TW202039697A - Composition for forming anisotropic dye film, anisotropic dye film and optical element - Google Patents

Abstract

The present invention provides a composition for forming an anisotropic dye film which enables the achievement of excellent optical performance, especially a sufficient dichroic ratio. A composition for forming an anisotropic dye film according to the present invention contains a dye and a polymerizable liquid crystal compound; and the dye contains a compound that is represented by formula (1). (1): A1-CH=CH-A2-(N=N-A3)n-X (In the formula, A1 represents a monovalent group of an aromatic hydrocarbon ring, which may have a substituent (excluding a sulfo group) or a monovalent group of an aromatic heterocyclic ring, which may have a substituent (excluding a sulfo group); each of A2 and A3 independently represents a divalent group of an aromatic hydrocarbon ring, which may have a substituent (excluding a sulfo group) or a divalent group of an aromatic heterocyclic ring, which may have a substituent (excluding a sulfo group); X represents a monovalent organic group; and n represents 1, 2 or 3.).

Description

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

The present invention relates to a polarized light for anisotropic pigment film formed by coating a liquid crystal composition, especially for dimming elements, liquid crystal elements (LCD), and organic electroluminescent elements (OLED) display elements. A composition for forming an anisotropic dye film, an anisotropic dye film, and an optical element exhibiting high dichroism are useful as a film. In this case, priority is claimed based on Japanese Patent Application No. 2019-037800 filed in Japan on March 1, 2019, and its content is cited herein.

In LCDs, linearly polarized films and circularly polarized films are used to control the optical rotation or birefringence during display. In OLED, circularly polarized film is used in order to prevent the reflection of outer boundary light in bright place.

Conventionally, as such a polarizing film, for example, a polarizing film (iodine-PVA polarizing film) obtained by dyeing polyvinyl alcohol (PVA) with a low concentration of iodine is 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 about a polarizing film containing a dichroic pigment 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, the combination with polymer liquid crystals cannot achieve a sufficient two-color ratio as a polarizing film. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 1-105204 [Patent Document 2] Japanese Patent Publication No. 2007-510946 [Non-Patent Literature]

[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 to be solved by the invention]

However, such a low-concentration iodine-PVA polarizer has the following problems: depending on the use environment, iodine sublimates or deteriorates and the color tone changes; or the extension of the PVA is eased, resulting in warping. In addition, regarding the polarizing film formed by coating the liquid crystal composition containing the pigment, there is a problem that high light absorption selective performance cannot be obtained.

Under such circumstances, it is desirable to have a polarizing film with high light absorption selectivity even if it is a thin film. In order to increase the dichroism of the anisotropic pigment film formed from the composition for forming an anisotropic pigment film, it is considered to increase the long axis and the short axis of the dichroic pigment contained in the composition for forming an anisotropic pigment film. The ratio of the axis, that is, the expansion of the π-conjugated system, increases the ratio of the long and short axis of the molecule.

However, if the π-conjugated system of the dichroic dye molecule is expanded to increase the ratio of the molecular length to the short axis, the dichroism is improved, but it becomes a dye that absorbs in the long-wavelength visible light region. On the other hand, in order to have absorption 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 relatively small molecular long and short axes and low dichroism. Therefore, it is particularly difficult to obtain a polarizing film with high light absorption selectivity in the short-wavelength visible light region from 380 nm to 520 nm. On the other hand, in the polarizing film covering the entire visible light region, since the two colors of the short-wavelength visible light region are relatively low, the light in the blue region cannot be sufficiently shielded but is transmitted 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 a dichroic pigment makes the dichroic ratio different. It is important to match the two colors of the liquid crystal molecule combination used Sex pigment. Under such circumstances, it is desired to develop a dichroic dye molecule capable of expressing high dichroism in an anisotropic dye film and a composition for forming an anisotropic dye film containing the dichroic dye molecule.

The object of the present invention is to provide a composition for forming an anisotropic dye film capable of achieving excellent optical properties, in particular, a sufficient two-color ratio. In addition, an object of the present invention is to provide an anisotropic dye film capable of achieving excellent optical performance, especially a sufficient two-color ratio. In addition, an object of the present invention is to provide an optical element including an anisotropic dye film capable of achieving excellent optical performance, particularly a sufficient two-color ratio. [Technical means to solve the problem]

The inventors of the present invention have discovered that the above-mentioned problems can be solved by using a compound having a specific structure as a dye in a composition for forming an anisotropic dye film containing a dye 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, and the dye includes the compound represented by formula (1). A ¹ -CH=CH-A ² -(N=NA ³ ) _n -X (1) (In the formula, A ¹ represents a monovalent group of an aromatic hydrocarbon ring that may have substituents (except sulfo groups) or may A monovalent group of an aromatic heterocyclic ring with substituents (except sulfo group); A ² and A ³ each independently represent a divalent group of an aromatic hydrocarbon ring that may have a substituent (except sulfo group) or may have Substituents (except sulfo groups) are aromatic heterocyclic divalent groups; X represents a monovalent organic group; n represents 1, 2 or 3) [2] For the formation of anisotropic pigment films as described in [1] The composition, wherein A ³ is a phenylene group which may have substituents (except sulfo groups). [3] The composition for forming an anisotropic dye film as described in [1] or [2], wherein A ² is a divalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group). [4] The composition for forming an anisotropic dye film as described in any one of [1] to [3], wherein A ¹ is the monovalent of an aromatic hydrocarbon ring which may have a substituent (except for a sulfo group) base. [5] The composition for forming an anisotropic pigment film as described in any one of [1] to [4], wherein X is -O-(R ^x ) or -N(-R ^x )-R ^y ; R ^x and R ^y each independently represent an alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 14 atoms constituting a ring; R ^x and R ^y can be integrated to indicate that they can have a branch The alkylene group having 2 to 15 carbon atoms; the alkylene group having 1 to 15 carbon atoms that may have a branch and the aryl group having 5 to 14 atoms constituting the ring may each have a substituent; the above may have a branch One or more of the methylene groups contained in the C2-15 alkylene group may be substituted with etheric oxygen atoms, thioether sulfur atoms, amine nitrogen atoms, carbonyl groups, ester bonds, amides The structure of bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ -; the above-mentioned amine nitrogen atom is -NH- or -N(R ^z )-; R ^z represents a straight line with 1 to 6 carbon atoms Chain or branched alkyl. [6] The composition for forming an anisotropic dye film as described in any one of [1] to [5], wherein the number of ring structures (r _n1 ) possessed by the polymerizable liquid crystal compound is the same as the above formula (1) The ratio (r _n1 /r _n2 ) of the number of ring structures (r _n2 ) possessed by the compound represented is 0.7 to 1.5. [7] The composition for forming an anisotropic dye film 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 composition for forming an anisotropic dye film as described in any one of [1] to [7], which further contains a polymerization initiator. [9] The composition for forming an anisotropic dye film as described in any one of [1] to [8], wherein the dye further includes one or more of the absorption curves in the wavelength region of 380 nm to 780 nm A compound whose wavelength showing the maximum value is greater than the wavelength showing the maximum value in the absorption curve of the compound represented by the above formula (1) in the wavelength region of 380 nm to 780 nm. [10] An anisotropic pigmented film formed using the composition for forming an anisotropic pigmented film as described in any one of [1] to [9]. [11] An optical element comprising the anisotropic pigment film as described in [10]. [Effects of Invention]

The composition for forming an anisotropic pigment film of the present invention can realize excellent optical properties, especially a sufficient two-color ratio. Since the anisotropic dye film of the present invention is formed by using the composition for forming an anisotropic dye film of the present invention, it can achieve excellent optical properties, especially a sufficient two-color ratio. Since the optical element of the present invention includes the anisotropic dye film of the present invention, it can achieve excellent optical performance, especially a sufficient two-color ratio.

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

In the present invention, the so-called anisotropic pigment film refers to the three-dimensional coordinate system selected from the thickness direction of the anisotropic pigment film and any two orthogonal directions in the plane. Tropic pigment film. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance. Examples of films having optical anisotropy such as absorption and refraction include polarizing films such as linearly polarizing films and circularly polarizing films, retardation films, and conductive anisotropic dye films. The anisotropic dye film of the present invention is preferably used as a polarizing film or a conductive anisotropic dye film, and more preferably used as a polarizing film.

[Composition for forming anisotropic pigment film] The composition for forming an anisotropic dye film of the present invention contains a dye and a polymerizable liquid crystal compound. As long as the composition for forming an anisotropic dye film of the present invention is in a state that does not cause phase separation, it may be in a solution, liquid crystal, or dispersed state. It is easy to use as a composition for forming an anisotropic dye film. From the viewpoint of coating on a substrate, a solution is preferred. On the other hand, the solid component obtained by removing the solvent from the composition for forming an anisotropic dye film is preferably in a state of a liquid crystal phase at any temperature from the viewpoint of being aligned on a substrate as described below. Furthermore, in the present invention, the so-called liquid crystal phase state specifically refers to the display liquid as described in "Basics and Applications of Liquid Crystals" (Matsumoto Masaichi, Kakuda City, 1991), pages 1-16 The liquid crystal state of the nature of both or between crystalline and crystalline is nematic phase, smectic phase, cholesterol phase, or disc-like phase.

(pigment) The pigment in the present invention refers to a substance or compound that absorbs at least a part of the wavelength of the visible light region (380 nm to 780 nm). Examples of dyes that can be used in the present invention include dichroic dyes. 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 of the molecule. In addition, the dye may be a dye having liquid crystallinity, or may not have liquid crystallinity. Furthermore, having liquid crystallinity means that it exhibits a liquid crystal phase at any temperature.

The dye contained in the composition for forming an anisotropic dye film of the present invention contains at least the compound represented by formula (1).

A ¹ -CH=CH-A ² -(N=NA ³ ) _n -X (1)

In the formula, A ¹ represents a monovalent group of an aromatic hydrocarbon ring that may have a substituent (except sulfo group) or a monovalent group of an aromatic heterocyclic ring that may have a substituent (except sulfo group); A ² and A ³ each independently represents a divalent group of an aromatic hydrocarbon ring that may have a substituent (except sulfo group) or a divalent group of an aromatic heterocyclic ring that may have a substituent (except sulfo group); X represents a monovalent organic基; n represents 1, 2 or 3.

The dye contained in the composition for forming an anisotropic dye film of the present invention has a structure represented by formula (1), and thus has a molecular length-to-minor axis ratio that is sufficiently large for a good two-color ratio. At the same time, since the elongation of the π-conjugated system is suppressed, it becomes absorbing in the short-wavelength visible light region. In addition, in the structure represented by formula (1), the combination with liquid crystal molecules and the intermolecular interaction between liquid crystal molecules and dye molecules are also good, so it can display higher without disturbing the molecular alignment of liquid crystal molecules. The two-color ratio. In terms of these effects, the pigment with the structure represented by formula (1) can simultaneously achieve the high dichroic ratio and the absorption in the short-wavelength visible region as the previous subject.

A ¹ 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.

環、聯三伸苯環、苊環、螢蒽環、茀環等。 該等中，作為A¹ 之芳香族烴環之1價基，較佳為苯環之1價基(苯基)、萘環之1價基(萘基)，就提高分子直線性之觀點而言，更佳為苯基。The aromatic hydrocarbon ring in A ¹ is a monocyclic or condensed aromatic hydrocarbon ring. The carbon number of the aromatic hydrocarbon ring is preferably 6 or more. Moreover, it is preferably 20 or less, more preferably 16 or less, and still more preferably 10 or less. By being in these ranges, the combination with liquid crystal tends to become better. For example, the carbon number of the aromatic hydrocarbon ring is preferably 6-20, more preferably 6-16, and still more preferably 6-10. In the case of a condensed ring, the number of rings is not particularly limited either, and the combination with the liquid crystal tends to become good, and it is preferably 2 or more, and more preferably 5 or less. As the aromatic hydrocarbon ring, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetrabenzene ring, a pyrene ring, a benzopyrene ring,

Ring, bis-terylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. In these, as the monovalent aromatic hydrocarbon rings A ^1, is preferably a monovalent benzene ring (phenyl group), a monovalent group (naphthyl) naphthalene rings, on the viewpoint of improving the linearity of the molecule In other words, phenyl is more preferred.

The aromatic heterocyclic ring in A ¹ is a monocyclic or condensed aromatic heterocyclic ring. The number of carbon atoms of the aromatic heterocyclic ring is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more. Furthermore, it is preferably 20 or less, more preferably 13 or less, and still more preferably 9 or less. By being in these ranges, the combination with liquid crystal tends to become better. For example, the number of carbon atoms in the aromatic heterocyclic ring is preferably 2-20, more preferably 3-13, and still more preferably 4-9. In the case of a condensed ring, the number of rings is not particularly limited either, and the combination with the liquid crystal tends to become good, and it is preferably 2 or more, and more preferably 5 or less.

Examples of aromatic heterocyclic rings include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolo Imidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzoazole ring Benzoisoxazole ring, benzothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyridine ring, pyrimidine ring, three ring, quinoline ring, isoquinoline ring, Oxoline ring, quinoline ring, phenanthridine ring, quinazoline ring, quinazolinone ring, etc. Among them, the aromatic heterocyclic ring of A ¹ is preferably a furan ring, a thiophene ring, a thienothiazole ring, a benzoxazole ring, a benzothiazole ring, and a benzothiazole ring from the viewpoint of improving the linearity of the molecule. The imidazole ring is particularly preferably a thienothiazole ring, benzoxazole ring, benzothiazole ring, and benzimidazole ring.

The monovalent aromatic heterocyclic monovalent group of A ¹ or in the ring of an aromatic hydrocarbon group other than a sulfo group tolerance of the substituent ^{include: -R A, -OH, -OR A} , -OC ( =O)-R ^A , -NH ₂ , -NH-R ^A , -N(-R ^B )-R ^A , -C(=O)-R ^A , -C(=O)-OR ^A , -C _{(= O) -NH 2, -C} (= O) -NH-R A, -C (= O) -N (-RB) -R A, -SH, -SR A, trifluoromethyl, amine sulfonamide Aceto, carboxy, cyano, nitro, halogen. Here, R ^A and R ^B each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms. One or more of the methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be substituted with ethereal oxygen atoms, thioether sulfur atoms, amine nitrogen atoms, The structure of carbonyl group, ester bond, amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ -can also be substituted for acryloxy, methacryloxy, glycidoxy The polymerizable base. In these, a divalent group other than a monovalent aromatic heterocyclic group of A ¹ or in the aromatic hydrocarbon ring of the addition of the sulfo substituent group, is preferably -R ^A, -OR ^A, include e.g. : N-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyl Oxy, 5,5-dimethyl-3-methylhexyloxy, 11-(propylene oxy)undecyloxy and the like. In addition, the above-mentioned amine nitrogen atom represents -NH-, -N(R ^z )-, and R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

As A ¹ , from the viewpoint of exhibiting a higher dichroic ratio, it is preferably a monovalent group of an aromatic hydrocarbon ring, more preferably a phenyl group or a naphthyl group, and further preferably a benzene from the viewpoint of improving linearity base. As the substituent group A ^1, is preferably selected from the group consisting of -R ^A, the group consisting of -OR ^A and -C (= O) -OR ^A group in the substituent, more preferably in the 4 position selected from the group consisting of -R ^A And the substituent in the group consisting of -OR ^A. By having the above-mentioned substituents, the combination with the liquid crystal tends to become better.

A ² and A ³ each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent (except for a sulfo group) or a divalent group of an aromatic heterocyclic ring which may have a substituent.

