be expressed by the dichroic ratio. As long as the dichroic ratio is 8 or more, it can function as a polarizing element. It is preferably 15 or more, more preferably 20 or more, more preferably 25 or more, particularly preferably 30 or more, and more preferably 40 or more. The higher the dichroic ratio, the better. By making the dichroic ratio above the above lower limit, it is useful as the following optical element, especially the polarizing element. When used as a polarizing element for an anti-reflection film for OLED, even if the performance of peripheral materials such as the phase difference film is low, as long as the performance of the polarizing element is high, the characteristics as an anti-reflection film are also improved. Therefore, as long as the performance of the polarizing element is high, it is easy to simplify the layer structure, and even if it is a thin film structure, it is easy to show sufficient functions and can be well used for uses including bending and bending. In addition, the cost can be suppressed to a low level.

The so-called dichroic ratio (D) in the present invention is expressed by the following formula when the pigment is uniformly aligned. D = _Az / _Ay Here, _Az is the absorbance observed when the polarization direction of the light incident on the anisotropic pigment film is parallel to the alignment direction of the anisotropic pigment, and _Ay is the absorbance observed when the polarization direction of the light incident on the anisotropic pigment film is perpendicular. There is no particular limitation as long as the same wavelength is used for each absorbance ( _Az , _Ay ), and any wavelength can be selected according to the purpose. When expressing the degree of alignment of the anisotropic pigment film, it is preferably a value corrected for the visual sensitivity in a specific wavelength region of 380 nm to 780 nm of the anisotropic pigment film, or a value of the maximum absorption wavelength in the visible region.

Furthermore, the transmittance of the anisotropic pigment film of the present invention is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more at the target wavelength used. Furthermore, the transmittance can be the upper limit corresponding to the application. When the anisotropic pigment film of the present invention is used as a pigment film having anisotropy in the entire visible light wavelength region, the transmittance of the anisotropic pigment film in the visible light wavelength region is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. Furthermore, the transmittance can be the upper limit corresponding to the application. For example, when the degree of polarization is increased, the transmittance is preferably 50% or less. By setting the transmittance in the above range, the optical element is useful as the following optical element, and is particularly useful as an optical element for a liquid crystal display for color display or an antireflection film obtained by combining an anisotropic dye film and a retardation film.

The film thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 100 nm or more, and further preferably 500 nm or more in terms of dry film thickness. On the other hand, it is preferably 30 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 3 μm or less. By making the film thickness of the anisotropic dye film within the above range, there is a tendency to obtain uniform orientation of the dye in the film and uniform film thickness.

[Method for producing anisotropic pigment film] The anisotropic pigment film of the present invention is preferably produced by a wet film-forming method using the anisotropic pigment film-forming composition of the present invention. The wet film-forming method in the present invention refers to a method of coating and aligning the anisotropic pigment film composition on a substrate by a certain method. Therefore, the anisotropic pigment film composition only needs to be fluid and may or may not contain a solvent. From the perspective of viscosity or film uniformity during coating, it is more preferable to contain a solvent.

The liquid crystal or pigment in the anisotropic dye film can be aligned by shearing or the like during the coating process, or can be aligned during the solvent drying process. In addition, the liquid crystal or pigment can be aligned and layered on the substrate by heating after coating and drying to realign the liquid crystal or pigment. In the wet film forming method, if the anisotropic dye film composition is applied to the substrate, the pigment or liquid crystal compound will be self-aggregated (molecular aggregation state such as liquid crystal state) in the anisotropic dye film composition, during the solvent drying process, or after the solvent is completely removed, thereby generating an alignment in a small area. By applying an external field in this state, it can be aligned in a certain direction in a large area, and an anisotropic dye film with the desired properties can be obtained. In this respect, it is different from the method of using a solution containing a pigment to dye a polyvinyl alcohol (PVA) film and stretch it, and the principle of aligning the pigment only by the stretching step. Furthermore, the so-called external field here can be listed as the influence of the orientation treatment layer applied to the substrate in advance, shear force, magnetic field, electric field, heat, etc., which can be used alone or in combination. A heating step can be performed as needed. The process of applying the anisotropic pigment film composition to the substrate to form a film, the process of applying an external field to align it, and the process of drying the solvent can be performed sequentially or simultaneously.

Examples of methods for applying the composition for forming an anisotropic dye film to a substrate in a wet film-forming method include coating, immersion coating, LB (Langmuir-Blodgett) film-forming method, and known printing methods. In addition, there is also a method of transferring the anisotropic dye film obtained in this way to another substrate.

Among them, it is preferred to apply the composition for forming an anisotropic dye film to the substrate by coating. The orientation direction of the anisotropic dye film may be different from the coating direction. Furthermore, the orientation direction of the anisotropic dye film in the present invention, for example, refers to the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, and refers to the phase advance axis or phase retardation axis in the case of a phase difference film.

The method for obtaining an anisotropic pigment film by coating the composition for anisotropic pigment film is not particularly limited, and examples thereof include the method described in "Coating Engineering" by Yuji Harasaki (Asakura Bookstore Co., Ltd., published on March 20, 1971), pages 253-277; "Creation and Application of Molecular Coordinating Materials" supervised by Kunihiro Ichimura (CMC Co., Ltd., published on March 20, 1971); Co., Ltd., published on March 3, 1998, pages 118 to 149; on a substrate with a step structure (which may also be pre-aligned), a coating method using a slot die coating method, a rotary coating method, a spray coating method, a rod coating method, a roller coating method, a doctor blade coating method, a curtain coating method, a spray method, an immersion method, etc. Among them, if a slot die coating method or a rod coating method is used, a more uniform anisotropic pigment film can be obtained, so it is better.

The die coating machine used for the narrow slot die coating method generally has a coating machine that sprays the coating liquid, the so-called narrow slot die. The slit die is disclosed in, for example, Japanese Patent Laid-Open No. 2-164480, Japanese Patent Laid-Open No. 6-154687, Japanese Patent Laid-Open No. 9-131559, "Basics and Applications of Dispersion, Coating, and Drying" (2014, Techno System Co., Ltd., ISBN9784924728707 C 305), "Wet Coating Technology in Displays and Optical Components" (2007, Information Agency, ISBN9784901677752), "Precision Coating and Drying Technology in Electronics" (2007, Association for Technical Information, ISBN9784861041389), etc. With regard to the known slit dies, coating can be performed even on flexible components such as films or tapes or on relatively hard components such as glass substrates.

The substrate used for forming the anisotropic dye film of the present invention may be glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetylcellulose or urethane film, etc. In order to control the orientation direction of the dye, the substrate surface may be subjected to orientation treatment (orientation film) by the known methods described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., October 30, 2000, pp. 226-239, etc.) (rubbing method, method of forming grooves (fine groove structure) on the surface of the orientation film, method of using polarized ultraviolet light/polarized laser (photo-orientation method), orientation method by LB film formation, orientation method by oblique evaporation of inorganic substances, etc.). In particular, alignment treatment using a rubbing method and a photo-alignment method can be well listed. As materials used in the rubbing method, polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin, etc. can be listed. As materials used in the photo-alignment method, polycinnamate series, polyamide/polyimide series, azobenzene series, etc. can be listed. When an alignment treatment layer is provided, it is believed that the liquid crystal compound or the pigment is aligned by the influence of the alignment treatment of the alignment treatment layer and the shear force applied to the anisotropic pigment film composition during coating.

