JP7363887B2 - Composition for forming an anisotropic pigment film, anisotropic pigment film, and optical element - Google Patents

Description

The present invention relates to an anisotropic dye film formed by applying a liquid crystal composition, particularly a polarizing film included in a display element such as a light control element, a liquid crystal element (LCD), and an organic electroluminescent element (OLED). The present invention relates to a composition for forming an anisotropic dye film, an anisotropic dye film, and an optical element that exhibit high dichroism and are useful for, etc.
This application claims priority based on Japanese Patent Application No. 2019-037800 filed in Japan on March 1, 2019, the contents of which are incorporated herein.

In LCDs, linearly polarizing films and circularly polarizing films are used to control optical rotation and birefringence in display. Circularly polarizing films are also used in OLEDs to prevent reflection of external light in bright places.

Conventionally, such polarizing films include, for example, polarizing films made by dyeing polyvinyl alcohol (PVA) with low concentration of iodine (iodine-PVA polarizing films) (Patent Document 1).
It is also known that an anisotropic dye film formed by applying a liquid crystal composition containing a dye functions as a polarizing film (Patent Document 2). However, there is no disclosure of a polarizing film containing a dichroic dye having 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 azo dye as a dichroic dye is also known (Non-Patent Document 1). However, in combination with a polymeric liquid crystal, a sufficient dichroic ratio as a polarizing film cannot be obtained.

Japanese Patent Publication No. 1-105204 Japan Special Table Publication No. 2007-510946

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

However, depending on the usage environment, the iodine-PVA polarizing plate with such a low concentration may suffer from problems such as the iodine sublimating or deteriorating, causing the color to change, and the stretching of PVA to be alleviated. There is a problem that warping occurs due to
In addition, a polarizing film formed by coating a liquid crystal composition containing a dye has a problem in that high light absorption selective performance cannot be obtained.

Under such circumstances, there is a demand for a polarizing film that has high light absorption selection performance 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 necessary to It is conceivable to increase the ratio of the minor axes, that is, to extend the π-conjugated system and increase the molecular long-minor axis ratio.

However, if the π-conjugated system of the dichroic dye molecule is extended and the molecule's long-minor axis ratio is increased, the dichroism becomes higher, but the dye becomes a dye that has absorption in the long wavelength visible region. On the other hand, in order to have absorption in the short wavelength visible light region, it is necessary to shorten the π-conjugated system, and yellow dichroic dyes that have absorption in the short wavelength visible light region have a small molecular long-minor axis ratio and are dichroic. tended to be less sensitive. Therefore, it has been difficult to obtain a polarizing film that has high light absorption selection performance particularly in the short wavelength visible light region of 380 nm to 520 nm. On the other hand, in polarizing films that cover the entire visible light range, due to the low dichroic ratio in the short wavelength visible light range, light in the blue range is not sufficiently blocked and passes through, which is known as ``blue bleeding''. It was getting worse.

Furthermore, in polarizing films formed by coating liquid crystal compositions containing dyes, it is known that the dichroic ratio differs depending on the combination of liquid crystal molecules and dichroic dyes. It is important to combine dichroic dyes.
Under these circumstances, it is desired to develop a dichroic dye molecule that allows an anisotropic dye film to exhibit high dichroism and a composition for forming an anisotropic dye film containing the dichroic dye molecule.

An object of the present invention is to provide a composition for forming an anisotropic dye film that can realize excellent optical performance, particularly a sufficient dichroic ratio.
Another object of the present invention is to provide an anisotropic dye film that can achieve excellent optical performance, particularly a sufficient dichroic ratio.
Another object of the present invention is to provide an optical element including an anisotropic dye film capable of realizing excellent optical performance, particularly a sufficient dichroic ratio.