The aromatic hydrocarbon ring in A ² and A ³ is the same as the aromatic hydrocarbon ring in A ¹ . The divalent group of the aromatic hydrocarbon ring of A ² is preferably the divalent group of the benzene ring (phenylene), the divalent group of the naphthalene ring (naphthylene), and more preferably 1,4-phenylene , 1,4-naphthylene, 2,6-naphthylene, more preferably 1,4-phenylene. As the divalent group of the aromatic hydrocarbon ring of A ³ , phenylene and naphthylene are preferred, phenylene is more preferred, and 1,4-phenylene is still more preferred. By using A ² and/or A ³ as the above-mentioned group, the effect of increasing the ratio of molecular long-to-short axis can be obtained, and the combination with the liquid crystal tends to become better.

The aromatic heterocycles in A ² and A ³ are the same as the aromatic heterocycles in A ¹ .

Examples of the divalent group A ² and A ³ in the aromatic hydrocarbon rings or heterocyclic divalent aromatic group of the permissible substituents other than the group sulfo group, or a monovalent group of A ¹ in the aromatic hydrocarbon ring The permitted substituents other than the sulfo group in the monovalent group of the aromatic heterocyclic ring are the same.

As A ² , from the viewpoint of exhibiting a higher dichroic ratio, it is preferably a divalent group of an aromatic hydrocarbon ring which may have a substituent (except for the sulfo group), and more preferably may have a substituent (except for the sulfo group) The phenylene group and naphthylene group of) are more preferably 1,4-phenylene group and 1,4-naphthylene group which may have substituents (except sulfo group). From the viewpoint of improving linearity, More preferably, it is 1,4-phenylene which does not have a substituent. As A ³ , from the viewpoint of expressing a higher dichroic ratio, a divalent group of an aromatic hydrocarbon ring which may have a substituent (except for a sulfo group) is preferred. Among these, more preferred are phenylene or naphthylene which may have substituents (except sulfo group), and more preferred are 1,4-phenylene and naphthylene which may have substituents (except sulfo group). ,4-Naphthylene. In particular, from the viewpoint of improving linearity, 1,4-phenylene which does not have a substituent is particularly preferred.

In the above A ¹ , A ² and A ³ , as the substituent, a substituent other than the sulfo group is allowed. When the substituent is a sulfo group, the compatibility with the liquid crystal and the solvent becomes low, and therefore the dichroic ratio is lowered and the pigment is precipitated, which may greatly impair the performance as an anisotropic dye film.

X represents a monovalent organic group. Examples of the monovalent organic group in X include hydrogen atom, hydroxyl group, amino group, cyano group, carbamoyl group, nitro group, halogen atom, -R ^x , -OR ^x , -NH-R ^x , -N (-R ^y )-R ^x , -C(=O)-R ^x , -C(=O)-OR ^x , -C(=O)-NH-R ^x , -C(=O)-N( -R ^y )-R ^x , -OC(=O)-R ^x , -NH-C(=O)-R ^x , -N(-R ^y )-C(=O)-R ^x and so on. Furthermore, R ^x and R ^y each independently represent an alkyl group having 1 to 15 carbon atoms or an aryl group having 5 to 14 atoms that may have a branch; R ^x and R ^y may be integrated to indicate that A branched alkylene group with 2 to 15 carbon atoms. The alkyl group having 1 to 15 carbon atoms and the aryl group having 5 to 14 atoms constituting the ring which may have a branch may each have a substituent. One or more methylene groups contained in the branched alkyl group with 1 to 15 carbon atoms and the branched alkylene group with 2 to 15 carbon atoms may be substituted (displaced) and ethereal Structure of oxygen atom, thioether sulfur atom, amine nitrogen atom, carbonyl group, ester bond, amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ -. In addition, the above-mentioned amine nitrogen atom represents -NH-, -N(R ^z )-, and R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

Examples of the permissible substituents in the alkyl group having 1 to 15 carbon atoms that may have a branch in R ^x include -OH, -OR ^A , -OC(=O)-R ^A , -NH ₂ , and -NH- R ^A , -N(-R ^B )-R ^A , -C(=O)-R ^A , -C(=O)-OR ^A , -C(=O)-NH ₂ , -C(=O) ^{-NH-R A, -C (=} O) -N (-R B) -R A, -SH, -SR A, acyl amine sulfo, carboxyl, cyano, nitro, halo. Here, R ^A and R ^B each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms. One or more of the methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be substituted with ethereal oxygen atoms, thioether sulfur atoms, amine nitrogen atoms, The structure of carbonyl group, ester bond, amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ -. In addition, one or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms may be substituted with acryloxy, methacryloxy, or glycidoxy Base polymerizable base. Among these, as a substituent allowed in the C1-C15 alkyl group in R ^x that may have a branch, there is a tendency to obtain a dye that can combine well with the liquid crystal, and -OR ^{A is} preferred Examples include: methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, propyleneoxy, methpropylene Glycidoxy, glycidoxy, etc. Furthermore, the above-mentioned amine nitrogen atoms are -NH-, -N(R ^z )-, and R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

Examples of atoms constituting the rings of R ^x is an aryl group of 5 to 14 in the permissible substituents ^{include: -R A, -OH, -OR A} , -OC (= O) -R A, -NH 2 , -NH-R ^A , -N(-R ^B )-R ^A , -C(=O)-R ^A , -C(=O)-OR ^A , -C(=O)-NH ₂ , -C (=O)-NH-R ^A , -C(=O)-N(-R ^B )-R ^A , -SH, -SR ^A , trifluoromethyl, sulfamoyl, carboxyl, cyano, nitro Base, halogen. Here, R ^A and R ^B each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms. In these, as the number of atoms constituting the rings of R ^x is aryl of 5 to 14 in the permissible substituent groups, preferably -R ^A, -OR ^A, for example, include: methyl, ethyl, n-propyl Group, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, N-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, 5,5-dimethyl-3-methylhexyloxy, etc.

Examples of the aryl group having 5 to 14 atoms constituting the ring include the monovalent ring exemplified as the aromatic hydrocarbon ring and the aromatic heterocyclic ring in A ¹ of formula (1). The monovalent group of the aromatic hydrocarbon ring is preferably a monovalent group of a benzene ring (phenyl) and a monovalent group of a naphthalene ring (naphthyl). The monovalent group of the aromatic heterocyclic ring is preferably 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 benzoazole ring, and a benzothiazole ring The monovalent group of the benzimidazole ring. By being a monovalent group of the above-mentioned aromatic hydrocarbon ring and aromatic heterocyclic ring, the linearity of the molecule tends to increase. Among them, from the viewpoint of expressing a higher dichroic ratio, a phenyl group is more preferable.

As R ^x and R ^y , there is a tendency to obtain a dye that is well combined with the liquid crystal, preferably an alkyl group having 1 to 15 carbon atoms that may have a branch, or R ^x and R ^{y are} integrated. A branched alkylene group having 2 to 15 carbon atoms; more preferably a branched alkyl group having 1 to 6 carbon atoms, or R ^x and R ^{y are} integrated to form a branched carbon number 2 to The alkylene group of 10; More preferably, it is an alkylene group having 1 to 3 carbons that may have a branch, or R ^x and R ^{y are} integrated to form an alkylene group of 2 to 6 carbons that may have a branch.

As the monovalent organic group in X, there is a tendency for the combination with the liquid crystal to become good, preferably -OR ^x , -NH-R ^x , -N(-R ^y )-R ^x , more preferably -OR ^x , -N(-R ^y )-R ^x , and more preferably -N(-R ^y )-R ^x . Specifically, for example, dimethylamino, diethylamino, di-n-propylamino, ethylmethylamino, methylpropylamino, azetidinyl, pyrrolidinyl, and piperidinyl are more preferred. , Azarinyl, azalinyl, piperazinyl, thiolinolinyl, and more preferably diethylamino, pyrrolidinyl, and piperidinyl.

n represents 1, 2 or 3. Regarding n, there is a tendency to become a pigment that has a sufficiently large ratio of molecular long-to-short axis and absorbs in a short-wavelength region, and is preferably 1 or 2, more preferably 1. When n represents 2 or 3, each A ³ may be the same or different.

In the formula (1), -CH=CH- is preferably an inverse type from the viewpoint of increasing the ratio of molecular length to short axis. In the formula (1), -N=N- is preferably inverted from the viewpoint of increasing the ratio of molecular long-to-short axis.

Specifically, as the compound represented by formula (1), the following compounds may be mentioned, but it is not limited to these.

[化1]

[化2]

[化3]

[化4]

[化5]

[化6]

[化7]

[化8]

[化9]

[化10]

The compound represented by formula (1) contained in the composition for forming an anisotropic dye film of the present invention can have a maximum absorption (λ) at any wavelength in the anisotropic dye film produced by the following method _max1 ), preferably has a maximum absorption in the range of 350-550 nm, more preferably has a maximum absorption in the range of 410-530 nm, and more preferably has a maximum absorption in the range of 430-520 nm. In addition, with regard to the compound represented by formula (1) contained in the composition for forming an anisotropic pigment film of the present invention, it is preferable that the maximum absorption (λ _max2 ) measured by dissolving in a solvent is anisotropic The maximum absorption in the sexual pigment film (the above λ _max1 ) exists at long wavelengths. This long-wavelength shift is a phenomenon that the compound represented by formula (1) is dispersed in a polymerizable liquid crystal compound and/or a polymer having units based on the polymerizable liquid crystal compound, and is represented by formula (1) The compound has a strong intermolecular interaction with the polymerizable liquid crystal compound and/or the polymer having a unit based on the polymerizable liquid crystal compound. It is believed that the compound represented by formula (1) can exhibit a higher two-color ratio due to the stronger intermolecular interaction. The so-called long wavelength shift means that the maximum difference in absorption (λ _max1- λ _max2 ) becomes a positive value. From the standpoint of expressing higher dichroism, the difference is preferably 5 nm or more, more preferably 10 nm or more, More preferably, it is 15 nm or more. In addition, the upper limit is not particularly limited, and for example, 50 nm or less can be mentioned.

The composition for forming an anisotropic dye film of the present invention may contain other dyes in addition to the compound represented by formula (1). Other pigments include: azo pigments, quinone pigments (including naphthoquinone pigments, anthraquinone pigments, etc.), stilbene pigments, cyanine pigments, phthalocyanine pigments, indigo pigments, condensation polycyclic Department of pigments (including perylene pigments, 㗁𠯤 pigments, acridine pigments, etc.). Among these dyes, azo dyes are preferred in terms of higher molecular arrangement in the anisotropic dye film. The so-called azo dyes refer to dyes with at least one azo group (-N=N-). The number of azo groups in one molecule is the solubility in solvents and the compatibility with liquid crystal compounds. From the viewpoint of color tone and ease of manufacture, it is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less.

As an azo dye, the compound represented by formula (A) is mentioned, for example.

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

In the 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 0-4; when p is an integer of 2 or more, a plurality of D ² may be the same or different from each other; 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 group is preferable in terms of the linearity of the molecule. The substitution position of the naphthylene group is preferably 1,4-naphthylene group or 2,6-naphthylene group in terms of the 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 viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production . Especially in terms of the tendency of the ratio of molecular length to minor axis to increase, a monocyclic or bicyclic heterocyclic group is preferred. Examples of atoms other than carbon constituting the divalent heterocyclic group include at least one selected from a nitrogen atom, a sulfur atom, and an oxygen atom. When the heterocyclic group has a plurality of atoms other than carbons constituting the ring, these may be the same or different. Specifically, include: pyridine diyl, quinolin diyl, isoquinolin diyl, thiazol diyl, benzothiazol diyl, thienothiazol diyl, thienothiophene diyl, benzimidazolidinone two Group, benzofuran diyl, phthalimide diyl, azolediyl, benzo azolediyl, etc.

Examples of the substituents optionally possessed by the phenylene, naphthylene, and divalent heterocyclic group in D ¹ , D ² and D ³ include: alkyl having 1 to 4 carbons; methoxy and ethoxy Alkoxy with 1 to 4 carbons such as butoxy; fluorinated alkyl with 1 to 4 carbons such as trifluoromethyl; cyano; nitro; hydroxy; halogen atom; amine, diethylamino, And pyrrolidinyl and other substituted or unsubstituted amine groups. Furthermore, the above-mentioned substituted amine group means an amine group having one or two alkyl groups having 1 to 4 carbons, or two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbons. Amine group. The unsubstituted amine group is -NH ₂ . Furthermore, as the C1-C4 alkyl group, a methyl group, an ethyl group, a butyl group, etc. are mentioned. Examples of alkanediyl groups having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and 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, it is preferably via methyl, methoxy, hydroxyl, fluorine atom, chlorine atom, dimethylamino group, pyrrolidinyl group , Piperidinyl substitution.

p represents an integer of 0-4. From the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, hue, and ease of production, it is preferably 1 or more, more 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 group in R ¹¹ and R ¹² include: a hydrogen atom, an alkyl group having 1 to 15 carbons which may have a branch; an alicyclic alkyl group having 1 to 15 carbons; a methoxy group, Ethoxy and butoxy, etc. may have branched C1-15 alkoxy; trifluoromethyl, etc. may have branched C1-15 fluorinated alkyl; cyano; nitro; Hydroxyl; halogen atom; substituted or unsubstituted amino groups such as amine group, diethylamino group, and pyrrolidinyl group; carboxyl group; butoxycarbonyl group, etc., which may have branched alkoxycarbonyl groups with 1 to 15 carbon atoms ; 2-(4-butylphenyl) vinyl and other alkyl phenyl alkenyl groups; carbamoyl; butylamino methanoyl and other branched alkylamino methanols with 1 to 15 carbon atoms ; Aminosulfonyl; Butylsulfonyl, etc. may have branched alkylsulfonyl with 1 to 15 carbons; Butylcarbonylamino, etc. may have branched C1-15 sulfonyl Amino; butylcarbonyloxy and other branched acyloxy groups with 1 to 15 carbons; mercapto; butylthio and other alkylthio groups with 1 to 15 carbons; among the following polymerizable liquid crystal compounds Q ¹ -R ¹ -and Q ² -R ² -. Furthermore, the above-mentioned substituted amine group means an amine group having one or two alkyl groups having 1 to 15 carbon atoms that may have a branch, or two substituted alkyl groups are bonded to each other to form a carbon number of 2-15 The amine group of alkanediyl. The unsubstituted amine group is -NH ₂ . Furthermore, examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, butyl, and the like. Examples of alkanediyl groups having 2 to 15 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and pentane-1 ,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

Examples of R ¹¹ and R ¹² include hydrogen atoms, chain groups, aliphatic organic groups ("aliphatic organic groups" include chain ones and cyclic ones), and a part of carbon is substituted with nitrogen and/or oxygen The aliphatic organic base, etc. In a certain aspect, a hydrogen atom or a chain group is preferable. In another aspect, a hydrogen atom or an aliphatic organic group is preferable. In another aspect, a part of the hydrogen atom or carbon is preferably substituted. It is an aliphatic organic group formed from nitrogen and/or oxygen. Furthermore, the aliphatic organic group in which a part of the carbon is substituted with nitrogen and/or oxygen" includes chain-like ones and cyclic ones, and a part of the methyl group containing aliphatic organic groups is substituted with hydroxyl groups and pendant oxygen groups. Group (=O), amine group, imine group, etc.