There is no particular limitation on the method and interval of supplying the anisotropic pigment film composition when applying the anisotropic pigment film composition. Since the supply operation of the coating liquid becomes complicated or the coating film thickness varies when the coating liquid is started and stopped, it is more preferable to apply the anisotropic pigment film composition while continuously supplying the anisotropic pigment film composition when the thickness of the anisotropic pigment film is thin.

The speed of coating the composition for anisotropic pigment film is usually 0.001 m/min or more, preferably 0.01 m/min or more, more preferably 0.1 m/min or more, further preferably 1.0 m/min or more, and particularly preferably 5.0 m/min or more. Also, it is usually 400 m/min or less, preferably 200 m/min or less, more preferably 100 m/min or less, and further preferably 50 m/min or less. By setting the coating speed within the above range, the anisotropic pigment film has an anisotropic property and tends to be coated uniformly. The coating temperature of the composition for anisotropic pigment film is usually 0°C or more and 100°C or less, preferably 80°C or less, and further preferably 60°C or less. The humidity when applying the composition for anisotropic dye film is preferably 10%RH or more and preferably 80RH% or less.

The anisotropic pigment film may also be subjected to an insolubilization treatment. Insolubilization means a treatment to improve the stability of the film by reducing the solubility of the compound in the anisotropic pigment film and controlling the dissolution of the compound from the anisotropic pigment film. Specifically, polymerization or coating of the film is better from the perspective of the ease of subsequent steps and the durability of the anisotropic pigment film.

When the film is polymerized, light, heat, and/or radiation are used to polymerize the film in which the liquid crystal molecules and the pigment molecules are aligned.

When light or radiation is used for polymerization, it is preferred to use active energy rays with a wavelength in the range of 190 to 450 nm. The light source of active energy rays with a wavelength of 190 to 450 nm is not particularly limited, and examples thereof include: xenon lamps, halogen lamps, tungsten filament lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and other light sources; argon ion lasers, YAG (Yttrium Aluminum Garnet) lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers, and other laser light sources. When using the device under irradiation with light of a specific wavelength, an optical filter may also be used. The exposure amount of the active energy ray is preferably 10 to 10,000 J/m ² .

When the polymerization is performed using heat, it is preferably performed at a temperature in the range of 50 to 200°C, more preferably in the range of 60 to 150°C.

Polymerization can also be performed using light, heat, and/or radiation. Photopolymerization or a combination of photopolymerization and thermal polymerization is preferred in terms of a shorter film formation process time and a simpler apparatus.

[Optical element] The optical element of the present invention includes the anisotropic pigment film of the present invention.

The optical element of the present invention refers to a polarizing element that utilizes the anisotropy of light absorption to obtain linear polarization, circular polarization, elliptical polarization, etc., a phase difference element, an element having functions such as refractive anisotropy or conductive anisotropy. These functions can be appropriately adjusted by the selection of the anisotropic pigment film formation process and the substrate or the composition containing the organic compound (pigment or transparent material).

The optical element of the present invention is preferably used as a polarizing element. The optical element of the present invention can be used for flexible displays and the like in that a polarizing element can be obtained by forming an anisotropic pigment film on a substrate by coating or the like.

In order to maintain and improve the function of the anisotropic pigment film, the optical element may also be provided with other layers. For example, there may be: a layer with a function of blocking a specific wavelength or a layer with a function of blocking a specific substance (barrier films such as oxygen blocking films and water vapor blocking films, etc.) to improve durability such as light resistance, heat resistance, and water resistance; a wavelength cutoff filter or a layer containing a material that absorbs a specific wavelength to change the color gamut or improve optical properties, etc.

[Polarizing element] The polarizing element of the present invention may have any other film (layer) as long as it has the anisotropic pigment film of the present invention. For example, it can be manufactured by providing an orientation film on a substrate and forming the anisotropic pigment film of the present invention on the surface of the orientation film. In addition, the polarizing element is not limited to the anisotropic pigment film, but can also be used in combination with an external coating having functions such as improving polarization performance and improving mechanical strength; an adhesive layer or an anti-reflection layer; an orientation film; a layer having optical functions such as a phase difference film, a brightness enhancement film, a reflection or anti-reflection film, a semi-transmissive reflection film, and a diffusion film. Specifically, the layers having the above-mentioned various functions can be formed by lamination by coating or bonding, and used in the form of a laminate. The layers can be appropriately arranged according to the manufacturing process, characteristics and functions, and the layering positions and order are not particularly limited. For example, the layers can be formed on the anisotropic pigment film or on the opposite side of the substrate on which the anisotropic pigment film is arranged. In addition, the layers can be formed before or after the anisotropic pigment film is formed.

The layers having optical functions can be formed by the following method.

The layer having the function of a phase difference film can be formed by coating or laminating the phase difference film on other layers constituting the polarizing element. The phase difference film can be formed by, for example, performing the stretching treatment described in Japanese Patent Laid-Open No. 2-59703, Japanese Patent Laid-Open No. 4-230704, or performing the treatment described in Japanese Patent Laid-Open No. 7-230007.

The layer having the function of a brightness enhancement film can be formed by coating or laminating the brightness enhancement film on other layers constituting the polarizing element. The brightness enhancement film can be formed, for example, by forming fine holes using the method described in Japanese Patent Publication No. 2002-169025 and Japanese Patent Publication No. 2003-29030, or by stacking two or more cholesterol liquid crystal layers having different central wavelengths for selective reflection.

The layer having the function of a reflective film or a semi-transmissive reflective film can be formed, for example, by coating or laminating a metal thin film obtained by evaporation or sputtering on other layers constituting a polarizing element. The layer having the function of a diffusion film can be formed, for example, by coating a resin solution containing microparticles on other layers constituting a polarizing element.

The layer having the function of a phase difference film or an optical compensation film can be formed by coating a liquid crystal compound such as a discotic liquid crystal compound, a nematic liquid crystal compound, a lamellar liquid crystal compound, or a cholesteric liquid crystal compound on other layers constituting a polarizing element and aligning them. In this case, an alignment film can also be provided on the substrate, and a phase difference film or an optical compensation film can be formed on the surface of the alignment film.

When the anisotropic pigment film of the present invention is used as an anisotropic pigment film in various display elements such as liquid crystal elements (LCD) or organic electroluminescent elements (OLED), the anisotropic pigment film of the present invention can be directly formed on the surface of the electrode substrate constituting the display element, and the substrate formed with the anisotropic pigment film of the present invention can also be used as a component of the display element. [Example]

The present invention is further specifically described by way of examples, but the present invention is not limited to the following examples as long as it does not exceed the gist of the invention. In the following description, "parts" means "parts by weight".

[Method for Identifying Liquid Crystal Phase] The liquid crystal properties of the obtained anisotropic dye film-forming composition were observed by differential scanning calorimetry (Seiko Instruments, "DSC220CU"), X-ray structural analysis (Rigaku Co., Ltd., "NANO-Viewer"), and a polarizing microscope (Nikon Instruments, "ECLIPSE LV100N POL") attached to a high temperature stage (Toyo Technology Co., Ltd., "HCS302-LN190"), and whether it was liquid crystal was identified according to the method described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000) pages 9 to 50 and 117 to 176.