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

[1]
Contains a dye and a polymerizable liquid crystal compound,
A composition for forming an anisotropic dye film, wherein the dye contains a compound represented by formula (1).
A ¹ -CH=CH-A ² -(N=NA ³ ) _n -X...(1)
(In the formula,
A ¹ may have a monovalent group of an aromatic hydrocarbon ring which may have a substituent (however, excluding a sulfo group) or a substituent (however, excluding a sulfo group) represents a monovalent group of an aromatic heterocycle;
A ² and A ³ are each independently a divalent group or substituent of an aromatic hydrocarbon ring that may have a substituent (excluding a sulfo group). represents a divalent group of an aromatic heterocycle which may have;
X represents a monovalent organic group;
n represents 1, 2, or 3. )
[2]
The composition for forming an anisotropic dye film according to [1], wherein A ³ is a phenylene group which may have a substituent (excluding a sulfo group).
[3]
Anisotropic dye film formation according to [1] or [2], wherein A ² is a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) Composition for use.
[4]
The anisotropy according to any one of [1] to [3], wherein A ¹ is a monovalent group of an aromatic hydrocarbon ring that may have a substituent (excluding a sulfo group). A composition for forming a pigment film.
[5]
X is -O-(R ^x ) or -N(-R ^x )-R ^y ; R ^x and R ^y are each independently an optionally branched alkyl group having 1 to 15 carbon atoms; or represents an aryl group having 5 to 14 ring atoms; R ^x and R ^y together represent an alkylene group having 2 to 15 carbon atoms, which may have a branch; The alkyl group having 1 to 15 carbon atoms which may have a branch and the aryl group having 5 to 14 atoms constituting the ring may each have a substituent; One or more methylene groups contained in the alkylene group having 2 to 15 carbon atoms which may have an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide The structure may be replaced by a bond, -CHF-, _-CF2- , -CHCl-, _-CCl2- ; the aminic nitrogen atom is -NH- or -N( ^Rz )-; The composition for forming an anisotropic dye film according to any one of [1] to [4], wherein R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.
[6]
The ratio (r _n1 /r _n2 ) of the number of ring structures (r _n1 ) possessed by the polymerizable liquid crystal compound to the number (r _n2 ) possessed by the compound represented by the formula (1) is 0. 7 to 1.5, the composition for forming an anisotropic dye film according to any one of [1] to [5].
[7]
The composition for forming an anisotropic dye film according to 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 according to any one of [1] to [7], further comprising a polymerization initiator.
[9]
The dye further has a wavelength showing a maximum value in an absorption curve in a wavelength range of 380 nm to 780 nm, which is a wavelength that shows a maximum value in an absorption curve in a wavelength range of 380 nm to 780 nm of the compound represented by formula (1) above. The composition for forming an anisotropic dye film according to any one of [1] to [8], which contains one or more long compounds.
[10]
An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of [1] to [9].
[11]
An optical element comprising the anisotropic dye film according to [10].

The composition for forming an anisotropic dye film of the present invention can realize excellent optical performance, particularly a sufficient dichroic ratio.
Since the anisotropic dye film of the present invention is formed using the composition for forming an anisotropic dye film of the present invention, it is possible to achieve excellent optical performance, particularly a sufficient dichroic ratio.
Since the optical element of the present invention includes the anisotropic dye film of the present invention, it can achieve excellent optical performance, particularly a sufficient dichroic ratio.

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

An anisotropic dye film as used in the present invention refers to electromagnetic properties in two arbitrary directions selected from a total of three directions in a three-dimensional coordinate system, including the thickness direction of the anisotropic dye film and two arbitrary orthogonal in-plane directions. It is a pigment film with anisotropy. 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.
The composition for forming an anisotropic pigment film of the present invention may be in a solution, liquid crystal, or dispersed state as long as it does not cause phase separation. The forming composition is preferably a solution from the viewpoint of ease of application to the base material. 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 liquid crystal phase state at any temperature from the viewpoint of alignment on a substrate as described later.
In the present invention, the liquid crystal phase state is specifically described in "Basics and Applications of Liquid Crystals" (Shoichi Matsumoto, Ichiyoshi Tsunoda; 1991), pages 1 to 16. As such, it is a liquid crystal state that exhibits both or intermediate properties of liquid and crystal, and is a nematic phase, smectic phase, cholesteric phase, or discotic phase.