Examples of the chain group include: the above-mentioned alkyl group having 1 to 15 carbons which may have a branch; an alkoxy group having 1 to 15 carbons which may have a branch; and a fluorine having 1-15 carbons which may have a branch. Alkyl group; substituted or unsubstituted amine group; carboxyl group; alkoxycarbonyl group with 1 to 15 carbon atoms which may have a branch; aminomethanyl group; alkyl group with 1 to 15 carbon atoms which may have a branch Carbamethanyl; Sulfamyl; Alkylsulfonyl with 1 to 15 carbons that may have a branch; Amino amino with 1 to 15 carbons that may have a branch; May have a branched carbon Alkyloxy with 1 to 15; mercapto; alkylthio with 1 to 15 carbons, etc. Furthermore, the above-mentioned substituted amine group means an amine group having one or two C1-C15 alkyl groups which may have a branch. The unsubstituted amine group is -NH ₂ .

Examples of the aliphatic organic group include the above-mentioned alkyl group having 1 to 15 carbon atoms, which may have a branch, and an alicyclic alkyl group having 1 to 15 carbon atoms. Examples of aliphatic organic groups in which a part of carbon is substituted with nitrogen and/or oxygen include: the above-mentioned alkoxy groups having 1 to 15 carbon atoms which may have a branch; substituted or unsubstituted amine groups; carboxyl groups ; May have a branched alkoxycarbonyl group with carbon number of 1-15; carbamate; may have a branched alkylaminomethyl group with 1-15 carbon atoms; may have a branched chain of carbon number 1-15 The acylamino group; may have a branched acyloxy group with 1 to 15 carbon atoms. Furthermore, the above-mentioned substituted amine group means an amine group having one or two alkyl groups having 1 to 15 carbon atoms that may have a branch, or two substituted alkyl groups are bonded to each other to form a carbon number of 2-15 The amine group of alkanediyl. The unsubstituted amine group is -NH ₂ . Furthermore, examples of the alkyl group having 1 to 15 carbon atoms include methyl, ethyl, butyl, and the like. Examples of alkanediyl groups having 2 to 15 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, and pentane- 1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

As R ¹¹ and R ¹² , in terms of the linearity of the molecule, they are each independently a hydrogen atom, or an alkane having 1 to 10 carbon atoms such as butyl, pentyl, hexyl, heptyl, and octyl. Group; butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and other C1-C10 alkoxy, diethylamino, pyrrolidinyl and piperidinyl substituted. Moreover, Q ¹ -R ¹ -and Q ² -R ² -in the following polymerizable liquid crystal compounds are also preferable.

Moreover, as a dye other than the compound represented by Formula (1) contained in the composition for anisotropic dye film formation of this invention, it does not specifically limit, A well-known dye can also be used. As well-known pigments, for example, the pigments described in the aforementioned 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).

Specifically, the dyes described below can be cited, but are not limited to these.

[化11]

[化12]

[化13]

[化14]

Furthermore, as a pigment other than the compound represented by formula (1) contained in the composition for forming an anisotropic pigment film of the present invention, it is preferable to show a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm. The wavelength of the value is greater than the wavelength at which the compound represented by formula (1) contained in the composition for forming an anisotropic dye film shows the maximum value in the absorption curve of the wavelength region from 380 nm to 780 nm, more preferably The wavelength showing the maximum value in the absorption curve in the wavelength region from 380 nm to 780 nm is higher than the absorption of the compound represented by formula (1) contained in the composition for forming anisotropic pigment film in the wavelength region from 380 nm to 780 nm The compound with a wavelength greater than 5 nm that shows the maximum value in the curve is more preferably the wavelength that shows the maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm than that contained in the composition for forming anisotropic pigment film The compound represented by formula (1) shows a maximum value in the absorption curve of the wavelength region from 380 nm to 780 nm, which is a compound with a wavelength greater than 10 nm. By setting the wavelength at which the absorption curve of the dye other than the compound represented by the formula (1) has a maximum value in the wavelength region of 380 nm to 780 nm within the above range, the color tone tends to be easily adjusted.

As the molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention (when two or more dyes are used in combination), it is preferably 300 or more, more preferably 350 or more, and more Preferably, it is 380 or more. Furthermore, it is preferably 1500 or less, more preferably 1200 or less, and still more preferably 1000 or less. Specifically, the molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention is preferably from 300 to 1,500, more preferably from 350 to 1,200, and still more preferably from 380 to 1,000. By being in the above range, there is a tendency for the ratio of molecular length to minor axis to become larger.

As the content of the pigment (dichroic pigment) in the composition for forming anisotropic pigment film (the sum of the content of each when two or more pigments are used in combination), for example, relative to the formation of anisotropic pigment film The solid content (100 parts by mass) of the composition 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, and more preferably 10 parts by mass or less. Specifically, as the content of the pigment (dichroic pigment) in the composition for forming an anisotropic pigment film, for example, relative to the solid content (100 parts by mass) of the composition for forming an anisotropic pigment film is 0.01-30 parts by mass, preferably 0.05-10 parts by mass. As long as the content of the dye (dichroic dye) is within the above range, the present invention can be made without disturbing the alignment of the liquid crystal compound contained in the composition for forming anisotropic dye film of the present invention. The tendency of the compound contained in the composition for forming anisotropic pigment film to polymerize. In addition, if the content of the dye (dichroic dye) is more than the above lower limit, there is a tendency that sufficient light absorption can be obtained and sufficient polarization performance can be obtained. In addition, if the content of the dye (dichroic dye) is less than the above upper limit value, there is a tendency that the inhibition of the alignment of the liquid crystal molecules can be easily suppressed.

The dye (dichroic dye) may be used depending on the purpose, and only the compound represented by formula (1) may be used, or the compound represented by formula (1) may be used in combination with other dyes. As described above, as the dye contained in the composition for forming an anisotropic dye film of the present invention, it is preferable to combine the compound represented by formula (1) with the absorption curve in the wavelength region of 380 nm to 780 nm The wavelength showing the maximum value is larger than that of the compound represented by formula (1) contained in the composition for forming an anisotropic pigment film in the absorption curve of the wavelength region from 380 nm to 780 nm. One of the compounds showing the wavelength of the maximum value Use the above. In particular, when the composition for forming an anisotropic dye film is used to form an anisotropic dye film as a polarizing element such as a display, it is preferable in terms of exhibiting polarization characteristics in a wider range of the visible light region.

The pigment contained in the composition for forming an anisotropic pigment film of the present invention can be obtained by alkylation reaction, esterification reaction, amination reaction, etherification reaction, ipso-substitution reaction, and diazonium reaction. It is produced by combining well-known chemical reactions such as coupling reaction and coupling reaction using metal catalysts. For example, the pigment contained in the composition for forming an anisotropic pigment film of the present invention can be in accordance with the method described in the examples, or, for example, "Shin Dye Chemistry" (Hosoda Toyosuke, December 21, Showa 48, Gihodo), Synthetic dyes are synthesized by the methods described in "Summons Synthetic Dyes" (Hiroguchi Hiroguchi, 1968, published by Sankyo), and "Theoretical Manufacturing Dyestuff Chemistry" (Hosoda Toyotomi, 1957, Gihodo).

(Polymerizable liquid crystal compound) In the present invention, the so-called liquid crystal compound refers to a substance that displays a liquid crystal state, specifically, as described on pages 1 to 28 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000), not self-crystallizing It is directly transformed into a liquid, and becomes a liquid compound through an intermediate state showing the properties of both crystal and liquid.

The polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is the following liquid crystal compound having a polymerizable group.

In the polymerizable liquid crystal compound, the polymerizable group can be arranged at any position in the molecule of the liquid crystal compound, and in terms of the tendency of intermolecular polymerization to become easy, it is preferably substituted at the end of the molecule of the liquid crystal compound. In the polymerizable liquid crystal compound, there may be more than one polymerizable group in the molecule of the liquid crystal compound, and when there are more than two, it is preferable to exist at both ends of the liquid crystal compound molecule.

In addition, the polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the molecule of the liquid crystal compound. If it is a compound with a carbon-carbon triple bond, the carbon-carbon triple bond can rotate and become the nucleus of liquid crystal molecules. The mobility of the molecules is high, and the liquid crystal molecules are π-conjugated to each other or dye molecules. The intermolecular interaction of the compound of the series is strong, and the molecular alignment tends to become higher.

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

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

(In the formula, 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 the following formula (3) The represented partial structure, divalent organic group, or single bond; A ¹² represents the partial structure or divalent organic group represented by the following formula (3); -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 A ¹¹ and A ¹³ is a partial structure represented by the following formula (3) or a divalent organic group; k is 1 or 2)

-Cy-X ² -C≡CX ^1- (3)

(In the formula, Cy represents a hydrocarbon ring group or a heterocyclic group; -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 A ¹¹ is a partial structure represented by formula (3), formula (2) can be Q ¹ -R ¹ -Cy-X ² -C≡CX ¹ -Y ¹ -A ¹² -(Y ² -A ¹³ ) _k -R ² -Q ² (2A), or Q ¹ -R ¹ -X ¹ -C≡CX ² -Cy-Y ¹ -A ¹² -(Y ² -A ¹³ ) _k- R ² -Q ² (2B). Also, when A ¹² is a partial structure represented by formula (3), formula (2) can be Q ¹ -R ¹ -A ¹¹ -Y ¹ -Cy-X ² -C≡CX ¹ -(Y ² -A ¹³ ) _k -R ² -Q ² (2C), can also be Q ¹ -R ¹ -A ¹¹ -Y ¹ -X ¹ -C≡CX ² -Cy-(Y ² -A ¹³ ) _k -R ² -Q ² (2D). Moreover, when A ¹³ is a partial structure represented by formula (3), formula (2) can be Q ¹ -R ¹ -A ¹¹ -Y ¹ -A ¹² -(Y ² -Cy-X ² -C ≡CX ¹ ) _k -R ² -Q ² (2E), or Q ¹ -R ¹ -A ¹¹ -Y ¹ -A ¹² -(Y ² -X ¹ -C≡CX ² -Cy) _k -R ² -Q ² (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.

Also, as described above, A ¹¹ , A ¹² , and A ¹³ are each independently a partial structure or a divalent organic group represented by formula (1); and, A ¹¹ and A ¹³ may be single bonds, but A ¹¹ does not exist And A ¹³ is a single bond case.

The hydrocarbon ring group in Cy includes aromatic hydrocarbon ring group and non-aromatic hydrocarbon ring group.

環、聯三伸苯環、苊環、螢蒽環、茀環等。 連結芳香族烴環基係複數個單環或縮合之芳香族烴環以單鍵鍵結，於構成環之原子上具有鍵結鍵的2價基。單環或縮合環之碳數較佳為6～20。例如為第1碳數6～20之單環或縮合之芳香族烴環與第2碳數6～20之單環或縮合之芳香族烴環以單鍵鍵結，於第1碳數6～20之單環或縮合之芳香族烴環之構成環之原子上具有第1鍵結鍵，於第2碳數6～20之單環或縮合之芳香族烴環之構成環之原子上具有第2鍵結鍵的2價基。作為連結芳香族烴環基，例如可列舉聯苯-4,4'-二基。 作為芳香族烴環基，較佳為非連結芳香族烴環基。 該等中，作為芳香族烴環基，較佳為苯環之2價基、萘環之2價基，更佳為苯環之2價基(伸苯基)。作為伸苯基，較佳為1,4-伸苯基。藉由具有上述基，而有液晶化合物之分子配向性變得良好之傾向。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 6-20. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetrabenzene ring, pyrene ring, benzopyrene ring,

Ring, bis-terylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. The linking aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond, and the atoms constituting the ring have a bonding bond. The carbon number of the monocyclic or condensed ring is preferably 6-20. For example, the first monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms and the second monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms are bonded by a single bond, and the first carbon number is 6 to 20 monocyclic or condensed aromatic hydrocarbon ring has the first bond on the atom constituting the ring, and the second carbon 6-20 monocyclic or condensed aromatic hydrocarbon ring has the first bond on the atom constituting the ring The divalent base of a 2-bonded bond. Examples of the linking aromatic hydrocarbon ring group include biphenyl-4,4'-diyl. The aromatic hydrocarbon ring group is preferably a non-linked aromatic hydrocarbon ring group. Among them, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring and a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene). As the phenylene group, 1,4-phenylene group is preferred. By having the above group, the molecular alignment of the liquid crystal compound tends to become better.

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 3-20. Examples of the non-aromatic hydrocarbon ring include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, nordane ring, and cyclohexane ring. Alkyl ring, adamantane ring, tetralin ring, bicyclic [2.2.2] octane ring, etc. The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group that does not have an unsaturated bond as the interatomic bond of the non-aromatic hydrocarbon ring, and one of the alicyclic hydrocarbon ring group that has an unsaturated bond as the non-aromatic hydrocarbon ring Unsaturated non-aromatic hydrocarbon ring group with interatomic bonds. The non-linked non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group. The non-aromatic hydrocarbon ring group is a divalent group consisting of multiple monocyclic or condensed non-aromatic hydrocarbon rings bonded by a single bond and having bonding bonds on the atoms constituting the ring; or selected from a monocyclic aromatic hydrocarbon One or more rings in the group consisting of a ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring have a single bond to a monocyclic or condensed non-aromatic hydrocarbon ring Bonding is a divalent group having a bonding bond on the atoms constituting the ring. The carbon number of the monocyclic ring or the condensed ring is preferably 3-20. For example, the first monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons and the second monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons are bonded by a single bond, at the first carbon number The atoms of the 3-20 monocyclic or condensed non-aromatic hydrocarbon ring have the first bond, and the second carbon number 3-20 monocyclic or condensed non-aromatic hydrocarbon ring constitutes the ring A divalent group with a second bond on the atom, such as a monocyclic or condensed aromatic hydrocarbon ring with 3 to 20 carbons and a monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons with a single bond Bonding, having the first bond on the atoms constituting the ring of a monocyclic or condensed aromatic hydrocarbon ring with 3-20 carbons, in a monocyclic or condensed non-aromatic hydrocarbon ring with 3-20 A divalent group having a second bonding bond on the atoms constituting the ring. Examples of the linked non-aromatic hydrocarbon ring group include bis(cyclohexane)-4,4'-diyl and 1-cyclohexylbenzene-4,4'-diyl. The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group from the viewpoint of the molecular orientation of the liquid crystal compound. Among them, the non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl). The cyclohexanediyl group is preferably cyclohexane-1,4-diyl group. By having the above-mentioned group, the solubility and the molecular alignment of the liquid crystal compound tend to become better.

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

The aromatic heterocyclic group includes a non-linked aromatic heterocyclic group and a connected aromatic heterocyclic group. The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic group, and the carbon number is preferably 4-20. Examples of aromatic heterocyclic rings include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolo Imidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzisoazole ring , Benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, phenanthridine Ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring, etc. The linking aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond, and the atoms constituting the ring have a bonding bond. The carbon number of the monocyclic ring or the condensed ring is preferably 4-20. For example, the first monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms and the second monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms are bonded by a single bond, and the first carbon number is 4 to 20 monocyclic or condensed aromatic heterocyclic ring has the first bond on the atom constituting the ring, and the second carbon number 4-20 monocyclic or condensed aromatic heterocyclic ring has the first bond on the atom constituting the ring The divalent base of a 2-bonded bond.