[Measurement of transmittance of anisotropic pigment film for polarized light in the direction of absorption axis/polarization axis and dichroic ratio] The transmittance of anisotropic pigment film for polarized light in the direction of absorption axis/polarization axis was measured using a spectrophotometer equipped with a Gran-Thomson polarizing element (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100"). The transmittance of the anisotropic pigment film for polarized light in the direction of absorption axis and the transmittance of the anisotropic pigment film for polarized light in the direction of polarization axis were measured, and the dichroic ratio (D) was calculated according to the following formula. D = _Az / _Ay (where _Ay = -log( _Ty ); _Az = -log( _Tz ); _Tz is the transmittance of the anisotropic pigment film for polarized light in the direction of the absorption axis; _Ty is the transmittance of the anisotropic pigment film for polarized light in the direction of the polarization axis)

Specifically, an anisotropic dye film composition was injected into an interlayer cell (cell gap: 8.0 μm, 10.0 μm, obtained by rubbing the formed polyimide film with cloth in advance) formed on a glass substrate with an alignment film of polyimide (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems) in an isotropic phase, and the anisotropic dye film was obtained by cooling to 80°C at 5°C/min, and then cooling to 0°C at 5°C/min, and the dichroic ratio was measured at each temperature. The dichroic ratio at the temperature and wavelength showing the maximum dichroic ratio was determined as the dichroic ratio of the anisotropic dye film. In the measurement at this temperature, the dichroic ratio at the wavelength at which the absorbance in the orthotropic position (absorption axis direction) in the anisotropic dye film shows a maximum value (the dichroic ratio at the wavelength at which the absorbance in the film shows a maximum value) is also measured.

[Synthesis of polymerizable liquid crystal compounds]

<Liquid crystal compound (I-1)> The liquid crystal compound (I-1) was synthesized by the method according to the compound described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

The structure was confirmed by NMR. The results are shown below. ¹ H NMR (CDCl ₃ , 400 MHz) δ1.23 - 1.72 (m, 38H), 1.76 - 1.86 (m, 2H), 2.11 - 2.23 (m, 4H), 2.48 - 2.60 (m, 1H), 3.20 - 3.30 (m, 1H), 3.47 (t, 2H, J = 6.8 Hz), 4.04 (t, 2H, J = 6.8 Hz), 4.15 (t, 2H, J = 6.8 Hz), 5.82 (d, 2H, J = 10.4 Hz), 6.12 (dd, 2H, J = 10.4, 17.4 Hz), 6.40 (d, 2H, J = 17.4 Hz), 6.97 (d, 2H, J = 9.2 Hz), 7.11 (d, 2H, J = 9.2 Hz), 7.21 (d, 2H, J = 9.0 Hz), 8.13 (d, 2H, J = 9.0 Hz)

[Chemistry 29]

<Liquid crystal compound (I-2)> The liquid crystal compound (I-2) was synthesized according to the synthesis method described below.

[Chemistry 30]

Synthesis of (I-2-a): Add ethyl propiolate (9.7 g, 99 mmol) and copper (I) oxide (7.5 g, 94 mmol) to a solution of p-iodophenol (11.0 g, 50 mmol) in N,N-dimethylformamide (150 mL), stir at 110°C for 9 hours, and cool naturally to room temperature. After filtering and separating the precipitate, add ethyl acetate, wash with water, and then wash with saturated brine. Purify by silica gel column chromatography (hexane/ethyl acetate) to obtain 7.3 g of brown crystals (I-2-a).

Synthesis of (I-2-b): (I-2-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. After filtration and separation, diethyl ether was added, and the mixture was washed with water and then with saturated saline. Purification was performed by silica gel column chromatography (hexane/ethyl acetate) to obtain 5.5 g of an orange solid (I-2-b).

Synthesis of (I-2-c): Mix (I-2-b) (3.6 g, 10 mmol), potassium hydroxide (1.7 g, 30 mmol), and water (20 mL), and stir at 100°C for 2 hours. Add water (20 mL), make it acidic with concentrated hydrochloric acid, and filter to separate the precipitate. The precipitate obtained was washed by suspension with acetonitrile to obtain 3.2 g of a milky white solid (I-2-c).

Synthesis of (I-2-d): Mix (I-2-c) (2.33 g, 7.0 mmol) and tetrahydrofuran (20 mL), and then add N,N-dimethylaniline (1.02 g, 8.4 mmol) and 2,5-di-tert-butylphenol (54 mg). After cooling in an ice bath, slowly add acryloyl chloride (0.76 g, 8.4 mmol). After stirring in an ice bath for 6 hours, add dichloromethane, and wash with 1 mol/L hydrochloric acid, saturated sodium bicarbonate water, and saturated saline water in sequence. Purify by silica gel column chromatography (chloroform/methanol) to obtain 2.0 g of a white solid (I-2-d).

Synthesis of (I-2-e): (I-2-e) was synthesized by the synthesis method described in Japanese Patent Publication No. 2014-262884.

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

Synthesis of (I-2-g): Mix (I-2-f) (2.6 g, 4.62 mmol), pyridinium p-toluenesulfonate (0.23 g, 0.92 mmol), 2,5-di-tert-butylphenol (44 mg), and ethanol (20 mL) and stir at 50°C for 2 hours. The reaction solution was released into water, and the precipitate was separated by filtration and dried to obtain 2.0 g of a white solid (I-2-g).

Synthesis of (I-2-h): Compound (I-2-h) was synthesized according to the synthesis method described below.

[Chemistry 31]

(I-2-i) was synthesized by the method according to the compound described in Lub et al., Recl. Trav. ChIm. Pays-Bas, 115, 321-328 (1996). Next, (I-2-i) (trans isomer only) (42.9 g, 107.6 mmol), pyridinium p-toluenesulfonate (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, dissolved in ethyl acetate (150 mL), hexane (750 mL) was added, and cooled. The precipitate was separated by filtration, washed with hexane, and dried to obtain 29.2 g of a white solid (I-2-j). Mix (I-2-j) (37.2 g, 118.3 mmol), N,N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-tert-butylphenol (0.24 g), and tetrahydrofuran (380 mL). After cooling in an ice bath, slowly add acryloyl chloride (16.1 g, 177.5 mmol). After the dropwise addition, stir at 50°C for 2 hours, remove the solvent by distillation until the liquid volume becomes 190 mL, and release it into 1 mol/L hydrochloric acid under ice bath cooling. Filter and separate the precipitate, and wash with water and hexane. The product was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 39.4 g of a white solid (I-2-h).

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

The results of liquid chromatography-mass spectrometry analysis of the compound are disclosed below. LC-MS (APCI) m/z 851.5 (M+Na ⁺ ) In addition, the structure was confirmed by NMR. The results are shown below. ¹ H NMR (CDCl ₃ , 400 MHz) 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 = 6.8 Hz), 3.99 (t, 2H, J = 6.8 Hz), 4.15 (t, 4H, J = 6.8 Hz), 5.80 (d, 2H, J = 10.4 Hz), 6.12 (dd, 2H, J = 17.2, 10.4 Hz), 6.39 (d, 2H, J = 17.2 Hz), 6.89 (d, 2H, J = 6.8 Hz), 7.10 (d, 2H, J = 6.8 Hz),7.19 (d, 2H, J = 6.8 Hz), 7.55 (d, 2H, J = 6.8 Hz)

Regarding the liquid crystal compound (I-1) and the liquid crystal compound (I-2), the isotropic phase appearance temperature (phase transition temperature from liquid crystal to liquid and phase transition temperature from liquid to liquid crystal) was determined by differential scanning calorimetry. In addition, the differential scanning calorimetry was performed using 0.2 parts by weight of 4-methoxyphenol added as a polymerization inhibitor relative to 100 parts by weight of the liquid crystal compound. The results are shown in Table 1. In addition, the temperature was confirmed to be the isotropic phase appearance temperature by polarizing microscope observation and X-ray structural analysis.