(dye)
In the present invention, a dye is a substance or compound that absorbs at least a portion of wavelengths in the visible light region (380 nm to 780 nm).
Examples of dyes that can be used in the present invention include dichroic dyes. Note that a dichroic dye refers to a dye that has a property that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. Further, the dye may be a dye having liquid crystallinity or may not have liquid crystallinity. Note that "having liquid crystallinity" means exhibiting a liquid crystal phase at an arbitrary temperature.

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

A ¹ -CH=CH-A ² -(N=NA ³ ) _n -X...(1)

During the ceremony,
A ¹ may have a monovalent group of an aromatic hydrocarbon ring which may have a substituent (however, excluding a sulfo group) or a substituent (however, excluding a sulfo group) represents a monovalent group of an aromatic heterocycle;
A ² and A ³ each independently represent a divalent group or substituent of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group). represents a divalent group of an aromatic heterocycle which may have;
X represents a monovalent organic group;
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 major axis ratio sufficiently large to provide a good dichroic ratio. At the same time, since the elongation of the π-conjugated system is suppressed, absorption occurs in the short wavelength visible region. In addition, the structure represented by formula (1) has good combination with liquid crystal molecules and good intermolecular interaction between liquid crystal molecules and dye molecules, so that it can be used without disturbing the molecular orientation of liquid crystal molecules. Can exhibit higher dichroic ratio. Based on these effects, the dye having the structure represented by formula (1) can achieve both a high dichroic ratio and absorption in the short wavelength visible region, which have been problems in the past.

A ¹ is a monovalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or a monovalent group of an aromatic heterocycle which may have a substituent. represent.

The aromatic hydrocarbon ring in A ¹ is a monocyclic or condensed aromatic hydrocarbon ring. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 or more. Further, it is preferably 20 or less, more preferably 16 or less, and even more preferably 10 or less. Within these ranges, the combination with liquid crystal tends to be favorable. For example, the aromatic hydrocarbon ring preferably has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and even more preferably 6 to 10 carbon atoms.
The number of rings in the case of condensed rings is also not particularly limited, but the number is preferably 2 or more, and 5 or less, since the combination with liquid crystal tends to be good.
Examples of aromatic hydrocarbon rings include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. .
Among these, as the monovalent group of the aromatic hydrocarbon ring of ^A1 , the monovalent group of the benzene ring (phenyl group) and the monovalent group of the naphthalene ring (naphthyl group) are preferable, and the phenyl group improves molecular linearity. It is more preferable from the viewpoint of increasing the height.

The aromatic heterocycle in A ¹ is a monocyclic or condensed aromatic heterocycle. The number of carbon atoms in the aromatic heterocycle is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. Further, it is preferably 20 or less, more preferably 13 or less, and even more preferably 9 or less. Within these ranges, the combination with liquid crystal tends to be favorable. For example, the aromatic heterocycle preferably has 2 to 20 carbon atoms, more preferably 3 to 13 carbon atoms, and even more preferably 4 to 9 carbon atoms.
The number of rings in the case of condensed rings is also not particularly limited, but the number is preferably 2 or more, and 5 or less, since the combination with liquid crystal tends to be good.

Examples of aromatic heterocycles include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroimidazole ring, pyrrolopyrazole ring, and pyrrolopyrrole. ring, thienopyrrole ring, thienothiophene ring, furopyrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzoxazole ring, benzisoxazole ring, benzothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Examples include a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a shinoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, and a quinazolinone ring.
Among these, the aromatic heterocycle of ^A1 is preferably a furan ring, a thiophene ring, a thienothiazole ring, a benzoxazole ring, a benzothiazole ring, or a benzimidazole ring, especially a thienothiazole ring, from the viewpoint of increasing molecular linearity. A thiazole ring, a benzoxazole ring, a benzothiazole ring, and a benzimidazole ring are preferred.