啶環等。 連結非芳香族雜環基係複數個單環或縮合之非芳香族雜環以單鍵鍵結，於構成環之原子上具有鍵結鍵的2價基。單環或縮合環之碳數較佳為4～20。例如為第1碳數4～20之單環或縮合之非芳香族雜環與第2碳數4～20之單環或縮合之非芳香族雜環以單鍵鍵結，於第1碳數4～20之單環或縮合之非芳香族雜環之構成環之原子上具有第1鍵結鍵，於第2碳數4～20之單環或縮合之非芳香族雜環之構成環之原子上具有第2鍵結鍵的2價基。The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a connected 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 4-20. The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbons. Examples of the non-aromatic heterocyclic ring include: tetrahydrofuran ring, tetrahydropyran ring, and two Alkane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperidine ring, tetrahydrothiazole ring, tetrahydroxazole ring, octahydroquinoline ring, four Hydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring,

Pyridine ring and so on. The linking 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 atoms constituting the ring have bonding bonds. The carbon number of the monocyclic ring or the condensed ring is preferably 4-20. For example, the first monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms and the second monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms are bonded by a single bond, at the first carbon number A 4-20 monocyclic or condensed non-aromatic heterocyclic ring has a first bonding bond on the atoms of the second monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms. A divalent group with a second bond on the atom.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy can be selected from R ^z , -OH, -OR ^z , -OC(=O)- R ^z , -NH ₂ , -NH-R ^z , -N(R ^z' )-R ^z , -C(=O)-R ^z , -C(=O)-OR ^z , -C(=O) -NH ₂ , -C(=O)-NH-R ^z , -C(=O)-N(R ^z' )-R ^z , -SH, -SR ^z , trifluoromethyl, sulfamoyl, One or more group substitutions in the group consisting of carboxyl, sulfo, cyano, nitro, and halogen. Here, R ^z and R ^z'each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. Regarding the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy, the linearity of the molecular structure is relatively high, and the molecules represented by formula (2) tend to gather together In terms of easily expressing the liquid crystal state, it is preferable to be independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, and a bromine atom, and it is more preferable to be unsubstituted. The substituents of the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different, and can be aromatic hydrocarbon ring group and non-aromatic hydrocarbon ring group , All of the aromatic heterocyclic groups and non-aromatic heterocyclic groups may be substituted, all may be unsubstituted, or partly substituted and partly unsubstituted.

As Cy, from the viewpoint of solubility and molecular orientation of the liquid crystal compound, a hydrocarbon ring group is preferable, and a phenylene group or a cyclohexanediyl group is more preferable. Furthermore, in terms of improving the linearity of the molecular structure of the liquid crystal compound, as Cy, 1,4-phenylene and cyclohexane-1,4-diyl are more preferred, and 1,4-phenylene is particularly preferred. Phenyl.

In terms of the linearity of the liquid crystal compound or the tendency to easily rotate around the short axis of the molecule, -X ¹ -is preferably -C(=O)O-, -OC(= O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O- , -OCH ₂ -, -CH ₂ S-, -SCH ₂ -, more preferably -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -. As a certain aspect, -X ¹ -is -C(=O)O- or -OC(=O)-, as another aspect, -X ¹ -is -CH ₂ CH ₂ -, -CH ₂ O -, or -OCH ₂ -.

From the viewpoint of increasing the size of the nucleus of the liquid crystal compound and increasing the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film, it is preferable to connect with a highly linear base -Cy- and -C≡C-, specifically, -X ² -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)- is more preferably a single bond in terms of higher linearity.

The polymerizable group in the present invention is a group having a partial structure that can be polymerized by light, heat, and/or radiation, and is a functional group or atomic group required to ensure a polymerization function. The polymerizable group is preferably a photopolymerizable group from the viewpoint of the production of an anisotropic dye film. As the polymerizable group, specifically, for example, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, ethylene Group, vinyloxy, ethynyl, ethynyloxy, 1,3-butadienyl, 1,3-butadienyloxy, oxiranyl, oxetanyl, glycidyl, glycidol Oxy, styryl, styryloxy, etc. Among these, preferred are acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, oxirane, and condensation. Glyceryl, glycidyloxy, more preferably acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, glycidyl , Glycidyloxy, more preferably acryloxy, methacryloxy, and glycidoxy. By having the above-mentioned polymerizable group, there is a tendency to easily control the polymerization.

The chain organic group in R ¹ and R ² is a divalent organic group without a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocyclic ring, and non-aromatic heterocyclic ring. Examples of such chain organic groups include -(alkylene)-, -O-(alkylene)-, -S-(alkylene)-, -NH-(alkylene)-, -N (Alkyl)-(alkylene)-, -OC(=O)-(alkylene)-, -C(=O)O-(alkylene)-. The chain organic group in R ¹ and R ² is preferably -(alkylene)- and -O-(alkylene)-. In a certain aspect, the chain organic group in R ¹ and R ² is -(alkylene)-, and in another aspect, such a chain organic group is -O-(alkylene)-.

Examples of the alkylene group in these chain organic groups include linear or branched alkylene groups having 1 to 25 carbon atoms. A part of the carbon-carbon bond of the alkylene may become an unsaturated bond, and one or more of the methylene groups contained in the alkylene may be replaced with ethereal oxygen atoms or thioether sulfur. Structure of atom, amine nitrogen atom, carbonyl group, ester bond, amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ -. Furthermore, examples of the amine nitrogen atom include -NH- and -N(R ^z ), and R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms. As the alkylene group in these chain organic groups, as far as the linearity of the molecule is higher, a part of the carbon of the alkylene group becomes an unsaturated bond, and one or more of the alkylene groups can also be The methyl group is a structure in which the above group is substituted, and is 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 3-25, more preferably 5-20, and still more preferably 6-20.

As a 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 -, -(O) _n1 -(CH ₂ ) _n2 -(CH ₂ CH ₂ O) _n3 -is preferable from the viewpoint of improving the molecular alignment of the liquid crystal compound. Furthermore, n in the formula is an integer of 1-24, preferably an integer of 2-24, more preferably an integer of 4-19, and still more preferably an integer of 5-19. In addition, n1, n2, and n3 in the formula 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 preferably 3 ~25, more preferably 5-20, more preferably 6-20, adjust appropriately.

R ¹ and R ² are each independently preferably -(alkylene)-, -O-(alkylene)-, more preferably -(alkylene)-, -O-(alkylene)-. With the above-mentioned molecular structure, there is a tendency to improve the molecular alignment of the liquid crystal compound. In the case where X ¹ and R ¹ or X ¹ and R ^{2 are} bonded as shown in formula (2B) and formula (2E), or for example, in the case where A ¹³ is a single bond in formula (2B), or in formula (2E) ) in the case of A ¹¹ is a single bond, R ¹ or the like with the case when R ² Y ¹ Y ² or the bonding, the Y and X ¹ or Y ² bonded to the R ¹ or R ² or ¹ to improve the liquid crystal molecules of the compound From the viewpoint of alignment, -(alkylene)- is preferred. In addition, in cases other than the above, R ¹ or R ² not bonded to X ¹ or 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 hydrocarbon ring group or a heterocyclic group.

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

環、聯三伸苯環、苊環、螢蒽環、茀環等。 連結芳香族烴環基係複數個單環或縮合之芳香族烴環以單鍵鍵結，於構成環之原子上具有鍵結鍵的2價基。單環或縮合環之碳數較佳為6～20。例如為第1碳數6～20之單環或縮合之芳香族烴環與第2碳數6～20之單環或縮合之芳香族烴環以單鍵鍵結，於第1碳數6～20之單環或縮合之芳香族烴環之構成環之原子上具有第1鍵結鍵，於第2碳數6～20之單環或縮合之芳香族烴環之構成環之原子上具有第2鍵結鍵的2價基。作為連結芳香族烴環基，例如可列舉聯苯-4,4'-二基。 作為芳香族烴環基，較佳為非連結芳香族烴環基。 該等中，作為芳香族烴環基，較佳為苯環之2價基、萘環之2價基，更佳為苯環之2價基(伸苯基)。作為伸苯基，較佳為1,4-伸苯基。藉由具有上述基，而有液晶化合物之分子配向性變得良好之傾向。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 6-20. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetrabenzene ring, pyrene ring, benzopyrene ring,

Ring, bis-terylene ring, acenaphthene ring, fluoranthene ring, stilbene ring, etc. The linking aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond, and the atoms constituting the ring have a bonding bond. The carbon number of the monocyclic or condensed ring is preferably 6-20. For example, the first monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms and the second monocyclic or condensed aromatic hydrocarbon ring with 6 to 20 carbon atoms are bonded by a single bond, and the first carbon number is 6 to 20 monocyclic or condensed aromatic hydrocarbon ring has the first bond on the atom constituting the ring, and the second carbon 6-20 monocyclic or condensed aromatic hydrocarbon ring has the first bond on the atom constituting the ring The divalent base of a 2-bonded bond. Examples of the linking aromatic hydrocarbon ring group include biphenyl-4,4'-diyl. The aromatic hydrocarbon ring group is preferably a non-linked aromatic hydrocarbon ring group. Among them, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring and a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene). As the phenylene group, 1,4-phenylene group is preferred. By having the above group, the molecular alignment of the liquid crystal compound tends to become better.

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 3-20. Examples of the non-aromatic hydrocarbon ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norethane ring, and cyclohexane ring. Ring, adamantane ring, tetralin ring, bicyclo[2.2.2] octane ring, etc. The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group that does not have an unsaturated bond as the interatomic bond of the non-aromatic hydrocarbon ring, and one of the alicyclic hydrocarbon ring group that has an unsaturated bond as the non-aromatic hydrocarbon ring Unsaturated non-aromatic hydrocarbon ring group with bonds between atoms. The non-linked non-aromatic hydrocarbon ring group is preferably an alicyclic hydrocarbon ring group. The non-aromatic hydrocarbon ring group is a divalent group consisting of multiple monocyclic or condensed non-aromatic hydrocarbon rings bonded by a single bond and having bonding bonds on the atoms constituting the ring; or selected from a monocyclic aromatic hydrocarbon One or more rings in the group consisting of a ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring, and a single ring or a condensed non-aromatic hydrocarbon ring A bond is a divalent group having a bond on the atoms constituting the ring. The carbon number of the monocyclic ring or the condensed ring is preferably 3-20. For example, the first monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons and the second monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons are bonded by a single bond, at the first carbon number The atoms of the 3-20 monocyclic or condensed non-aromatic hydrocarbon ring have the first bond, and the second carbon number 3-20 monocyclic or condensed non-aromatic hydrocarbon ring constitutes the ring A divalent group with a second bond on the atom. In addition, for example, a monocyclic or condensed aromatic hydrocarbon ring with 3 to 20 carbons and a monocyclic or condensed non-aromatic hydrocarbon ring with 3 to 20 carbons are bonded by a single bond. A ring or condensed aromatic hydrocarbon ring has a first bond on the atoms constituting the ring, and a second bond on a carbon number 3-20 monocyclic or condensed non-aromatic hydrocarbon ring. The divalent base. Examples of the linked non-aromatic hydrocarbon ring group include bis(cyclohexane)-4,4'-diyl and 1-cyclohexylbenzene-4,4'-diyl. The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group. Among them, the non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl). The cyclohexanediyl group is preferably cyclohexane-1,4-diyl group from the viewpoint of solubility and molecular orientation of the liquid crystal compound.

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

The aromatic heterocyclic group includes a non-linked aromatic heterocyclic group and a connected aromatic heterocyclic group. The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic group, and the carbon number is preferably 4-20. Examples of aromatic heterocyclic rings include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolo Imidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzisoazole ring , Benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, quinoline ring, phenanthridine Ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring, etc. The linking aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond, and the atoms constituting the ring have a bonding bond. The carbon number of the monocyclic ring or the condensed ring is preferably 4-20. For example, the first monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms and the second monocyclic or condensed aromatic heterocyclic ring with 4 to 20 carbon atoms are bonded by a single bond, and the first carbon number is 4 to 20 monocyclic or condensed aromatic heterocyclic ring has the first bond on the atom constituting the ring, and the second carbon number 4-20 monocyclic or condensed aromatic heterocyclic ring has the first bond on the atom constituting the ring The divalent base of a 2-bonded bond.

啶環等。 連結非芳香族雜環基係複數個單環或縮合之非芳香族雜環以單鍵鍵結，於構成環之原子上具有鍵結鍵的2價基。單環或縮合環之碳數較佳為4～20。例如為第1碳數4～20之單環或縮合之非芳香族雜環與第2碳數4～20之單環或縮合之非芳香族雜環以單鍵鍵結，於第1碳數4～20之單環或縮合之非芳香族雜環之構成環之原子上具有第1鍵結鍵，於第2碳數4～20之單環或縮合之非芳香族雜環之構成環之原子上具有第2鍵結鍵的2價基。The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a connected 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 4-20. The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbons. Examples of the non-aromatic heterocyclic ring include: tetrahydrofuran ring, tetrahydropyran ring, and two Alkane ring, tetrahydrothiophene ring, tetrahydrothiopyran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperidine ring, tetrahydrothiazole ring, tetrahydroxazole ring, octahydroquinoline ring, four Hydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring,

Pyridine ring and so on. The linking 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 atoms constituting the ring have bonding bonds. The carbon number of the monocyclic ring or the condensed ring is preferably 4-20. For example, the first monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms and the second monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms are bonded by a single bond, at the first carbon number A 4-20 monocyclic or condensed non-aromatic heterocyclic ring has a first bonding bond on the atoms of the second monocyclic or condensed non-aromatic heterocyclic ring with 4 to 20 carbon atoms. A divalent group with a second bond on the atom.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q3 can be selected from R ^z , -OH, -OR ^z , -OC(=O)- R ^z , -NH ₂ , -NH-R ^z , -N(R ^z' )-R ^z , -C(=O)-R ^z , -C(=O)-OR ^z , -C(=O) -NH ₂ , -C(=O)-NH-R ^z , -C(=O)-N(R ^z' )-R ^z , -SH, -SR ^z , trifluoromethyl, sulfamoyl, One or more group substitutions in the group consisting of carboxyl, sulfo, cyano, nitro, and halogen. Here, R ^z and R ^z'each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms. Regarding the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q ³ , the linearity of the molecular structure is relatively high, and the molecules represented by formula (2) are easy to each other In terms of aggregation and easy expression of a liquid crystal state, it is preferable to be independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and it is more preferable to be unsubstituted. The substituents of the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be the same or different, and can be aromatic hydrocarbon ring group and non-aromatic hydrocarbon ring group , All of the aromatic heterocyclic groups and non-aromatic heterocyclic groups may be substituted, all may be unsubstituted, or partly substituted and partly unsubstituted. Furthermore, the substituents of the divalent organic groups in A ¹¹ , A ¹² , and A ¹³ may be the same or different, and all of the divalent organic groups in A ¹¹ , A ¹² and A ¹³ may be substituted, and all of them may be substituted Unsubstituted, or partly replaced and partly unsubstituted.

As Q ³ , a hydrocarbon ring group is preferred, and phenylene and cyclohexanediyl are more preferred. In addition, in terms of improving the linearity of the molecular structure of the liquid crystal compound, Q ^{3 is more} preferably 1,4-phenylene and cyclohexane-1,4-diyl.

As the divalent organic group, it is preferable that Q ³ is a hydrocarbon ring group, that is, the divalent organic group is a hydrocarbon ring group. In addition, as the divalent organic group, phenylene and cyclohexanediyl are more preferred. In terms of improving the linearity of the molecular structure of the liquid crystal compound, 1,4-phenylene and cyclohexane are more preferred. -1,4-diyl.

As formula (2), preferably one of A ¹¹ , A ¹² , and A ¹³ is a partial structure represented by formula (3), and the other two are independently divalent organic groups, preferably A The Cy of the partial structure represented by formula (3) in ¹¹ , A ¹² and A ¹³ is a hydrocarbon ring group, and the divalent organic group is particularly preferably a hydrocarbon ring group. Furthermore, it is preferable that the hydrocarbon ring group is 1,4-phenylene or cyclohexane-1,4-diyl. Furthermore, it is preferable that one of A ¹¹ and A ¹³ is cyclohexane-1,4-diyl. Moreover, it is more preferable that one of A ¹¹ and A ¹³ is a partial structure represented by formula (3), and the other one and A ¹² are a divalent organic group. In this case, it is preferable that one of the divalent organic groups in A ¹¹ and A ¹³ is cyclohexane-1,4-diyl, and it is particularly preferable that A ¹² is 1,4-phenylene. With the above structure, the molecular alignment of the liquid crystal compound tends to become better.