[Table 1] Liquid crystal compounds I-1 I-2 Phase transition temperature from liquid crystal to liquid (℃) 111.0 103.1 Phase transition temperature from liquid to liquid crystal (℃) 109.4 101.9

[Synthesis of polymerizable liquid crystal compound] <Liquid crystal compound (I-3)> The liquid crystal compound (I-3) was synthesized according to the synthesis method described below.

[Chemistry 32]

Synthesis of (I-3-a): (I-3-a) was synthesized by the method according to the compound described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996).

Synthesis of (I-3-b): 4-iodophenol (3.62 g, 16.5 mmol), (I-3-a) (6.43 g, 16.1 mmol), N,N-dimethylamino-4-pyridine (0.39 g, 3.20 mmol), and dichloromethane (80 mL) were mixed, cooled in an ice bath, and then 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) (3.39 g, 17.7 mmol) was added and stirred for 5 minutes. Then, the mixture was stirred at room temperature for 2 hours, washed with a saturated aqueous solution of ammonium chloride, and then washed with saturated sodium chloride water. The solution was concentrated and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 8.49 g of a white solid (I-3-b).

Synthesis of (I-3-c): Add (I-3-b) (5.00 g, 8.33 mmol) to diisopropylamine (70 mL). After complete dissolution, mix dichlorobis(triphenylphosphine)palladium (II) (58 mg, 0.08 mmol) and copper (I) iodide (48 mg, 0.25 mmol), and add trimethylsilyl acetylene (0.98 g, 9.99 mmol). After stirring at room temperature for 30 minutes, extract with water-ethyl acetate and wash with saturated brine. Concentrate the solution and purify it by silica gel column chromatography (hexane/ethyl acetate) to obtain 4.30 g of a white solid (I-3-c).

Synthesis of (I-3-d): Mix (I-3-c) (4.30 g, 7.53 mmol) and chloroform (100 mL), cool in an ice bath, and add tetrabutylammonium fluoride (TBAF) tetrahydrofuran solution (1 mol/L, 9 mL). Stir for 20 minutes, extract with water-chloroform, and wash with saturated brine. Concentrate the solution and purify by silica gel column chromatography (hexane/ethyl acetate) to obtain 3.80 g of a white solid (I-3-d).

Synthesis of (I-3-e): (I-3-b) (3.56 g, 5.93 mmol), tetrakistriphenylphosphine palladium (0) (68 mg, 0.06 mmol), copper (I) iodide (34 mg, 0.18 mmol), and diisopropylamine (120 mL) were mixed and cooled in an ice bath, and then a solution of (I-3-d) (2.96 g, 5.93 mmol) in diisopropylamine (40 mL) was added. After stirring at room temperature for 1 hour, extraction was performed with water-chloroform, and then washed with saturated brine. The solution was concentrated and purified by silica gel column chromatography (chloroform) to obtain a white solid (I-3-e).

Synthesis of (I-3-f): Mix (I-3-e) obtained by the above operation and tetrahydrofuran (60 mL), and add ethanol (60 mL) after completely dissolving at 50°C. Add pyridinium p-toluenesulfonate (PPTS) (0.54 g, 2.13 mmol) to the slurry solution, heat at 60°C for 2 hours, and leave overnight. The next day, heat to 60°C again and completely dissolve, then add the reaction solution to ice water. After extracting with chloroform and concentrating the solution, the obtained solid was suspended and washed with hexane to obtain 4.02 g of a white solid (I-3-f).

Synthesis of (I-3): (I-3-f) (4.00 g, 4.98 mmol), acrylic acid (0.72 g, 9.96 mmol), N,N-dimethyl-4-aminopyridine (0.12 g, 0.10 mmol), and dichloromethane (100 mL) were mixed and cooled in an ice bath, and then 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (2.10 g, 11.0 mmol) was added. After stirring for 2 hours, acrylic acid (0.36 g, 4.98 mmol) and EDC (1.05 g, 5.5 mmol) were added. After 18 hours, acrylic acid (0.36 g, 4.98 mmol) and EDC (1.05 g, 5.5 mmol) were further added, and the mixture was stirred for 5 hours. The reaction solution was washed with a saturated aqueous ammonium chloride solution and then with saturated saline solution, and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 2.30 g of a white solid (I-3).

The structure was confirmed by NMR. The results are shown below. ¹ H NMR (CDCl3, 400 MHz) δ7.52 (d, 4H, J = 8.8 Hz), 7.06 (d, 4H, J = 8.8 Hz), 6.40 (d, 2H, J = 17.2 Hz), 6.12 (dd, 2H, J = 10.4, 17.2 Hz), 5.81 (d, 2H, J = 10.4 Hz), 4.15 (t, 4H, J = 6.8 Hz), 3.46 (t, 4H, J = 9.2 Hz), 3.30 - 3.20 (m, 2H), 2.60 - 2.45 (m, 2H), 2.22 - 2.10 (m, 8H), 1.70 - 1.50 (m, 8H), 1.45 - 1.25 (m, 36H)

The fact that the compound (I-3) exhibits liquid crystal properties was confirmed by adding 0.2 parts by weight of 4-methoxyphenol as a polymerization inhibitor to 100 parts by weight of the liquid crystal compound and observing birefringence at 70° C. using a polarizing microscope attached to a high temperature stage.

[Synthesis of pigment] <Pigment (II-1)> Pigment (II-1) was synthesized according to the synthesis method described below.

[Chemistry 33]

Synthesis of (II-1-a): In a reactor cooled in an ice bath, tetrahydrofuran (100 mL) and sodium hydroxide (60% purity, 6.7 g, 168.0 mmol) were added, 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. After rinsing with tetrahydrofuran (30 mL), the mixture was stirred at 50°C for 0.5 hours. The reaction solution was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was dissolved in ethyl acetate (20 mL) by heating, and then hexane (50 mL) was added and cooled. The precipitate was separated by filtration, washed with hexane, and dried under reduced pressure to obtain 15.0 g of (II-1-a).

Synthesis of (II-1-b): Mix (II-1-a) (15.0 g, 53.3 mmol), tetrahydrofuran (150 mL), and iron powder (13.9 g, 248.9 mmol), add dropwise ammonium chloride (13.3 g, 248.6 mmol) dissolved in water (30 mL), and stir at 50°C for 3 hours. Filter through diatomaceous earth, extract with ethyl acetate, wash with water and saturated brine, and distill off the solvent. Suspend the obtained crude product with hexane, separate the precipitate by filtration, wash with hexane, and dry to obtain 10.9 g of (II-1-b).