Permissible substituents for the monovalent group of the aromatic hydrocarbon ring or the monovalent group of the aromatic heterocycle in A ¹ , excluding the sulfo group, include -R ^A , -OH, -O-R ^A , -O -C(=O)-R ^A , -NH ₂ , -NH-R ^A , -N(-R ^B )-R ^A , -C(=O)-R ^A , -C(=O)-O- R ^A , -C(=O)-NH ₂ , -C(=O)-NH-R ^A , -C(=O)-N(-RB)-R ^A , -SH, -S-R ^A , Examples include trifluoromethyl group, sulfamoyl group, carboxy group, cyano group, nitro group, and 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 methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms include an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, and an ester bond. , an amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ - may be substituted with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group. You may do so.
Among these, -R ^A and -O-R ^A are preferable as substituents other than sulfo groups that are permissible for the monovalent group of the aromatic hydrocarbon ring or the monovalent group of the aromatic heterocycle in ^A1 . , for example, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy , 5,5-dimethyl-3-methylhexyloxy, 11-(acryloyloxy)undecyloxy, and the like.
The aminic nitrogen atom represents -NH-, -N(R ^z )-, and R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

A ¹ is preferably a monovalent group of an aromatic hydrocarbon ring from the viewpoint of expressing a high dichroic ratio, more preferably a phenyl group or a naphthyl group, and a phenyl group from the viewpoint of improving linearity. It is even more preferable. The substituent for A ¹ is preferably a substituent selected from the group consisting of -R ^A , -O-R ^A and -C(=O)-O-R ^A , and -R ^A and -O It is more preferable to have a substituent selected from the group consisting of ^-RA . Having the above substituents tends to provide good combination with liquid crystals.

A ² and A ³ are each independently a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group) or an aromatic group which may have a substituent; Represents a divalent heterocyclic group.

The aromatic hydrocarbon rings in A ² and A ³ are similar to the aromatic hydrocarbon rings in A ¹ .
The divalent group of the aromatic hydrocarbon ring of ^A2 is preferably a divalent group of a benzene ring (phenylene group) or a divalent group of a naphthalene ring (naphthylene group), such as a 1,4-phenylene group, a 1,4- Naphthylene group and 2,6-naphthylene group are more preferred, and 1,4-phenylene group is even more preferred.
The divalent group of the aromatic hydrocarbon ring of A ³ is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,4-phenylene group.
When A ² and/or A ³ are the above-mentioned groups, the effect of increasing the molecular long-short axis ratio is obtained, and the combination with liquid crystal tends to be good.

The aromatic heterocycle in A ² and A ³ is the same as the aromatic heterocycle in A ¹ .

Substituents other than sulfo groups that are permissible for the divalent group of the aromatic hydrocarbon ring or the divalent group of the aromatic heterocycle in A ² and A ³ include the monovalent group of the aromatic hydrocarbon ring in A ¹ Alternatively, it is the same as the substituents allowed for monovalent groups of aromatic heterocycles, excluding sulfo groups.

From the viewpoint of achieving a high dichroic ratio, ^A2 is preferably a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group); A phenylene group and a naphthylene group, which may have a substituent (excluding a sulfo group), are more preferable; a 1,4-phenylene group, which may have a substituent (excluding a sulfo group); A 4-naphthylene group is more preferable, and a 1,4-phenylene group having no substituent is even more preferable from the viewpoint of improving linearity.
From the viewpoint of developing a high dichroic ratio, A ³ is preferably a divalent group of an aromatic hydrocarbon ring which may have a substituent (excluding a sulfo group). Among these, a phenylene group or a naphthylene group, which may have a substituent (however, excluding a sulfo group), is more preferable, and a phenylene group or a naphthylene group, which may have a substituent (however, excluding a sulfo group), is more preferable. , 1,4-phenylene group, and 1,4-naphthylene group are more preferred. In particular, a 1,4-phenylene group having no substituents is particularly preferred from the viewpoint of improving linearity.