In terms of the linearity of the liquid crystal compound or the tendency of easy rotational movement around the short axis of the molecule, -Y ¹ -and -Y ² -are preferably independently single bonds with less π bonding, -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 -, more preferably a single bond, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -.

In formula (. 2A), the formula (2C), the formula (2D), the formula (2F) as X ¹ when the case of Y ¹ or X ¹ and Y ² bonded to it, and X ¹ bonded to the Y ¹ or X The Y ^{2 of the 1} bond is preferably a single bond; the other of -X ¹ -, -Y ¹ -and -Y ² -is preferably -C(=O)O- or -OC(=O)-. In addition, when X ¹ and Y ¹ and Y ² are not bonded as in formula (2B) and formula (2E), -X ¹ -is preferably -CH ₂ CH ₂ -, -CH ₂ O-, Or -OCH ₂ -; -Y ¹ -and -Y ² -are preferably both -C(=O)O- or -OC(=O)-. With the above structure, the molecular alignment of the liquid crystal compound tends to become better.

As formula (2), said formula (2A), said formula (2B), said (2E), and said (2F) are preferable. In another aspect, as formula (2), preferably one of A ¹¹ , A ¹² , and A ¹³ is a 1,4-phenylene group, and the other two are each independently a divalent organic group , Particularly preferably, the divalent organic group is a hydrocarbon ring group. More preferably, the hydrocarbon ring group is 1,4-phenylene or cyclohexane-1,4-diyl. With the above structure, the linearity of the molecule tends to be higher.

k is 1 or 2. As a certain aspect, k is 1 preferably. As another aspect, k is 2 preferably. By becoming the above-mentioned value, the molecular alignment of the liquid crystal compound tends to become better. When k is 2, each Y ² may be the same or different from each other, and each A ¹³ may be the same or different from each other.

Specific examples of the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention include the polymerizable liquid crystal compound described below, but it is not limited to these. Furthermore, in the formula, C ₅ H ₁₁ means n-pentyl, and C ₆ H ₁₃ means n-hexyl.

[化15]

[化16]

[化17]

[化18]

[化19]

[化20]

[化21]

[化22]

[化23]

[化24]

[化25]

[化26]

[化27]

[化28]

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

Regarding the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention, from the viewpoint of the manufacturing process, the isotropic phase appearance temperature is preferably 160°C or less, more preferably 140°C or less, and further It is preferably 115°C or lower, more preferably 110°C or lower, and particularly preferably 105°C or lower. 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 preferable that at least one of the phase transition temperatures is in the above range, and it is more preferable that both of the phase transition temperatures are in the above range.

The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be combined by alkylation reaction, esterification reaction, amination reaction, etherification reaction, local substitution reaction, and metal catalyst It is produced by combining well-known chemical reactions such as reactions. For example, the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be in accordance with the method described in the examples, or "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000) 449 Synthesis method described on page 468.

(Relationship between polymerizable liquid crystal compound and compound represented by formula (1)) From the point of view that it is easy to improve the orientation of anisotropic pigment film formed using the composition for forming anisotropic pigment film, in the composition for forming anisotropic pigment film, the molecular length of the liquid crystal compound and the molecular length of the pigment When the difference between is smaller, the interaction between the liquid crystal molecules and the dye molecules is stronger, and the dye molecules are not easy to hinder the aggregation of the liquid crystal molecules with each other, so it is better.

Therefore, in the composition for forming anisotropic dye film of the present invention, the number of ring structures (r _n1 ) possessed by the polymerizable liquid crystal compound contained in the composition for forming anisotropic dye film and the anisotropic dye film The ratio (r _n1 /r _n2 ) of the number of ring structures (r _n2 ) contained in the compound represented by the formula (1) contained in the composition for formation is preferably 0.7 to 1.5. Furthermore, a condensed ring formed by condensation of two or more rings is counted as one ring structure.

Here, the number (r _n2 ) of the ring structure of the compound represented by formula (1) refers to the sum 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 a pyrrolidinyl group or a piperidinyl group, the ring structure contained in X is not included in the number (r _n2 ) of the ring structure of the compound represented by the formula (1).

More specifically, when n is 1, r _n2 is 3, so r _n1 is 3 or 4; when n is 2, r _n2 is 4, so r _n1 is 3, 4, 5, or 6; When n is 3, r _n2 is 5, so r _n1 is 4, 5, 6, or 7, so that the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film has a ring number of number of ring structure (r _n1) of the structure anisotropic dye film is formed with a compound of formula (1) contained in the composition of the indicated having the (r _n2) ratio (r _n1 / r _n2) becomes 0.7 ~1.5, so it is better.

Furthermore, the number (r _n1 ) of the ring structure of the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film does not include the ring structure contained in the polymerizable group in the polymerizable liquid crystal compound (for example, ring Oxyethane ring or oxetane ring, etc.).

(Polymerization initiator) The composition for forming an anisotropic dye film of the present invention may optionally contain a polymerization initiator. The polymerization initiator is a compound that can start the polymerization reaction of the polymerizable liquid crystal compound. As the polymerization initiator, a photopolymerization initiator that generates living radicals by the action of light is preferred.

衍生物類；苯甲酸酯衍生物類；吖啶衍生物類；啡𠯤衍生物類；蒽酮衍生物類等。 該等光聚合起始劑中，更佳為烷基苯酮衍生物類、肟酯系衍生物類、雙咪唑衍生物類、苯乙酮衍生物類、及9-氧硫𠮿

衍生物類。The polymerization initiators that can be used include, for example, titanocene derivatives; bisimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-s-triazole derivatives; alkyl groups Benzophenone Derivatives; Oxime Esters Derivatives; Benzoins; Benzophenone Derivatives; Amino Phosphine Oxide Derivatives; Iodonium Salts; Aluminium Salts; Anthraquinone Derivatives; Acetophenone Derivatives Species; 9-oxysulfur 𠮿

Derivatives; benzoate derivatives; acridine derivatives; phenanthrene derivatives; anthrone derivatives, etc. Among these photopolymerization initiators, more preferred are alkyl phenone derivatives, oxime ester derivatives, bisimidazole derivatives, acetophenone derivatives, and 9-oxysulfur.

Derivatives.

Specifically, as the titanocene derivatives, 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, dicyclopentadienyl bis(2,4-di) Fluorophenyl-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 and the like.

In addition, examples of 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, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, etc.

Moreover, as the halomethylated oxadiazole derivatives, there may be mentioned: 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4-oxadiazole, 2-trichloro Methyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6' '-Benzofuranyl)vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

In addition, examples of halomethyl-s-tris-tris derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-ss-triss, 2-(4- Methoxynaphthyl)-4,6-bis(trichloromethyl)-s-tris, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-ss-tris , 2-(4-Ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-tris, etc.

In addition, as alkylphenone derivatives, diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-𠰌linylpropane-1- Ketone, 2-benzyl-2-dimethylamino-1-(4-𠰌linephenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4- 𠰌linylphenyl)butan-1-one, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4 -Dimethylaminopropiophenone, 1,4-dimethylaminobenzoic acid 2-ethylhexyl ester, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7- Diethylamino-3-(4-diethylaminobenzyl) coumarin, 4-(diethylamino)chalcone and the like.

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

Moreover, as benzoin, benzoin, benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, etc. are mentioned.

Also, as benzophenone derivatives, benzophenone, Michelone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone can be cited , 2-Chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, methyl phthalate, 4-phenylbenzophenone, 4-benzophenone -4'-Methyl diphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone Ketones and so on.

In addition, as acylphosphine oxide derivatives, 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzyl)- 2,4,4-Trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, etc.

In addition, examples of iodonium salts include diphenyl iodonium-tetrakis (pentafluorophenyl) borate, diphenyl iodonium-hexafluorophosphate, diphenyl iodonium-hexafluoroantimonate, bis(4- Nonylphenyl) iodo-hexafluorophosphate and the like.

-六氟銻酸鹽、7-[二(對甲苯甲醯基)鋶基]-2-異丙基9-氧硫𠮿

-四(五氟苯基)硼酸鹽、4-苯基羰基-4'-二苯基鋶基-二苯基硫醚-六氟磷酸鹽、4-(對第三丁基苯基羰基)-4'-二苯基鋶基-二苯基硫醚-六氟銻酸鹽、4-(對第三丁基苯基羰基)-4'-二(對甲苯甲醯基)鋶基-二苯基硫醚-四(五氟苯基)硼酸鹽等。In addition, examples of the sulfonium salts include triphenylsulfonium-hexafluorophosphate, triphenylsulfonium-hexafluoroantimonate, triphenylsulfonium-tetrakis(pentafluorophenyl) borate, and diphenyl[ 4-(Phenylthio)phenyl] sulfonium-hexafluorophosphate, 4,4'-bis[diphenyl sulfonyl]diphenyl sulfide-bishexafluorophosphate, 4,4'-bis[di (β-Hydroxyethoxy) Phenyl Aranyl] Diphenyl Sulfide-Bishexafluoroantimonate, 4,4'-Bis[Bis(β-Hydroxyethoxy) Phenyl Aranyl] Diphenyl Thioether-bishexafluorophosphate, 7-[bis(p-tolylmethyl)ethanyl]-2-isopropyl 9-oxysulfur𠮿

-Hexafluoroantimonate, 7-[bis(p-tolylmethyl)ethanyl]-2-isopropyl 9-oxysulfur 𠮿

-Tetra(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylarunyl-diphenylsulfide-hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)- 4'-Diphenylarunyl-diphenylsulfide-hexafluoroantimonate, 4-(p-tertiary butylphenylcarbonyl)-4'-bis(p-tolylmethyl)epoxy-diphenyl Sulfide-tetrakis (pentafluorophenyl) borate and the like.

In addition, examples of anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and the like.

In addition, as acetophenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone , Α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl) ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone , 2-Methyl-(4'-methylthiophenyl)-2-𠰌line-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl)ketone, etc.

衍生物類，可列舉：9-氧硫𠮿

、2-乙基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

、2-氯9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

等。Also, as 9-oxysulfur 𠮿

Derivatives, including: 9-oxysulfur 𠮿

, 2-ethyl 9-oxysulfur 𠮿

, 2-isopropyl 9-oxysulfur 𠮿

, 2-Chloro 9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

Wait.

Moreover, as benzoate derivatives, ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, etc. are mentioned.

Moreover, as acridine derivatives, 9-phenyl acridine, 9-(p-methoxyphenyl) acridine, etc. are mentioned.

In addition, as phenanthrene derivatives, 9,10-dimethylbenzophenone and the like can be cited.

Moreover, as anthrone derivatives, benzoanthrone etc. are mentioned.

A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

As the polymerization initiator, commercially available products may also be used. Examples of commercially available products include: IRGACURE (registered trademark, the same applies hereinafter) 250, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCRIN 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 (Dow Chemical Co., Ltd.); Adeka Optomer SP-152, and SP-170 (made by ADEKA Co., Ltd.); TAZ-A, and TAZ-PP (manufactured by Nihon SiberHegner Co., Ltd.); and TAZ-104 (Sanwa Chemical 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, it is difficult to confuse the alignment of the polymerizable liquid crystal compound. The content of the polymerization initiator in the composition of the present invention is relative to 100% of the polymerizable liquid crystal compound. The parts by mass are usually 0.1-30 parts by mass, preferably 0.5-10 parts by mass, and more preferably 0.5-8 parts by mass.

Optionally, a polymerization accelerator may be used in combination with the polymerization initiator. As the polymerization accelerator used, for example, N,N-dialkylaminobenzoic acid alkyl esters such as ethyl N,N-dimethylaminobenzoate; 2-mercaptobenzothiazole, 2 -Mercapto compounds such as mercaptobenzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds, etc.

系色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報等所記載之具有雜環之香豆素系色素；日本專利特開平3-239703號公報、日本專利特開平5-289335號公報等所記載之3-酮基香豆素系色素；日本專利特開平6-19240號公報等所記載之吡咯亞甲基系色素；日本專利特開昭47-2528號公報、日本專利特開昭54-155292號公報、日本專利特公昭45-37377號公報、日本專利特開昭48-84183號公報、日本專利特開昭52-112681號公報、日本專利特開昭58-15503號公報、日本專利特開昭60-88005號公報、日本專利特開昭59-56403號公報、日本專利特開平2-69號公報、日本專利特開昭57-168088號公報、日本專利特開平5-107761號公報、日本專利特開平5-210240號公報、日本專利特開平4-288818號公報等所記載之具有二烷基胺基苯骨架之色素等。 又，增感色素亦可單獨使用1種，亦可併用2種以上。In addition, if necessary, a sensitizing dye may be used in combination for the purpose of improving the sensitivity. The sensitizing dye can be appropriately used according to the wavelength of the exposure light source. For example, the sensitizing dye may be described in Japanese Patent Laid-Open No. 4-221958, Japanese Patent Laid-Open No. 4-219756, etc.

Pigments; Coumarin-based pigments with heterocycles described in Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open No. 5-289335, etc.; Japanese Patent Laid-Open No. 3-239703, Japanese Patent Laid-Open Hei 3-ketocoumarin-based pigments described in 5-289335, etc.; pyrromethene-based pigments described in Japanese Patent Laid-Open No. 6-19240, etc.; Japanese Patent Laid-Open No. 47-2528, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication 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 Dye having a dialkylaminobenzene skeleton described in Kaihei 5-107761, Japanese Patent Laid-Open No. 5-210240, and Japanese Patent Laid-Open No. 4-288818. Moreover, a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

(Solvent) The composition for forming an anisotropic dye film of the present invention may optionally contain a solvent. The usable solvent is not particularly limited as long as it can sufficiently disperse or dissolve the dye or other additives in the liquid crystal compound, and examples include methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, and ethylenedioxide. Alcohol solvents such as methyl alcohol ether, ethylene glycol butyl ether, propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate Ester solvents such as esters; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; toluene , Xylene and other aromatic hydrocarbon solvents; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; perfluorobenzene, perfluorotoluene, perfluoro Fluorine-containing solvents such as hydronaphthalene, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene. One type of these solvents may be used, or two or more types may be used in combination.

The solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound and the dye, and more preferably a solvent that can completely dissolve the polymerizable liquid crystal compound and the dye. Also, a solvent that is inert to the polymerization reaction is preferred. In addition, from the viewpoint of coating the composition for forming an anisotropic dye film of the present invention described below, a solvent having a boiling point in the range of 50 to 200°C is preferred.

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

(Other additives) The composition for forming anisotropic pigment film of the present invention may further contain a polymerization inhibitor, a polymerization assistant, a polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a coupling agent, a pH adjuster, and a dispersing agent as necessary. , Antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, metal oxides and other additives. By containing additives, it is possible to improve the coatability or stability of the composition for forming anisotropic pigment film, or to improve the stability of the anisotropic pigment film formed from the composition for forming anisotropic pigment film situation.

[Method for producing composition for forming anisotropic pigment film] The method for producing the composition for anisotropic dye film of the present invention is not particularly limited. For example, a dye, a polymerizable liquid crystal compound, a solvent as necessary, other additives, etc. are mixed, and the dye is dissolved by stirring and shaking at 0 to 80°C. In the case of poor solubility, a homogenizer, bead mill disperser, etc. can also be used. As a method for producing the composition for anisotropic dye film of the present invention, it can also have a filtration step for the purpose of removing foreign matter in the composition.