Synthesis of (II-1): Mix (II-1-b) (2.51 g, 10.0 mmol), N-methylpyrrolidone (40 mL), concentrated hydrochloric acid (2.2 mL), and water (20 mL), cool to 3°C, add sodium nitrite (789 mg, 11.4 mmol), and stir at 15°C for 3.5 hours. Mix 1-phenylpyrrolidine (1.47 g, 10.0 mmol), methanol (60 mL), and water (30 mL), and adjust the pH to 3.5 with concentrated hydrochloric acid. While adding aqueous sodium hydroxide solution to maintain the pH at 3-5, add dropwise the liquid containing the above diazonium salt, and stir at 15°C for 3 hours. The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane) to obtain 3.06 g of a red solid (II-2).

The maximum absorption wavelength (λ _max ) of the compound in a 10 ppm chloroform solution was 459 nm, and the gram absorption coefficient was 107.6 Lg ^-1 cm ^-1 . The structure was confirmed by NMR. The results are shown below. ¹ H-NMR (CDCl ₃ , 400 MHz) δ0.94 (t, 3H, J = 7.2 Hz), 1.32 - 1.43 (m, 2H), 1.55 - 1.68 (m, 2H), 2.00 - 2.12 (m, 4H), 2.62 (t, 2H, J = 7.6 Hz), 3.41 (t, 4H, J = 6.4 Hz), 6.63 (d, 2H, J = 8.8 Hz), 7.14 (d, 2H, J = 8.8 Hz), 7.19 (d, 2H, J = 8.0 Hz), 7.45 (d, 2H, J = 8.0 Hz), 7.60 (d, 2H, J = 8.4 Hz), 7.84 (d, 2H, J = 8.4 Hz), 7.88 (d, 2H, J = 9.2 Hz)

The solubility of the compound in cyclopentanone was determined. 3 mg of the pigment (II-1) was added to 97 mg of cyclopentanone, and the mixture was stirred at 80°C for 5 minutes. After that, the mixture was allowed to stand at room temperature for 1 hour, and the obtained mixture was filtered using a syringe equipped with a syringe filter (PTFE13045, 0.45 μm, manufactured by Membrane Solutions) to obtain a saturated solution of the pigment (II-1) in cyclopentanone. The solution was diluted with 800 mg of tetrahydrofuran, and the concentration was determined using HPLC (L-2300 series manufactured by Hitachi High-Technologies Corporation). A solution in which 0.1% by weight of the pigment (II-1) was dissolved in tetrahydrofuran was prepared, and a calibration curve was prepared at an absorption wavelength of 254 nm. Using this calibration curve, the concentration of cyclopentanone saturated solution was determined to be 1.0%.

<Pigment (II-2)> The pigment (II-2) was synthesized according to the synthesis method described below.

[Chemistry 34]

Synthesis of (II-2): A mixture of (II-1-b) (1.26 g, 5.0 mmol), N-methylpyrrolidone (20 mL), concentrated hydrochloric acid (1.1 mL), and water (20 mL) was cooled to 3°C, sodium nitrite (380 mg, 5.5 mmol) was added, and the mixture was stirred at 15°C for 3.5 hours. N,N-diethylaniline (751 mg, 5.0 mmol), methanol (40 mL), and water (20 mL) were mixed, and the pH value was adjusted to 3.5 with concentrated hydrochloric acid. While adding an aqueous sodium hydroxide solution to maintain the pH value at 3 to 6, the liquid containing the above-mentioned diazonium salt was added dropwise, and the mixture was stirred at 15°C for 1 hour. The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane) to obtain 1.15 g of a red solid (II-2).

The maximum absorption wavelength (λ _max ) of the compound in a 10 ppm chloroform solution was 458 nm, and the gram absorption coefficient was 105.7 Lg ^-1 cm ^-1 . The structure was confirmed by NMR. The results are shown below. ¹ H-NMR (CDCl ₃ , 400 MHz) δ0.96 (t, 3H, J - 7.2 Hz), 1.24 (t, 6H, J - 7.2 Hz), 1.33 - 1.44 (m, 2H), 1.57 - 1.67 (m, 2H), 2.64 (t, 2H, J - 7.2 Hz), 3.47 (q, 4H, J - 7.2 Hz), 6.74 (d, 2H, J - 9.2 Hz), 7.15 (d, 2H, J - 8.0 Hz), 7.20 (d, 2H, J - 8.0 Hz), 7.47 (d, 2H, J - 8.0 Hz), 7.61 (d, 2H, J - 8.8 Hz), 7.85 (d, 2H, J - 8.0 Hz), 7.88 (d, 2H, J - 8.8 Hz) The solubility of this compound in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and the result was more than 3.0%.

<Pigment (II-3)> Synthetic pigment (II-3) was synthesized according to the synthesis method described below.

[Chemistry 35]

Synthesis of (II-3-a): In a reactor cooled in an ice bath, add tetrahydrofuran (200 mL) and sodium hydroxide (purity 60%, 10.1 g, 252.6 mmol), and dropwise add a mixture of diethyl (4-nitrobenzyl)phosphonate (23.0 g, 84.2 mmol), 4-heptyloxybenzaldehyde (18.6 g, 84.2 mmol), and tetrahydrofuran (200 mL) over 10 minutes. After rinsing with tetrahydrofuran (30 mL), stir at 50°C for 2 hours. Pour the reaction solution into water, extract with ethyl acetate, wash with water and saturated brine, and remove the solvent by distillation. The obtained crude product was dissolved in ethyl acetate (35 mL) by heating, and then hexane (80 mL) was added and cooled. The precipitate was separated by filtration, washed with hexane, and dried under reduced pressure to obtain 23.1 g of (II-3-a).

Synthesis of (II-3-b): Mix (II-3-a) (23.1 g, 68.1 mmol), tetrahydrofuran (200 mL), and iron powder (19.0 g, 340.5 mmol), add dropwise ammonium chloride (18.2 g, 340.5 mmol) dissolved in water (50 mL), and stir at 50°C for 5 hours. Filter using diatomaceous earth, extract with ethyl acetate, wash with water and saturated brine, and remove the solvent by distillation. Purify the obtained crude product by silica gel column chromatography (hexane/ethyl acetate), suspend with hexane, separate the precipitate by filtration, and wash with hexane. After drying under reduced pressure, 10.7 g of (II-3-b) was obtained.

Synthesis of (II-3): A mixture of (II-3-b) (1.6 g, 5.0 mmol), N-methylpyrrolidone (20 mL), concentrated hydrochloric acid (1.1 mL), and water (20 mL) was cooled to 3°C, sodium nitrite (380 mg, 5.5 mmol) was added, and the mixture was stirred at 15°C for 5 hours. N,N-diethylaniline (751 mg, 5.0 mmol), methanol (40 mL), and water (20 mL) were mixed, and the pH value was adjusted to 3.5 with concentrated hydrochloric acid. While adding an aqueous sodium hydroxide solution to maintain the pH value at 7, the liquid containing the above-mentioned diazonium salt was added dropwise, and the mixture was stirred at 15°C for 1 hour. The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane) to obtain 152 mg of an orange solid (II-2).