In A ¹ , A ² and A ³ above, substituents other than sulfo groups are allowed as substituents. When the substituent is a sulfo group, the compatibility with the liquid crystal and solvent decreases, resulting in a decrease in dichroic ratio and precipitation of the dye, which significantly impairs the performance as an anisotropic dye film. There is a fear.

X represents a monovalent organic group.
Monovalent organic groups in X include hydrogen atom, hydroxy group, amino group, cyano group, carbamoyl group, nitro group, halogen atom, -R ^x , -O-R ^x , -NH-R ^x , -N -R ^y )-R ^x , -C(=O)-R ^x , -C(=O)-O-R ^x , -C(=O)-NH-R ^x , -C(=O)-N (-R ^y )-R ^x , -O-C(=O)-R ^x , -NH-C(=O)-R ^x , -N(-R ^y )-C(=O)-R ^x, etc. can be mentioned. Note that R ^x and R ^y each independently represent an optionally branched alkyl group having 1 to 15 carbon atoms ^or an aryl group having 5 to 14 ring atoms; R ^y together may represent an alkylene group having 2 to 15 carbon atoms which may have a branch.
The optionally branched alkyl group having 1 to 15 carbon atoms and the aryl group having 5 to 14 ring atoms may each have a substituent. One or more methylene groups contained in the optionally branched alkyl group having 1 to 15 carbon atoms and the optionally branched alkylene group having 2 to 15 carbon atoms are etheric oxygen atoms. , a thioether sulfur atom, an aminic nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ - may be substituted (displace) structure. . Note that the above-mentioned aminic nitrogen atom represents -NH-, -N(R ^z )-, and R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

Permissible substituents for the optionally branched alkyl group having 1 to 15 carbon atoms in R ^x include -OH, -O-R ^A , -O-C(=O)-R ^A , - NH ₂ , -NH-R ^A , -N(-R ^B )-R ^A , -C(=O)-R ^A , -C(=O)-O-R ^A , -C(=O)-NH ₂ , -C(=O)-NH-R ^A , -C(=O)-N(-R ^B )-R ^A , -SH, -S-R ^A , sulfamoyl group, carboxy group, cyano group, nitro and 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 methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms include an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, and an ester bond. , an amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ - may be substituted. Furthermore, one or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms are substituted with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group. You may do so.
Among these, the permissible substituents for the optionally branched alkyl group having 1 to 15 carbon atoms in R ^x include -OR ^A is preferred, and examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, acryloyloxy, methacryloyloxy, glycidyloxy and the like.
Note that the above-mentioned aminic nitrogen atom is -NH-, -N(R ^z )-, and R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

Permissible substituents for the aryl group having 5 to 14 ring atoms in R ^x include -R ^A , -OH, -O-R ^A , -O-C(=O)-R ^A , -NH ₂ , -NH-R ^A , -N(-R ^B )-R ^A , -C(=O)-R ^A , -C(=O)-O-R ^A , -C(=O) -NH ₂ , -C(=O)-NH-R ^A , -C(=O)-N(-R ^B )-R ^A , -SH, -S-R ^A , trifluoromethyl group, sulfamoyl group, Examples include carboxy group, cyano group, nitro group, and halogen. Here, R ^A and R ^B each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms.
Among these, -R ^A , -O-R ^A are preferable as substituents permissible for the aryl group having 5 to 14 ring atoms in R ^x , such as methyl, ethyl, n- Propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, Examples include n-octoxy, 2-ethylhexyloxy, 5,5-dimethyl-3-methylhexyloxy, and the like.