Regarding the composition for forming an anisotropic dye film of the present invention, the composition obtained by removing the solvent from the composition for forming an anisotropic dye film may be liquid crystal at any temperature or not at any temperature, and is preferably Display liquid crystallinity at any temperature. The composition obtained by removing the solvent from the composition for forming an anisotropic dye film. From the viewpoint of the coating process described below, the isotropic phase appearance temperature is preferably less than 160°C, more preferably less than 140 °C, more preferably less than 115°C, still more preferably less than 110°C, and particularly preferably less than 105°C.

[Anisotropic Pigment Film] The anisotropic dye film of the present invention is formed using the composition for forming an anisotropic dye film of the present invention. Therefore, the anisotropic dye film of the present invention includes a dye, one or both of a polymerizable liquid crystal compound and a polymer having a unit based on the polymerizable liquid crystal compound, and the dye includes the compound represented by formula (1). The anisotropic dye film of the present invention may also contain a non-polymerizable liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a polymerization assistant, a polymerizable non-liquid crystal compound, a non-polymerizable non-liquid crystal compound, a surfactant, and a leveling agent , Coupling agent, pH adjuster, dispersant, antioxidant, organic/inorganic filler, organic/inorganic nanosheet, organic/inorganic nanofiber, metal oxide, etc.

The anisotropic dye film of the present invention can be formed using the composition for forming an anisotropic dye film of the present invention.

The anisotropic pigment film in the present invention can be used as a polarizing film to obtain linear polarization, circular polarization, elliptical polarization, etc. by using the anisotropy of light absorption, and can also be formed by a film forming process and a substrate or containing organic compounds. The composition of (pigment or transparent material) is selected to be functionalized as various anisotropic pigment films such as refractive anisotropy or conduction anisotropy.

When the anisotropic dye film of the present invention is used as a polarizing element for liquid crystal displays or anti-reflection films for OLEDs, the alignment characteristics of the anisotropic dye film can be expressed by the two-color ratio. As long as the dichroic ratio is 8 or more, it functions as a polarizing element, and it is preferably 15 or more, more preferably 20 or more, still more preferably 25 or more, particularly preferably 30 or more, and still more preferably 40 or more. Also, the higher the two-color ratio, the better. By making the dichroic ratio more than the said lower limit, it is useful as the following optical element, especially a polarizing element. When used as a polarizing element of an anti-reflection film for OLED, even if the performance of the peripheral materials such as retardation film is low, as long as the performance of the polarizing element is high, the characteristics of the anti-reflection film will be improved. Therefore, as long as the performance of the polarizing element is high, it is easy to simplify the layer structure, even if it is made of a thin film, it is easy to exhibit sufficient functions, and it can also be used well for use after deformation including bending and bending. In addition, the cost can also be kept low.

In the present invention, the dichroic ratio (D) is expressed by the following formula when the pigments are uniformly aligned. D=A _z /A _y where A _z 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 A _y is incident in the opposite direction The absorbance observed when the polarized light direction of the sex pigment film is vertical. The absorbance (A _z , A _y ) is not particularly limited as long as the same wavelength is used. Any wavelength can be selected depending on the purpose. When the degree of the alignment of the anisotropic pigment film is expressed, it is preferably used for anisotropic The specific wavelength range of 380 nm ~ 780 nm of the pigment film is the value after the correction of the visual sensitivity, or the value of the maximum absorption wavelength in the visible region.

In addition, the transmittance of the anisotropic dye film of the present invention is preferably 25% or more at the target wavelength used, more preferably 35% or more, and particularly preferably 40% or more. Moreover, the transmittance may 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, and more preferably It is more than 35%, particularly preferably more than 40%. Moreover, the transmittance may 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, it is useful as the following optical element, especially as an optical element for liquid crystal displays for color display, or as an optical element for antireflection film obtained by combining anisotropic dye film and retardation film it works.

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

[Method of manufacturing anisotropic pigment film] The anisotropic dye film of the present invention is preferably produced by a wet film forming method using the composition for forming an anisotropic dye film of the present invention. The so-called wet film forming method in the present invention refers to a method of coating and aligning the anisotropic dye film composition on a substrate by some method. Therefore, as long as the composition for anisotropic dye films has fluidity, it may contain a solvent or may not contain a solvent. From the viewpoint of viscosity during coating or film uniformity, it is more preferable to contain a solvent.

The alignment of the liquid crystals or pigments in the anisotropic dye film can be oriented by shearing etc. during the coating process, and can also be oriented during the solvent drying process. In addition, it is also possible to perform a process of realigning liquid crystals or pigments by heating after coating and drying, so that the liquid crystals or pigments can be aligned and stacked on the substrate. In the wet film forming method, if the composition for anisotropic dye film is applied to the substrate, it is already in the composition for the anisotropic dye film, or in the process of solvent drying, or after the solvent is completely removed , The pigment or liquid crystal compound obtains self-aggregation (molecular aggregation state such as liquid crystal state), thereby generating 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 to obtain an anisotropic pigment film with required performance. In this respect, it is different from a method in which a polyvinyl alcohol (PVA) film or the like is dyed and stretched using a solution containing a pigment, and the pigment is aligned only by the stretching step. Furthermore, the term “external field” here includes the influence of the alignment treatment layer applied to the substrate in advance, shear force, magnetic field, electric field, heat, etc., which can be used alone or in combination. If necessary, a heating step can be passed. The process of applying the anisotropic dye film composition to the substrate to form a film, the process of applying an external field for alignment, and the process of drying the solvent can be performed sequentially or simultaneously.

As a method of applying the composition for forming an anisotropic dye film to the substrate in the wet film forming method, for example, a coating method, a dip coating method, LB (Langmuir-Blodgett, Langmuir-Blodgett ) Film formation method, well-known printing method, etc. There is also a method of transferring the anisotropic dye film thus obtained to another substrate.

Among these, it is preferable to apply the composition for forming an anisotropic dye film to the substrate by a coating method. The alignment direction of the anisotropic pigment film may also be different from the coating direction. Furthermore, the orientation direction of the anisotropic pigment film in the present invention, for example, if it is a polarizing film, it refers to the transmission axis (polarization axis) or absorption axis of polarized light, and if it is a retardation film, it refers to the phase advance axis or Slow axis.

The method of applying the composition for anisotropic pigment film to obtain an anisotropic pigment film is not particularly limited. For example, it can be cited: Harasaki Yuji "Coating Engineering" (Asakura Shoten Co., Ltd., March 1971 Issued on the 20th) on pages 253 to 277; Supervised by Ichimura Guohong, "Creation and Application of Molecular Coordination Materials" (published by CMC Co., Ltd., issued on March 3, 1998), pages 118 to 149 Method; on a substrate with a stepped structure (or pre-alignment treatment can also be performed) by slit die nozzle coating method, spin coating method, spray coating method, bar coating method, roll coating method , Blade coating method, curtain coating method, injection method, dipping method and other coating methods. Among them, if the slit die nozzle coating method or the bar coating method is adopted, an anisotropic pigment film with higher uniformity can be obtained, which is preferable.

The die nozzle coating machine used for the slit die nozzle coating method generally includes a coating machine that ejects a coating liquid, a so-called slit die. The slit die is disclosed, for example, in Japanese Patent Laid-Open No. 2-164480, Japanese Patent Laid-Open No. 6-154687, Japanese Patent Laid-Open No. 9-131559, "The basis and application 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 the Field of Electronics" ( 2007, Technology Information Association, ISBN9784861041389) etc. Regarding these well-known slit die, even if it is a flexible member such as a film or a tape, or a harder member such as a glass substrate, it can be coated.

As the substrate used for the formation of the anisotropic dye film of the present invention, glass, or triacetate, acrylic, polyester, polyimide, polyetherimine, polyetheretherketone, poly Carbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl cellulose or urethane-based film, etc. In addition, in order to control the alignment direction of the pigments, it is also possible to use the well-known method (rubbing method) described on pages 226 to 239 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000) on the surface of the substrate. , The method of forming grooves (fine groove structure) on the surface of the alignment film, the method of using polarized ultraviolet light/polarized laser (photoalignment method), the alignment method formed by the LB film, and the oblique evaporation of inorganic substances Alignment method of plating, etc.) implement alignment treatment (alignment film). In particular, the alignment treatment using the rubbing method and the photo-alignment method can be cited well. Examples of materials used in the friction method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin, and the like. Examples of materials used for the photo-alignment method include polycinnamate series, polyamide acid/polyimide series, azobenzene series, and the like. When an alignment treatment layer is provided, it is considered that the liquid crystal compound or the dye is aligned by the influence of the alignment treatment of the alignment treatment layer and the shear force applied to the composition for anisotropic dye film during coating.

The supply method and supply interval of the composition for anisotropic dye films when applying the composition for anisotropic dye films are not particularly limited. Since the supply operation of the coating liquid becomes complicated, or the coating film thickness varies between the start and stop of the coating liquid, when the film thickness of the anisotropic pigment film is thin, it is preferable to It is applied while continuously supplying the composition for anisotropic dye film.

The speed of coating the anisotropic dye film composition is usually 0.001 m/min or more, preferably 0.01 m/min or more, more preferably 0.1 m/min or more, and still more preferably 1.0 m/min or more, More preferably, it is 5.0 m/min or more. In addition, it is usually 400 m/min or less, preferably 200 m/min or less, more preferably 100 m/min or less, and still more preferably 50 m/min or less. By setting the coating speed within the above-mentioned range, the anisotropy of the anisotropic pigment film can be obtained and uniform coating tends to be possible. The coating temperature of the composition for anisotropic dye film is usually 0°C or higher and 100°C or lower, preferably 80°C or lower, and more preferably 60°C or lower. The humidity when applying the composition for anisotropic dye film is preferably 10% RH or more, and preferably 80 RH% or less.

The anisotropic pigment film can also be insolubilized. The so-called insolubilization refers to the treatment of controlling the dissolution of the compound from the anisotropic pigment film by reducing the solubility of the compound in the anisotropic pigment film and improving the stability of the film. Specifically, the polymerization or overcoating of the film is preferable in terms of the ease of subsequent steps and the durability of the anisotropic dye film.

In the case of film polymerization, light, heat, and/or radiation are used to polymerize the film in which liquid crystal molecules and dye molecules are aligned.

In the case of polymerization using light or radiation, it is preferable to irradiate active energy rays with a wavelength in the range of 190 to 450 nm. The light source of the active energy line with a wavelength of 190-450 nm is not particularly limited. Examples include: xenon lamp, halogen lamp, tungsten lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, medium-pressure mercury lamp, low-pressure mercury lamp, carbon Light sources such as arcs and fluorescent lamps; argon ion lasers, YAG (Yttrium Aluminum Garnet) lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers and other laser light sources Wait. When irradiating light of a specific wavelength for use, an optical filter can also be used. The exposure amount of active energy rays is preferably 10 to 10,000 J/m ² .

In the case of using heat to perform polymerization, it is preferably carried out in the range of 50 to 200°C, and more preferably in the range of 60 to 150°C.

It is also possible to use light, heat, and/or radiation to perform polymerization. The use of photopolymerization, or the combined use of photopolymerization and thermal polymerization is preferable in terms of a shorter film forming process time and a simple device.

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

The optical element of the present invention refers to a polarizing element that obtains linear polarization, circular polarization, elliptical polarization, etc., using the anisotropy of light absorption, a phase difference element, and an element having functions such as refractive anisotropy or conduction anisotropy. These functions can be appropriately adjusted by the anisotropic dye film forming process and the selection of 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 also be suitably used for applications such as flexible displays in that a polarizing element can be obtained by forming an anisotropic dye 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 can also be provided with other layers. Examples include: a layer with a function of blocking a specific wavelength or a layer with a function of blocking a specific substance (oxygen blocking film, water vapor blocking film, etc.) to improve durability such as light resistance, heat resistance, and water resistance Barrier film, etc.); wavelength cut filters used to change the color gamut or improve optical characteristics, or layers containing materials that absorb specific wavelengths.

[Polarizing element] The polarizing element of the present invention may have any other film (layer) as long as it has the anisotropic dye film of the present invention. For example, it can be manufactured by providing an alignment film on a substrate and forming the anisotropic dye film of the present invention on the surface of the alignment film. In addition, the polarizing element is not limited to anisotropic pigment film, but can also be combined with an external coating that has the functions of improving polarization performance and improving mechanical strength; adhesion layer or anti-reflection layer; alignment film; having the function of retardation film. The function of the brightness enhancement film, the function of the reflection or anti-reflection film, the function of the semi-transmitting reflection film, the function of the diffuser film and other optical function layers are used in combination. Specifically, it can also be used in the form of a laminated body by laminating layers having the above-mentioned various functions by coating or bonding. The layers can be appropriately set according to the manufacturing process, characteristics, and functions, and the stacking position, order, etc. are not particularly limited. For example, the position for forming each layer may be formed on the anisotropic dye film, or may be formed on the opposite surface of the substrate provided with the anisotropic dye film. In addition, the order of forming each layer may be before forming an anisotropic dye film or after forming an anisotropic dye film.

The layers with optical functions can be formed by the following methods.

The layer having a function as a retardation film can be formed by coating or bonding the retardation film to other layers constituting the polarizing element. For the retardation film, for example, the stretching process described in Japanese Patent Laid-Open No. 2-59703, Japanese Patent Laid-Open No. 4-230704, etc., or the treatment described in Japanese Patent Laid-Open No. 7-230007, etc. And formed.

The layer having a function as the brightness enhancement film can be formed by coating or bonding the brightness enhancement film to other layers constituting the polarizing element. The brightness-enhancing film can be formed by forming fine pores, for example, by using the method described in Japanese Patent Laid-Open No. 2002-169025 and Japanese Patent Laid-Open No. 2003-29030, or by overlapping two or more layers of cholesterol with different central wavelengths of selective reflection. The liquid crystal layer is formed.

The layer having a function as a reflective film or a semi-transmissive reflective film can be formed, for example, by coating or bonding a metal thin film obtained by vapor deposition or sputtering to other layers constituting the polarizing element. The layer having a function as a diffusion film can be formed, for example, by coating a resin solution containing fine particles on another layer constituting the polarizing element.

A layer with a function as a retardation film or an optical compensation film can be coated on a discotic liquid crystal compound, nematic liquid crystal compound, smectic liquid crystal compound, cholesteric liquid crystal compound and other liquid crystal compounds. The other layers constituting the polarizing element are formed by the alignment. At this time, an alignment film can also be arranged on the substrate, and a retardation film or an optical compensation film can be formed on the surface of the alignment film.

When the anisotropic dye film of the present invention is used as an anisotropic dye film or the like for various display elements such as liquid crystal devices (LCD) or organic electroluminescence devices (OLED), it can be used to form electrodes of such display elements. The anisotropic dye film of the present invention is directly formed on the surface of a substrate or the like, and the substrate on which the anisotropic dye film of the present invention is formed can also be used as a constituent member of these display elements. [Example]

The present invention will be explained in more detail with examples, but as long as the gist is not exceeded, the present invention is not limited to the following examples. In the following description, "parts" means "parts by weight".

[Method of Identification of Liquid Crystal Phase] The liquid crystallinity of the obtained anisotropic dye film forming composition was measured by differential scanning calorimetry (Seiko Instruments, "DSC220CU"), X-ray structure analysis (Rigaku Co., Ltd., "NANO-Viewer"), and high temperature The polarizing microscope (Nikon Instruments Co., Ltd., "ECLIPSE LV100N POL") attached to the stage (Toyo Technology Co., Ltd., "HCS302-LN190") was used for observation according to the "Liquid Crystal Handbook" (Maruzen Co., Ltd., October 2000) Issued on 30th) using the methods described on pages 9-50, 117-176, etc., to determine whether it is liquid crystal.