The maximum absorption wavelength (λ _max ) of the compound in a 10 ppm chloroform solution was 459 nm, and the gram absorption coefficient was 96.4 Lg ^-1 cm ^-1 . The structure was confirmed by NMR. The results are shown below. ¹ H-NMR (CDCl ₃ , 400 MHz) δ0.90 (t, 3H, J = 7.0 Hz), 1.30 (t, 6H, J = 7.0 Hz), 1.28 - 1.41 (m, 6H), 1.42 - 1.52 (m, 2H), 1.74 - 1.86 (m, 2H), 3.45 (q, 4H, J = 7.2 Hz), 3.98 (t, 2H, J = 6.6 Hz), 6.73 (d, 2H, J = 9.6 Hz), 6.90 (d, 2H, J = 8.8 Hz), 7.01 (d, 1H, J = 16.4 Hz), 7.13 (d, 1H, J = 16.4 Hz), 7.46 (d, 2H, J = 8.8 Hz), 7.58 (d, 2H, J = 8.4 Hz), 7.80 - 7.87 (m, 4H) The solubility of this compound in cyclopentanone was measured by the same method as that of the dye (II-1) (detection absorption wavelength: 254 nm) and the result was more than 3.0%.

<Pigment (II-4)> According to the synthesis method described below, pigment (II-4) was synthesized.

[Chemistry 36]

Synthesis of (II-4): Mix (II-1-b) (1.0 g, 4.0 mmol) and N-methylpyrrolidone (13 mL), add concentrated hydrochloric acid (1.0 g, 10.0 mmol), cool in an ice bath, add sodium nitrite (0.3 g, 4.4 mmol) dissolved in water (1.3 mL), and stir for 1 hour. The reaction solution was coupled with 1-phenylpiperidine (0.6 g, 4.0 mnmol) dissolved in methanol (25 mL) and water (6.5 mL) at pH = 7, and the precipitate was separated by filtration, washed with water, and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/dichloromethane) to obtain 760 mg of orange solid (II-4).

The maximum absorption wavelength (λ _max ) of the compound in a 10 ppm chloroform solution was 431 nm, and the gram absorption coefficient was 94.3 Lg ^-1 cm ^-1 . The structure was confirmed by NMR. The results are shown below. ¹ H-NMR (CDCl ₃ , 400 MHz) δ0.94 (t, 3H, J = 7.4 Hz), 1.30 - 1.44 (m, 2H), 1.57 - 1.75 (m, 8H), 2.62 (t, 2H, J = 8.0 Hz), 3.37 (t, 4H, J = 5.2 Hz), 6.96 (d, 2H, J = 9.2 Hz), 7.13 - 7.20 (m, 4H), 7.45 (d, 2H, J = 8.0 Hz), 7.60 (d, 2H, J = 8.4 Hz), 7.84 - 7.87 (m, 4H) Measured by the same method as for dye (II-1) (detection absorption wavelength: 254 nm) The solubility of the compound in cyclopentanone was 2.4%.

＜Pigment (II-5)＞ Pigment (II-5) was synthesized according to the method described in Color Materials, 73, 221-226 (2000).

[Chemistry 37]

The maximum absorption wavelength (λ _max ) of the compound in a 10 ppm chloroform solution was 459 nm, and the gram absorption coefficient was 52.6 Lg ^-1 cm ^-1 . The structure was confirmed by NMR. The results are shown below. ¹ H-NMR (CDCl ₃ , 400 MHz) δ0.98 (t, 3H, J = 7.2 Hz), 1.16 (t, 6H, J = 7.2 Hz), 1.39 - 1.45 (m, 2H), 1.67 - 1.71 (m, 2H), 2.74 (t, 2H, J = 7.6 Hz), 3.38 (q, 4H, J = 7.2 Hz), 7.20 (d, 1H, J = 8.4 Hz), 7.37 (d, 2H, J = 8.4 Hz), 7.57 - 7.61 (m, 1H), 7.65 - 7.70 (m, 1H), 7.90 - 7.95 (m, 3H), 8.10 (d, 2H, J = 8.8 Hz), 8.17 (d, 2H, J = 8.8 Hz), 8.31 (d, 1H, J = 8.4 Hz), 9.05 (d, 1H, J = 8.0 Hz) The solubility of this compound in cyclopentanone was measured by the same method as that of dye (II-1) (detection absorption wavelength: 254 nm) and the result was 2.2%.

The chemical structures of the liquid crystal compound and the pigment synthesized above are shown below. In the formula, C ₁₁ H ₂₂ means that there are 11 methylene chains bonded in a straight chain.

[Chemistry 38]

[Chemistry 39]

[Chemistry 40]

[Chemistry 41]

[Chemistry 42]

[Chemistry 43]

[Chemistry 44]

[Chemistry 45]

[Chemistry 46]

[Chemistry 47]

Furthermore, the solubility of the pigment (III-1) in cyclopentanone was measured by the same method as the pigment (II-1) (detection absorption wavelength: 254 nm), and the result was 0.7%. Furthermore, the solubility of the pigment (III-2) in cyclopentanone was measured by the same method as the pigment (II-1) (detection absorption wavelength: 254 nm), and the result was 0.8%.

Example 1 20.00 parts of liquid crystal compound (I-1) and 0.40 parts of pigment (II-1) were added to 399.6 parts of chloroform, stirred and dissolved, and then the solvent was removed to obtain an anisotropic pigment film-forming composition 1. The fact that the anisotropic pigment film-forming composition 1 exhibited liquid crystallinity was confirmed by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. In order to determine the dichroic ratio using the obtained anisotropic pigment film-forming composition 1 by the above method, an anisotropic pigment film 1 was prepared using a sandwich cell with a cell gap of 8.0 μm, and the dichroic ratio of the anisotropic pigment film 1 was determined. The results are shown in Table 2.

Example 2 Anisotropic pigment film-forming composition 2 and anisotropic pigment film 2 were obtained in the same manner as Example 1 except that 0.30 parts of pigment (II-2) was used instead of 0.40 parts of pigment (II-1). The fact that the anisotropic pigment film-forming composition 2 exhibited liquid crystallinity was confirmed by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. With respect to the anisotropic pigment film 2, the dichroic ratio of the anisotropic pigment film 2 was determined. The results are shown in Table 2.

Example 3 Anisotropic pigment film-forming composition 3 and anisotropic pigment film 3 were obtained in the same manner as Example 1 except that 0.30 parts of pigment (II-3) was used instead of 0.40 parts of pigment (II-1). The fact that the anisotropic pigment film-forming composition 3 exhibited liquid crystallinity was confirmed by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. With respect to the anisotropic pigment film 3, the dichroic ratio of the anisotropic pigment film 3 was determined. The results are shown in Table 2.

Example 4 Anisotropic pigment film-forming composition 4 and anisotropic pigment film 4 were obtained in the same manner as in Example 1 except that 20.00 parts of liquid crystal compound (I-2) were used instead of 20.00 parts of liquid crystal compound (I-1), and 0.28 parts of pigment (II-1) were used instead of 0.40 parts of pigment (II-1). The fact that the anisotropic pigment film-forming composition 4 exhibited liquid crystallinity was confirmed by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. With respect to the anisotropic pigment film 4, the dichroic ratio of the anisotropic pigment film 4 was determined. The results are shown in Table 2.

Example 5 Anisotropic pigment film-forming composition 5 and anisotropic pigment film 5 were obtained in the same manner as in Example 1 except that 20.00 parts of liquid crystal compound (I-2) was used instead of 20.00 parts of liquid crystal compound (I-1), 0.32 parts of pigment (II-4) was used instead of 0.40 parts of pigment (II-1), and an interlayer cell with a cell gap of 10.0 μm was used instead of an interlayer cell with a cell gap of 8.0 μm. The fact that the anisotropic pigment film-forming composition 5 exhibited liquid crystallinity was confirmed by observing birefringence at 40°C using a polarizing microscope attached to a high temperature stage. With respect to the anisotropic pigment film 5, the dichroic ratio of the anisotropic pigment film 5 was determined. The results are shown in Table 2.