[Measurement of the transmittance of the polarized light in the absorption axis/polarization axis direction and the dichroic ratio of the anisotropic pigment film] The obtained anisotropic pigment film has the transmittance of the polarized light in the absorption axis/polarization axis direction. -Thomson polarizing element spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100") for measurement. The linearly polarized measuring light is incident on the anisotropic dye film, and the transmittance of the anisotropic dye film to the polarized light in the direction of the absorption axis and the transmittance of the anisotropic dye film to the polarized light in the direction of the polarization axis are measured, and the two colors are calculated according to the following formula Than (D). D=A _z /A _y (where A _y =-log(T _y ); A _z =-log(T _z ); T _z is the transmittance of the anisotropic pigment film to polarized light in the direction of the absorption axis; T _y is the transmittance of the anisotropic pigment film to polarized light in the direction of the polarization axis)

Specifically, a sandwich cell (cell gap: 8.0 μm, 10.0 μm) formed with an alignment film of polyimide (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems) on glass as a base In the polyimide film obtained by rubbing treatment), inject the composition for anisotropic pigment film in an isotropic phase, and cool to 80°C at 5°C/min to obtain the anisotropic pigment film. Cool down to 0°C at 5°C/min, and measure the dichroic ratio at each temperature. Among them, the two-color ratio at the temperature and wavelength showing the maximum two-color ratio is determined as the two-color ratio of the anisotropic pigment film. Also, in the measurement at this temperature, the two-color ratio at the wavelength at which the absorbance in the vertical position (the direction of the absorption axis) in the anisotropic pigment film shows the maximum value (the second at the wavelength where the absorbance in the film shows the maximum value) is also measured Color ratio).

[Synthesis of polymerizable liquid crystal compound]

＜Liquid crystal compound (I-1)＞ The liquid crystal compound (I-1) was synthesized by a method based on 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)

[化29]

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

[化30]

Synthesis of (I-2-a): Add ethyl propiolate (9.7 g, 99 mmol) and copper(I) (7.5 g) to the N,N-dimethylformamide solution (150 mL) of p-iodophenol (11.0 g, 50 mmol) , 94 mmol), stirred at 110°C for 9 hours, and naturally cooled to room temperature. After the precipitation was separated by filtration, ethyl acetate was added, washed with water, and then washed with saturated brine. It was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 7.3 g of brown crystals (I-2-a).

Synthesis of (I-2-b): Combine (I-2-a) (4.20 g, 22.1 mmol), 11-bromo-1-undecol (5.55 g, 22.1 mmol), potassium carbonate (6.10 g, 44.2 mmol), N,N-dimethyl Formamide (30 mL) was mixed and stirred at 80°C for 4 hours. After the precipitate was separated by filtration, diethyl ether was added, washed with water, and then washed with saturated brine. It was purified 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): (I-2-b) (3.6 g, 10 mmol), potassium hydroxide (1.7 g, 30 mmol), and water (20 mL) were mixed, and stirred at 100°C for 2 hours. After adding water (20 mL) and making it acidic with concentrated hydrochloric acid, the precipitated precipitate was separated by filtration. The obtained precipitate was suspended and washed with acetonitrile to obtain 3.2 g of a milky white solid (I-2-c).

Synthesis of (I-2-d): (I-2-c) (2.33 g, 7.0 mmol), tetrahydrofuran (20 mL) were mixed, and then N,N-dimethylaniline (1.02 g, 8.4 mmol), 2,5-di-tert-butyl were added Base phenol (54 mg). After cooling in an ice bath, acrylic chloride (0.76 g, 8.4 mmol) was slowly added. After stirring for 6 hours in an ice bath, add dichloromethane, and wash with 1 mol/L hydrochloric acid, saturated sodium bicarbonate water, and saturated brine in this order. It was purified by silica gel column chromatography (chloroform/methanol) to obtain 2.0 g of a white solid (I-2-d).

Synthesis of (I-2-e): It was synthesized by the synthesis method described in JP 2014-262884 A (I-2-e).

Synthesis of (I-2-f): Add (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). After cooling in an ice bath, add 1-ethyl-3-(3-dimethylaminopropyl) Yl)carbodiimide hydrochloride (1.09 g, 5.69 mmol). After standing overnight, it was washed with a saturated aqueous solution of ammonium chloride, and then washed with saturated brine. It was purified 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): Combine (I-2-f) (2.6 g, 4.62 mmol), pyridinium p-toluenesulfonate (0.23 g, 0.92 mmol), 2,5-di-tertiary butylphenol (44 mg), ethanol (20 mL ) Was mixed and stirred at 50°C for 2 hours. The reaction solution was released into water, and the deposited precipitate was separated by filtration and dried to obtain 2.0 g of a white solid (I-2-g).

Synthesis of (I-2-h): According to the synthesis method described below, compound (I-2-h) was synthesized.

[化31]

It was synthesized by the method (I-2-i) 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), ethanol (430 mL) were mixed, and the mixture was heated at 78°C. Stir for 2 hours. The solvent was distilled off, dissolved in ethyl acetate (150 mL), added hexane (750 mL), and cooled. The deposited precipitate was separated by filtration, washed with hexane, and dried to obtain 29.2 g of a white solid (I-2-j). (I-2-j) (37.2 g, 118.3 mmol), N,N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-tertiary butylphenol (0.24 g), tetrahydrofuran (380 mL) to mix. After cooling in an ice bath, acrylic chloride (16.1 g, 177.5 mmol) was slowly added. After the dropwise addition, after stirring for 2 hours at 50°C, the solvent was distilled off until the liquid volume became 190 mL, and released into 1 mol/L hydrochloric acid under ice cooling. The deposited precipitate was separated by filtration, and washed with water and hexane. It was purified by silica gel column chromatography (hexane/ethyl acetate) to obtain 39.4 g of a white solid (I-2-h).

(I-2) Synthesis: The (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, cooled in an ice bath, and then 1-ethyl-3-(3-dimethylaminopropyl) was added Yl)carbodiimide hydrochloride (230 mg, 1.19 mmol). After stirring for 4 hours in an ice bath, it was washed with a saturated aqueous solution of ammonium chloride, and then washed with saturated brine. It was purified 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) δ 1.20-1.70 (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 obtained by differential scanning calorimetry. In addition, in the differential scanning calorimetry, a product obtained by adding 0.2 parts by weight of 4-methoxyphenol as a polymerization inhibitor to 100 parts by weight of the liquid crystal compound was used. The results are shown in Table 1. In addition, this temperature is the isotropic phase appearance temperature, which is confirmed by polarizing microscope observation and X-ray structure analysis.

[Table 1] Liquid crystal compound 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)＞ According to the synthesis method described below, the liquid crystal compound (I-3) was synthesized.

[化32]

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

Synthesis of (I-3-b): The 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), two Methyl chloride (80 mL) was mixed, and after cooling in an ice bath, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) (3.39 g, 17.7) was added. mmol), stirring for 5 minutes. After that, it was stirred at room temperature for 2 hours, washed with a saturated aqueous solution of ammonium chloride, and then washed with saturated brine. 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 it is completely dissolved, mix dichlorobis(triphenylphosphine)palladium(II) (58 mg, 0.08 mmol) , Copper (I) iodide (48 mg, 0.25 mmol), add trimethylsilyl acetylene (0.98 g, 9.99 mmol). After stirring at room temperature for 30 minutes, it was extracted with water-ethyl acetate, and washed with saturated brine. The solution was concentrated and purified 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). After cooling in an ice bath, add tetra-n-butylammonium fluoride (TBAF) tetrahydrofuran solution (1 mol/L, 9 mL). After stirring for 20 minutes, it was extracted with water-chloroform, and washed with saturated brine. The solution was concentrated and purified 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): Combine (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), diisopropylamine (120 mL) was mixed, and after cooling in an ice bath, a solution of (I-3-d) (2.96 g, 5.93 mmol) in diisopropylamine (40 mL) was added. After stirring for 1 hour at room temperature, 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): The (I-3-e) obtained by the above operation and tetrahydrofuran (60 mL) were mixed and completely dissolved at 50°C, and ethanol (60 mL) was added. Pyridium p-toluenesulfonate (PPTS) (0.54 g, 2.13 mmol) was added to the slurry solution, heated at 60°C for 2 hours, and then left overnight. After heating to 60°C again the next day to completely dissolve, the reaction solution was added 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).

(I-3) Synthesis: (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), dichloromethane ( 100 mL) was mixed, and after cooling with an ice bath, 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 added, and the mixture was stirred for 5 hours. . The reaction liquid was washed with a saturated aqueous solution of ammonium chloride, and then washed with saturated brine, 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 liquid crystallinity of the compound (I-3) was confirmed by adding 0.2 parts by weight of 4-methoxyphenol as a polymerization inhibitor with respect to 100 parts by weight of the liquid crystal compound, attached by a high-temperature stage With a polarizing microscope, birefringence was observed at 70°C.

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

[化33]

Synthesis of (II-1-a): In a reactor cooled in an ice bath, tetrahydrofuran (100 mL), sodium hydride (purity 60%, 6.7 g, 168.0 mmol) were added, and (4-nitrobenzyl) diethyl phosphonate ( A mixture of 18.0 g, 65.9 mmol), 4-butylbenzaldehyde (9.1 g, 56.1 mmol), and tetrahydrofuran (50 mL) was washed with tetrahydrofuran (30 mL) and stirred at 50°C for 0.5 hours. The reaction liquid was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude was heated and dissolved in ethyl acetate (20 mL), hexane (50 mL) was added and cooled, the precipitated precipitate was separated by filtration, washed with hexane, and dried under reduced pressure to obtain (II-1-a) 15.0 g.

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

(II-1) Synthesis: Mix (II-1-b) (2.51 g, 10.0 mmol), N-methylpyrrolidone (40 mL), concentrated hydrochloric acid (2.2 mL), and water (20 mL). After cooling to 3°C, add Sodium nitrite (789 mg, 11.4 mmol) was stirred 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 an aqueous sodium hydroxide solution to maintain the pH at 3 to 5, while dropping the liquid containing the above-mentioned diazonium salt, the mixture was stirred at 15°C for 3 hours. The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude 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 this compound in a 10 ppm chloroform solution is 459 nm, and the gram absorption coefficient is 107.6 Lg ^-1 cm ^-1 . In addition, 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 to cyclopentanone was determined. Add 3 mg of dye (II-1) to 97 mg of cyclopentanone, and stir at 80°C for 5 minutes. After that, the mixture was allowed to stand at room temperature for 1 hour, and the obtained mixed solution was filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm) to obtain the pigment (II-1 ) The saturated solution of cyclopentanone. The solution was diluted with 800 mg of tetrahydrofuran, and the concentration was determined by HPLC (L-2300 series manufactured by Hitachi High-Technologies Corporation). Prepare a solution obtained by dissolving 0.1% by weight of pigment (II-1) in tetrahydrofuran, and prepare a calibration curve at an absorption wavelength of 254 nm. Using this calibration curve, the concentration of cyclopentanone saturated solution was determined, and the result was 1.0%.

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

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(II-2) Synthesis: Cool 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) to 3°C, and add nitrous acid Sodium (380 mg, 5.5 mmol), stirred at 15°C for 3.5 hours. Mix N,N-diethylaniline (751 mg, 5.0 mmol), methanol (40 mL), and water (20 mL), and adjust the pH to 3.5 with concentrated hydrochloric acid. After adding the aqueous sodium hydroxide solution to maintain the pH at 3-6, the liquid containing the above diazonium salt was added dropwise, followed by stirring at 15°C for 1 hour. The obtained precipitate was filtered, washed with water, and dried under reduced pressure. The obtained crude 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 this compound in a 10 ppm chloroform solution is 458 nm, and the gram absorption coefficient is 105.7 Lg ^-1 cm ^-1 . In addition, 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 the compound for cyclopentanone was determined by the same method as the dye (II-1) (detection absorption wavelength: 254 nm), and the result was 3.0% or more.

＜Pigment (II-3)＞ The synthetic dye (II-3) was synthesized according to the synthesis method described below.

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Synthesis of (II-3-a): In a reactor cooled in an ice bath, tetrahydrofuran (200 mL), sodium hydride (purity 60%, 10.1 g, 252.6 mmol) were added, and diethyl (4-nitrobenzyl)phosphonate ( A mixture of 23.0 g, 84.2 mmol), 4-heptyloxybenzaldehyde (18.6 g, 84.2 mmol), and tetrahydrofuran (200 mL) was washed with tetrahydrofuran (30 mL) and stirred at 50°C for 2 hours. The reaction liquid was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. After heating and dissolving the obtained crude in ethyl acetate (35 mL), adding hexane (80 mL) and cooling, the deposited precipitate was separated by filtration, washed with hexane, and dried under reduced pressure to obtain (II-3-a) 23.1 g.

Synthesis of (II-3-b): Mix (II-3-a) (23.1 g, 68.1 mmol), tetrahydrofuran (200 mL), iron powder (19.0 g, 340.5 mmol), and add dropwise ammonium chloride (18.2 g) dissolved in water (50 mL) , 340.5 mmol) and stirred at 50°C for 5 hours. Filter with diatomaceous earth, extract with ethyl acetate, wash with water and saturated brine, and distill off the solvent. After purifying the obtained crude body by silica gel column chromatography (hexane/ethyl acetate), it was suspended in hexane, the precipitate was separated by filtration, and washed with hexane. It was dried under reduced pressure to obtain 10.7 g of (II-3-b).

(II-3) Synthesis: Cool 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) to 3°C, and add nitrous acid Sodium (380 mg, 5.5 mmol), stir at 15°C for 5 hours. Mix N,N-diethylaniline (751 mg, 5.0 mmol), methanol (40 mL), and water (20 mL), and adjust the pH to 3.5 with concentrated hydrochloric acid. After adding the aqueous sodium hydroxide solution to maintain the pH at 7 and dropping the liquid containing the diazonium salt, 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 was purified by silica gel column chromatography (hexane/dichloromethane) to obtain 152 mg of orange solid (II-2).

The maximum absorption wavelength (λ _max ) of this compound in a 10 ppm chloroform solution is 459 nm, and the gram absorption coefficient is 96.4 Lg ^-1 cm ^-1 . In addition, 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 the compound for cyclopentanone was determined by the same method as the pigment (II-1) (detection absorption wavelength: 254 nm), and the result was 3.0% or more.

＜Pigment (II-4)＞ The dye (II-4) was synthesized according to the synthesis method described below.

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(II-4) Synthesis: 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, and add until dissolved Mix sodium nitrite (0.3 g, 4.4 mmol) in water (1.3 mL) and stir for 1 hour. After coupling the reaction solution with 1-phenylpiperidine (0.6 g, 4.0 mnmol) dissolved in methanol (25 mL) and water (6.5 mL) at pH=7, the precipitate was separated by filtration and washed with water. Dry under reduced pressure. The obtained crude 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 this compound in a 10 ppm chloroform solution is 431 nm, and the gram absorption coefficient is 94.3 Lg ^-1 cm ^-1 . In addition, 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) The solubility of the compound for cyclopentanone was determined by the same method as the pigment (II-1) (detection absorption wavelength: 254 nm), The result was 2.4%.

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

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The maximum absorption wavelength (λ _max ) of this compound in a 10 ppm chloroform solution is 459 nm, and the gram absorption coefficient is 52.6 Lg ^-1 cm ^-1 . In addition, 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) Measured by the same method as dye (II-1) (detection absorption wavelength: 254 nm). For the solubility of cyclopentanone, the result was 2.2%.