Comparative Example 1 Anisotropic pigment film-forming composition 7 and anisotropic pigment film 7 were obtained in the same manner as in Example 1 except that 0.2 parts of pigment (II-5) was used instead of 0.40 parts of pigment (II-1). The fact that the anisotropic pigment film-forming composition 7 exhibited liquid crystallinity was confirmed by observing birefringence at 60°C using a polarizing microscope attached to a high-temperature stage. With respect to the anisotropic pigment film 7, the dichroic ratio of the anisotropic pigment film 7 was determined. The results are shown in Table 2.

[Table 2] Embodiment Comparison Example 1 2 3 4 5 1 Liquid crystal compounds I-1 I-1 I-1 I-2 I-2 I-1 pigment II-1 II-2 II-3 II-1 II-4 II-5 Display the temperature of the maximum color ratio (℃) 40.0 40.0 40.0 40.0 40.0 60.0 Wavelength showing maximum dichroic ratio (nm) 515 515 500 515 500 485 Two-color ratio 32.1 22.6 25.3 36.2 28.5 3.3 Wavelength at which the absorbance in the membrane shows a maximum value (nm) 470 480 465 495 450 465 Dichroic ratio at the wavelength where the absorbance in the membrane shows a maximum value 27.4 16.0 22.0 34.2 24.3 3.2

Example 6 34.28 parts of liquid crystal compound (I-2), 0.34 parts of azo dye of formula (III-1) (manufactured by Hayashibara Co., Ltd.), 0.84 parts of azo dye of formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), 0.28 parts of azo dye of formula (II-1), and 0.21 parts of azo dye of color (II-4) were added to 399.6 parts of chloroform, stirred and dissolved, and then the solvent was removed to obtain anisotropic dye film-forming composition 8. The fact that anisotropic dye film-forming composition 8 exhibited liquid crystallinity was confirmed by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. In order to determine the dichroic ratio using the obtained anisotropic dye film-forming composition 8 by the above method, an anisotropic dye film 8 was prepared, and the dichroic ratio of the anisotropic dye film 8 was determined. The maximum dichroic ratio of the anisotropic dye film 8 was 48.7 at 40°C and a wavelength of 675 nm. The dichroic ratio of the azo dye of formula (II-1) at a wavelength of 495 nm, where the absorbance showed a maximum value in the liquid crystal compound (I-2), was 31.7.

Example 7 To 717.9 parts of cyclopentanone were added 243.6 parts of the liquid crystal compound (I-2), 4.35 parts of the azo dye of formula (II-1), 5.58 parts of IRGACURE (registered trademark) 369 (manufactured by BASF), and 3.62 parts of BYK-361N (manufactured by BYK-Chemie), and after heating and stirring at 80°C, the mixture was filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm), thereby obtaining anisotropic dye film composition 9. The composition 9 for anisotropic dye film was formed by spin coating on a substrate having a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems, alignment film formed by rubbing method) formed on glass, and then dried by heating at 120°C for 2 minutes, cooled to a liquid crystal phase, and polymerized at an exposure dose of 500 mj/cm ² (365 nm basis) to obtain anisotropic dye film 9. It was confirmed that when the obtained anisotropic dye film 9 was placed on a commercially available polarizing plate and rotated, light and dark were generated, indicating good performance that it can be used as a polarizing film.

Example 8 In 2615.7 parts of chloroform, 19.65 parts of liquid crystal compound (I-2), 0.06 parts of azo dye of formula (III-1) (manufactured by Hayashibara Co., Ltd.), 0.15 parts of azo dye of formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), and 0.05 parts of dye (II-2) were added, stirred and dissolved, and then the solvent was removed to obtain an anisotropic dye film-forming composition 10. The anisotropic dye film-forming composition 10 exhibited liquid crystallinity by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. In order to determine the dichroic ratio using the obtained anisotropic dye film-forming composition 10 by the above method, an anisotropic dye film 10 was prepared, and the dichroic ratio of the anisotropic dye film 10 was determined. The maximum dichroic ratio of the anisotropic pigment film 10 is 31.0 at 40° C. and a wavelength of 595 nm. The dichroic ratio of the pigment (II-2) at a wavelength of 485 nm, where the absorbance shows a maximum value in the liquid crystal compound (I-2), is 20.4.

Example 9 In 79.67 parts of chloroform, 20.00 parts of liquid crystal compound (I-2), 0.18 parts of azo dye of formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), and 0.14 parts of dye (II-1) were added, stirred and dissolved, and then the solvent was removed to obtain an anisotropic dye film-forming composition 11. The anisotropic dye film-forming composition 11 exhibited liquid crystallinity by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. In order to determine the dichroic ratio using the obtained anisotropic dye film-forming composition 11 by the above method, an anisotropic dye film 11 was prepared, and the dichroic ratio of the anisotropic dye film 11 was determined. The maximum dichroic ratio of the anisotropic pigment film 11 is 34.2 at 40°C and a wavelength of 515 nm. The dichroic ratio of the pigment (II-1) at a wavelength of 470 nm, where the absorbance shows a maximum value in the liquid crystal compound (I-2), is 28.7.

Example 10 Anisotropic pigment film-forming composition 12 and anisotropic pigment film 12 were obtained in the same manner as Example 9 except that 20.00 parts of liquid crystal compound (I-3) was used instead of 20.00 parts of liquid crystal compound (I-1). The fact that the anisotropic pigment film-forming composition 12 exhibited liquid crystallinity was confirmed by observing birefringence at 70°C using a polarizing microscope attached to a high temperature stage. In order to determine the dichroic ratio using the obtained anisotropic pigment film-forming composition 12 by the above method, an anisotropic pigment film 12 was prepared, and the dichroic ratio of the anisotropic pigment film 12 was determined. The maximum dichroic ratio of the anisotropic pigment film 12 was 28.8 at 70°C and a wavelength of 515 nm. The colorant (II-1) has a dichroic ratio of 25.5 at a wavelength of 470 nm at which the absorbance of the pigment (II-1) shows a maximum value in the liquid crystal compound (I-3).

Comparative Example 2 Anisotropic pigment film-forming composition 13 was obtained in the same manner as in Example 1 except that 0.2 parts of pigment (II-6) was used instead of 0.40 parts of pigment (II-1). The solubility of pigment (II-6) in cyclopentanone was measured by the same method as that of pigment (II-1) (detection absorption wavelength: 254 nm), and the result was 0.0%. Regarding the anisotropic pigment film-forming composition 13, precipitates were observed at 60°C using a polarizing microscope attached to a high temperature stage. It is believed that the reason for this is that the solubility of pigment (II-6) is relatively low, and it is difficult to show a sufficient dichroic ratio when an anisotropic pigment film is formed from the anisotropic pigment film-forming composition 13.

[Chemistry 48]

Comparative Example 3 In 79.66 parts of chloroform, 20.00 parts of the liquid crystal compound (I-2), 0.18 parts of the azo dye of formula (III-2) (manufactured by Showa Chemical Industry Co., Ltd.), and 0.15 parts of the dye (II-5) were added, stirred and dissolved, and then the solvent was removed to obtain an anisotropic dye film-forming composition 14. The anisotropic dye film-forming composition 14 exhibited liquid crystal properties by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. In order to determine the dichroic ratio using the obtained anisotropic dye film-forming composition 14 by the above method, an anisotropic dye film 14 was prepared, and the dichroic ratio of the anisotropic dye film 14 was determined. The maximum dichroic ratio of the anisotropic pigment film 14 is 6.6 at 40° C. and a wavelength of 485 nm. The dichroic ratio of the pigment (II-5) at a wavelength of 465 nm, where the absorbance shows a maximum value among the liquid crystal compounds (I-2), is 6.6.

Comparative Example 4 Anisotropic pigment film-forming composition 15 and anisotropic pigment film 15 were obtained in the same manner as in Example 10 except that 0.17 parts of pigment (II-5) was used instead of 0.17 parts of pigment (II-1). The fact that the anisotropic pigment film-forming composition 15 exhibited liquid crystallinity was confirmed by observing birefringence at 70°C using a polarizing microscope attached to a high temperature stage. In order to determine the dichroic ratio using the obtained anisotropic pigment film-forming composition 15 by the above method, an anisotropic pigment film 15 was prepared, and the dichroic ratio of the anisotropic pigment film 15 was determined. The maximum dichroic ratio of the anisotropic pigment film 15 was 4.3 at 70°C and a wavelength of 485 nm. The colorant (II-5) has a dichroic ratio of 3.5 at a wavelength of 465 nm, where the absorbance of the colorant (II-5) shows a maximum value in the liquid crystal compound (I-3). The results of Examples 6, 8 to 10 and Comparative Examples 3 to 4 are shown in Table 3.

[table 3] Embodiment Comparison Example 6 8 9 10 3 4 Liquid crystal compounds I-2 I-2 I-2 I-3 I-2 I-3 pigment II-1 II-4 III-1 III-2 II-2 III-1 III-2 II-1 III-2 II-1 III-2 II-5 III-2 II-5 III-2 Display the temperature of the maximum color ratio (℃) 40.0 40.0 40.0 70.0 40.0 70.0 Wavelength showing maximum dichroic ratio (nm) 675 595 515 515 485 485 Two-color ratio 48.7 31.0 34.2 28.8 6.6 4.3 Measurement wavelength (nm) 495 485 470 470 465 465 Measuring the color ratio at the wavelength 31.7 20.4 28.7 25.5 6.6 3.5 [Industrial Availability]

The anisotropic pigment film-forming composition of the present invention can achieve excellent optical performance, especially a sufficient dichroic ratio. In particular, a sufficient dichroic ratio can be achieved in the wavelength region of 430 nm to 550 nm. The anisotropic pigment film of the present invention is formed by using the anisotropic pigment film-forming composition of the present invention, so it can achieve excellent optical performance, especially a sufficient dichroic ratio. The optical element of the present invention can achieve excellent optical performance, especially a sufficient dichroic ratio, because it includes the anisotropic pigment film of the present invention.

Claims (13)

A composition for forming an anisotropic dye film comprises a dye and a polymerizable liquid crystal compound, wherein the dye comprises a compound represented by formula (1): ^A1 -CH=CH- ^A2- (N= ^NA3 ) _n -X (1) (wherein ^A1 represents a phenyl group which may have a substituent (but excluding a sulfo group); ^A2 and ^A3 each independently represent a phenylene group which may have a substituent (but excluding a sulfo group); X represents a monovalent organic group; and n represents 1, 2 or 3). A composition for forming an anisotropic dye film comprises a dye and a polymerizable liquid crystal compound, wherein the dye comprises a compound represented by formula (1): ^A1 -CH=CH- ^A2- (N= ^NA3 ) _n -X (1) (wherein ^A1 represents a phenyl group which may have a substituent (but excluding a sulfonic group); the permissible substituent of the phenyl group is ^-RA or ^-ORA , and ^RA independently represents a linear or branched alkyl group having 1 to 15 carbon atoms; ^A2 represents a phenylene group which may have a substituent (but excluding a sulfonic group); ^A3 represents a phenylene group which does not have a substituent; X represents a monovalent organic group; and n represents 1, 2 or 3). A composition for forming an anisotropic dye film comprises a dye and a polymerizable liquid crystal compound, wherein the dye comprises a compound represented by formula (1): ^A1 -CH=CH- ^A2- (N= ^NA3 ) _n -X (1) (wherein ^A1 represents a phenyl group which may have a substituent (but excluding a sulfo group); the permissible substituent of the phenyl group is ^-RA or ^-ORA , ^RA independently represents a linear or branched alkyl group having 1 to 15 carbon atoms; ^A2 and ^A3 independently represent a phenylene group which does not have a substituent; X is -N( ^-Rx ) ^-Ry ; ^Rx and ^Ry independently represent an alkyl group having 1 to 3 carbon atoms which may have a branch or ^Rx and ^Ry may be combined to represent an alkylene group having 2 to 6 carbon atoms which may have a branch; and n represents 1, 2 or 3). The composition for forming anisotropic pigment film as claimed in claim 1, wherein n is 1. As in claim 2, the composition for forming anisotropic pigment film, wherein n is 1. As in claim 3, the composition for forming anisotropic pigment film, wherein n is 1. The anisotropic dye film-forming composition of claim 1 or 4, wherein X is -O-( ^Rx ) or -N( ^-Rx ) ^-Ry ; ^Rx and ^Ry are independently an alkyl group having 1 to 15 carbon atoms which may have a branch or an aryl group having 5 to 14 atoms constituting a ring; ^Rx and ^Ry may be combined to represent an alkylene group having 2 to 15 carbon atoms which may have a branch; the alkyl group having 1 to 15 carbon atoms which may have a branch and the aryl group having 5 to 14 atoms constituting a ring may each have a substituent; one or more methylene groups contained in the alkylene group having 2 to 15 carbon atoms which may have a branch may be substituted with an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, _-CF2- , -CHCl-, _-CCl2- - structure; the above-mentioned amine nitrogen atom is -NH- or -N(R ^z )-; R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms. The anisotropic dye film-forming composition of any one of claims 1 to 6, wherein the ratio (r n1 /r n2 ) of the number of ring structures possessed by the polymerizable liquid crystal compound (r _n1 ) to the number of ring structures possessed by the compound represented by the formula ( ₁ ) (r _n2 ) is 0.7 to _1.5 . A composition for forming an anisotropic pigment film as claimed in any one of claims 1 to 6, wherein the polymerizable liquid crystal compound is a compound having a carbon-carbon triple bond. The composition for forming an anisotropic pigment film according to any one of claims 1 to 6 further comprises a polymerization initiator. The anisotropic pigment film-forming composition of any one of claims 1 to 6, wherein the pigment further comprises one or more compounds having an absorption curve showing a maximum value in the wavelength range of 380nm to 780nm at a wavelength greater than the wavelength at which the compound represented by the above formula (1) shows a maximum value in the absorption curve in the wavelength range of 380nm to 780nm. An anisotropic pigment film formed using the anisotropic pigment film forming composition as described in any one of claims 1 to 11. An optical element comprising an anisotropic pigment film as claimed in claim 12.