The chemical structure of the liquid crystal compound and dye synthesized in the above is shown below. Furthermore, in the formula, C ₁₁ H ₂₂ means that 11 methylene chains are bonded in a straight chain.

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

Example 1 20.00 parts of the liquid crystal compound (I-1) and 0.40 parts of the dye (II-1) were added to 399.6 parts of chloroform, stirred and dissolved, and then the solvent was removed, thereby obtaining an anisotropic dye film forming composition 1. The liquid crystallinity of the composition 1 for forming an anisotropic dye film was confirmed by observing birefringence at 40°C using a polarizing microscope attached to a high-temperature stage. In order to use the obtained anisotropic pigment film forming composition 1 to determine the two-color ratio by the above-mentioned method, and to make an anisotropic pigment film 1 using sandwich cells with a cell gap of 8.0 μm, determine the second of the anisotropic pigment film 1 Color ratio. The results are shown in Table 2.

Example 2 Except that 0.30 part of pigment (II-2) was used instead of 0.40 part of pigment (II-1), the anisotropic pigmented film forming composition 2 and the anisotropic pigmented film 2 were obtained in the same manner as in Example 1 . The liquid crystallinity of the composition 2 for forming an anisotropic dye film was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a high-temperature stage. Regarding the anisotropic pigmented film 2, the two-color ratio of the anisotropic pigmented film 2 is determined. The results are shown in Table 2.

Example 3 Except that 0.30 part of dye (II-3) was used instead of 0.40 part of dye (II-1), the anisotropic pigmented film forming composition 3 and the anisotropic pigmented film 3 were obtained in the same manner as in Example 1 . The liquid crystallinity of the composition 3 for forming an anisotropic dye film was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a high temperature stage. Regarding the anisotropic pigmented film 3, the two-color ratio of the anisotropic pigmented film 3 is determined. The results are shown in Table 2.

Example 4 20.00 parts of the liquid crystal compound (I-2) was used instead of 20.00 parts of the liquid crystal compound (I-1), and 0.28 parts of the dye (II-1) was used instead of 0.40 parts of the dye (II-1). In the same manner, a composition 4 for forming an anisotropic dye film and an anisotropic dye film 4 were obtained. The liquid crystallinity of the composition 4 for forming an anisotropic dye film was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a high-temperature stage. Regarding the anisotropic pigmented film 4, the two-color ratio of the anisotropic pigmented film 4 is determined. The results are shown in Table 2.

Example 5 Use 20.00 parts of liquid crystal compound (I-2) instead of 20.00 parts of liquid crystal compound (I-1), 0.32 parts of pigment (II-4) instead of 0.40 parts of pigment (II-1), and use a sandwich cell with a cell gap of 10.0 μm instead of the cell Except for the sandwich unit with a gap of 8.0 μm, the anisotropic dye film forming composition 5 and the anisotropic dye film 5 were obtained in the same manner as in Example 1. The composition 5 for forming an anisotropic dye film showed liquid crystallinity, and it was confirmed by observing birefringence at 40 degreeC using the polarizing microscope attached to a high temperature stage. Regarding the anisotropic pigmented film 5, the two-color ratio of the anisotropic pigmented film 5 is determined. The results are shown in Table 2.

Comparative example 1 Except that 0.2 part of pigment (II-5) was used instead of 0.40 part of pigment (II-1), the anisotropic pigmented film forming composition 7 and the anisotropic pigmented film 7 were obtained in the same manner as in Example 1 . The liquid crystallinity of the composition 7 for forming an anisotropic dye film was confirmed by observing birefringence at 60° C. using a polarizing microscope attached to a high temperature stage. Regarding the anisotropic pigment film 7, the two-color ratio of the anisotropic pigment film 7 is determined. The results are shown in Table 2.

[Table 2] Example Comparative example 1 2 3 4 5 1 Liquid crystal compound 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 two-color ratio (℃) 40.0 40.0 40.0 40.0 40.0 60.0 Display wavelength of 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 The wavelength at which the absorbance in the film shows the maximum value (nm) 470 480 465 495 450 465 The two-color ratio at the wavelength where the absorbance in the film shows the maximum value 27.4 16.0 22.0 34.2 24.3 3.2

Example 6 Add 34.28 parts of liquid crystal compound (I-2), 0.34 parts of azo pigment of formula (III-1) (manufactured by Hayashibara Co., Ltd.), and azo pigment of formula (III-2) (Showa Chemical Co., Ltd.) to 399.6 parts of chloroform Co., Ltd.) 0.84 parts, 0.28 parts of azo pigment of formula (II-1), 0.21 part of azo pigment of color (II-4), after stirring and dissolving, remove the solvent to obtain anisotropic pigment Composition for film formation 8. The composition 8 for forming an anisotropic dye film showed liquid crystallinity, and it was confirmed by observing birefringence at 40 degreeC using the polarizing microscope attached to a high temperature stage. In order to use the obtained anisotropic dye film forming composition 8 to determine the two-color ratio by the above-mentioned method, an anisotropic dye film 8 is produced, and the two-color ratio of the anisotropic dye film 8 is determined. The maximum dichroic ratio of the anisotropic pigment film 8 is 48.7 at 40°C and a wavelength of 675 nm. The absorbance of the azo dye of formula (II-1) shows a maximum value in the liquid crystal compound (I-2) at a wavelength of 495 nm, and the dichroic ratio is 31.7.

Example 7 To 717.9 parts of cyclopentanone, 243.6 parts of liquid crystal compound (I-2), 4.35 parts of azo dye of formula (II-1), 5.58 parts of IRGACURE (registered trademark) 369 (product of BASF company) were added, 3.62 parts of BYK-361N (manufactured by BYK-Chemie), heated and stirred at 80°C, filtered with a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm) to obtain a different direction Composition for sex pigment film 9. The composition 9 for anisotropic pigment films was formed by a spin coating method on a glass with an alignment film (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems, formed by a rubbing method) with polyimide The substrate was heated and dried at 120° C. for 2 minutes, then cooled to a liquid crystal phase, and polymerized at an exposure amount of 500 mj/cm ² (365 nm reference) to obtain an anisotropic dye film 9. It can be confirmed that if the obtained anisotropic pigment film 9 is placed on a commercially available polarizing plate and rotated, light and darkness are generated, and it shows good performance as a polarizing film.

Example 8 Add 19.65 parts of liquid crystal compound (I-2), 0.06 parts of azo pigment of formula (III-1) (manufactured by Hayashibara Co., Ltd.), and azo pigment of formula (III-2) (Showa Chemical Co., Ltd.) to 2615.7 parts of chloroform Co., Ltd.) 0.15 parts and dye (II-2) 0.05 parts are stirred and dissolved together, and then the solvent is removed, thereby obtaining an anisotropic dye film forming composition 10. The composition 10 for forming an anisotropic dye film showed liquid crystallinity, and it was confirmed by observing birefringence at 40 degreeC using the polarizing microscope attached to a high temperature stage. In order to use the obtained anisotropic dye film forming composition 10, the two-color ratio is determined by the above-mentioned method to produce an anisotropic dye film 10, and the two-color ratio of the anisotropic dye film 10 is determined. The maximum dichroic ratio of the anisotropic pigment film 10 is 31.0 at 40°C and a wavelength of 595 nm. The absorbance of the pigment (II-2) shows a maximum value in the liquid crystal compound (I-2). The dichroic ratio at a wavelength of 485 nm is 20.4.

Example 9 To 79.67 parts of chloroform, 20.00 parts of liquid crystal compound (I-2), 0.18 parts of azo dye (manufactured by Showa Chemical Co., Ltd.) of formula (III-2), and 0.14 parts of dye (II-1) were added and stirred to After the compatibility, the solvent is removed, thereby obtaining the composition 11 for forming an anisotropic dye film. The liquid crystal display of the composition 11 for forming an anisotropic dye film was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a high-temperature stage. In order to use the obtained anisotropic dye film formation composition 11, the two-color ratio was determined by the above-mentioned method, and an anisotropic dye film 11 was produced, and the two-color 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 absorbance of the pigment (II-1) showed a maximum value in the liquid crystal compound (I-2) and the dichroic ratio at a wavelength of 470 nm was 28.7.

Example 10 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 anisotropic dye film forming composition 12 and the anisotropic dye were obtained in the same manner as in Example 9膜12。 Film 12. The liquid crystallinity of the composition 12 for forming an anisotropic dye film was confirmed by observing birefringence at 70° C. using a polarizing microscope attached to a high-temperature stage. In order to use the obtained anisotropic dye film forming composition 12, the two-color ratio is determined by the above-mentioned method, and the anisotropic dye film 12 is produced, and the two-color ratio of the anisotropic dye film 12 is determined. The maximum dichroic ratio of the anisotropic pigment film 12 is 28.8 at 70°C and a wavelength of 515 nm. The absorbance of the pigment (II-1) shows a maximum value in the liquid crystal compound (I-3) and the dichroic ratio at a wavelength of 470 nm is 25.5.

Comparative example 2 Except having used 0.2 part of dye (II-6) instead of 0.40 part of dye (II-1), in the same manner as in Example 1, an anisotropic dye film forming composition 13 was obtained. The solubility of the pigment (II-6) for cyclopentanone was measured by the same method as the pigment (II-1) (detection absorption wavelength: 254 nm), and the result was 0.0%. Regarding the composition 13 for forming an anisotropic dye film, the precipitate was observed at 60°C with a polarizing microscope attached to the high-temperature stage. The reason for this is considered to be that the solubility of the dye (II-6) is low, and it is difficult to show a sufficient two-color ratio even when the anisotropic dye film is formed from the anisotropic dye film formation composition 13.

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Comparative example 3 To 79.66 parts of chloroform, 20.00 parts of liquid crystal compound (I-2), 0.18 parts of azo dye (manufactured by Showa Chemical Co., Ltd.) of formula (III-2), and 0.15 parts of dye (II-5) were added, and stirred to After the compatibility, the solvent is removed, thereby obtaining the composition 14 for forming an anisotropic dye film. The liquid crystallinity of the composition 14 for forming an anisotropic dye film was confirmed by observing birefringence at 40° C. using a polarizing microscope attached to a high temperature stage. In order to use the obtained anisotropic dye film forming composition 14 to determine the two-color ratio by the above-mentioned method, an anisotropic dye film 14 is produced, and the two-color ratio of the anisotropic dye film 14 is determined. The maximum dichroic ratio of the anisotropic pigment film 14 is 6.6 at 40°C and a wavelength of 485 nm. The absorbance of the pigment (II-5) shows a maximum value in the liquid crystal compound (I-2) and the dichroic ratio at a wavelength of 465 nm is 6.6.

Comparative example 4 Except that 0.17 part of pigment (II-5) was used instead of 0.17 part of pigment (II-1), the anisotropic pigmented film forming composition 15 and the anisotropic pigmented film 15 were obtained in the same manner as in Example 10 . The liquid crystallinity of the composition 15 for forming an anisotropic dye film was confirmed by observing birefringence at 70° C. using a polarizing microscope attached to a high-temperature stage. In order to use the obtained anisotropic dye film forming composition 15 to determine the two-color ratio by the above-mentioned method, an anisotropic dye film 15 is produced, and the two-color ratio of the anisotropic dye film 15 is determined. The maximum dichroic ratio of the anisotropic pigment film 15 is 4.3 at 70°C and a wavelength of 485 nm. The absorbance of the pigment (II-5) shows a maximum value in the liquid crystal compound (I-3). The dichroic ratio at a wavelength of 465 nm is 3.5. Table 3 shows the results of Examples 6, 8 to 10 and Comparative Examples 3 to 4.

[table 3] Example Comparative example 6 8 9 10 3 4 Liquid crystal compound 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 two-color ratio (℃) 40.0 40.0 40.0 70.0 40.0 70.0 Display wavelength of 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 Determination of the two-color ratio at the wavelength 31.7 20.4 28.7 25.5 6.6 3.5 [Industrial availability]

The composition for forming an anisotropic pigment film of the present invention can realize excellent optical properties, especially a sufficient two-color ratio. Especially in the wavelength region of 430 nm ~ 550 nm, a sufficient two-color ratio can be achieved. Since the anisotropic dye film of the present invention is formed by using the composition for forming an anisotropic dye film of the present invention, it can achieve excellent optical properties, especially a sufficient two-color ratio. Since the optical element of the present invention includes the anisotropic dye film of the present invention, it can achieve excellent optical performance, especially a sufficient two-color ratio.

Claims (11)

A composition for forming an anisotropic dye film, comprising a dye and a polymerizable liquid crystal compound, the dye including a compound represented by formula (1): A ¹ -CH=CH-A ² -(N=NA ³ ) _n- X (1) (In the formula, A ¹ represents a monovalent group of an aromatic hydrocarbon ring which may have a substituent (except sulfo group) or a monovalent group of an aromatic heterocyclic ring which may have a substituent (except sulfo group) ; A ² and A ³ each independently represent a divalent group of an aromatic hydrocarbon ring that may have a substituent (except a sulfo group) or a divalent group of an aromatic heterocyclic ring that may have a substituent (except a sulfo group); X represents a monovalent organic group; n represents 1, 2 or 3). The composition for forming an anisotropic dye film according to claim 1, wherein A ³ is a phenylene group which may have a substituent (except a sulfo group). The composition for forming an anisotropic dye film according to claim 1 or 2, wherein A ² is a divalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group). The composition for forming an anisotropic dye film according to any one of claims 1 to 3, wherein A ¹ is a monovalent group of an aromatic hydrocarbon ring which may have a substituent (except a sulfo group). The composition for forming an anisotropic pigment film according to any one of claims 1 to 4, wherein X is -O-(R ^x ) or -N(-R ^x )-R ^y ; R ^x and R ^y are independent of each other Ground means an alkyl group with 1 to 15 carbon atoms or an aryl group with 5 to 14 atoms constituting the ring; R ^x and R ^y can be integrated to indicate a branch with 2 to 15 carbon atoms Alkylene; the above-mentioned alkyl group having 1 to 15 carbon atoms and the above-mentioned aryl group having 5 to 14 atoms constituting the ring may each have a substituent; the above-mentioned branched alkyl group having 2 to 15 carbon atoms One or more methylene groups contained in the alkylene group may be substituted with etheric oxygen atoms, thioetheric sulfur atoms, amine nitrogen atoms, carbonyl groups, ester bonds, amide bonds, -CHF-,- The structure of CF ₂ -, -CHCl-, -CCl ₂ -; the above-mentioned amine nitrogen atom is -NH- or -N(R ^z )-; R ^z represents a linear or branched chain with 1 to 6 carbon atoms alkyl. The composition for forming an anisotropic dye film according to any one of claims 1 to 5, wherein the number (r _n1 ) of the ring structure possessed by the polymerizable liquid crystal compound and the ring structure of the compound represented by the formula (1) number of structures (r _n2) ratio (r _n1 / r _n2) of 0.7 to 1.5. The composition for forming an anisotropic dye film according to 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 dye film according to any one of claims 1 to 7, which further contains a polymerization initiator. The composition for forming an anisotropic dye film according to any one of claims 1 to 8, wherein the above-mentioned dye further comprises one or more kinds of wavelengths showing a maximum value in the absorption curve in the wavelength region of 380 nm to 780 nm, which is greater than the above-mentioned The compound represented by the formula (1) shows the maximum wavelength in the absorption curve of the wavelength region from 380 nm to 780 nm. An anisotropic pigmented film formed using the composition for forming an anisotropic pigmented film according to any one of claims 1 to 9. An optical element comprising the anisotropic pigment film as claimed in claim 10.