Examples of the aryl group having 5 to 14 ring atoms include monovalent groups of the rings exemplified as aromatic hydrocarbon rings and aromatic heterocycles in A ¹ of formula (1).
As the monovalent group of the aromatic hydrocarbon ring, a monovalent group of a benzene ring (phenyl group) and a monovalent group of a naphthalene ring (naphthyl group) are preferable. Monovalent groups of aromatic heterocycles include a monovalent group of a furan ring, a monovalent group of a thiophene ring, a monovalent group of a thienothiazole ring, a monovalent group of a benzoxazole ring, a monovalent group of a benzothiazole ring, and a monovalent group of a benzothiazole ring. A monovalent group of an imidazole ring is preferred. The monovalent groups of the aromatic hydrocarbon ring and aromatic heterocycle tend to have high molecular linearity. Among these, phenyl groups are more preferred from the viewpoint of developing a high dichroic ratio.

R ^x and R ^y tend to be alkyl groups having 1 to 15 carbon atoms, which may have branches, or R ^x and R ^y are Together, it is preferably an alkylene group having 2 to 15 carbon atoms which may have a branch; an alkyl group having 1 to 6 carbon atoms which may have a branch, or R ^x and R ^y together are more preferably an alkylene group having 2 to 10 carbon atoms which may have a branch; an alkyl group having 1 to 3 carbon atoms which may have a branch. or R ^x and R ^y together are more preferably an alkylene group having 2 to 6 carbon atoms which may have a branch.

^{As the monovalent organic} group in -R ^x and -N(-R ^y )-R ^x are more preferred, and -N(-R ^y )-R ^x is even more preferred. Specifically, for example, dimethylamino group, diethylamino group, di-n-propylamino group, ethylmethylamino group, methylpropylamino group, azetidinyl group, pyrrolidinyl group, piperidinyl group, azepanyl group, morpholinyl group, piperazinyl group, thiomorpholinyl group. A group is more preferred, and a diethylamino group, a pyrrolidinyl group, and a piperidinyl group are even more preferred.

n represents 1, 2, or 3.
n is preferably 1 or 2, and more preferably 1, since the molecular length axis ratio is sufficiently large and the dye tends to have absorption in a short wavelength region.
When n represents 2 or 3, each A ³ may be the same or different.

—CH═CH— in formula (1) is preferably trans-type from the viewpoint of increasing the ratio of the major axis to the minor axis of the molecule.
-N=N- in formula (1) is preferably trans-type from the viewpoint of increasing the molecular major-minor axis ratio.

Specifically, the compounds represented by formula (1) include the following compounds, but are not limited thereto.

The compound represented by formula (1) contained in the composition for forming an anisotropic dye film of the present invention has maximum absorption (λ _max1 ), but it preferably has maximum absorption in the range of 350 to 550 nm, more preferably in the range of 410 to 530 nm, even more preferably in the range of 430 to 520 nm. are doing.
Furthermore, the compound represented by formula (1) contained in the composition for forming an anisotropic dye film of the present invention has a lower maximum absorption (λ _max2 ) measured by dissolving it in a solvent. It is preferable that the maximum absorption in the film (the above-mentioned λ _max1 ) exists at a long wavelength. This long wavelength shift is a phenomenon that occurs when the compound represented by formula (1) is dispersed in a polymerizable liquid crystal compound and/or a polymer having units based on the polymerizable liquid crystal compound, and is ) and a polymerizable liquid crystal compound and/or a polymer having a unit based on a polymerizable liquid crystal compound have strong intermolecular interactions. It is thought that this strong intermolecular interaction allows the compound represented by formula (1) to exhibit a high dichroic ratio. Long wavelength shift means that the difference in absorption maximum (λ _max1 - λ _max2 ) becomes a positive value, and from the viewpoint of expressing high dichroism, the difference is preferably 5 nm or more, The thickness is more preferably 10 nm or more, and even more preferably 15 nm or more. Further, the upper limit is not particularly limited, but may be, for example, 50 nm or less.

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 dyes include azo dyes, quinone dyes (including naphthoquinone dyes, anthraquinone dyes, etc.), stilbene dyes, cyanine dyes, phthalocyanine dyes, indigo dyes, and fused polycyclic dyes (perylene dyes). dyes, oxazine dyes, acridine dyes, etc.). Among these dyes, azo dyes are preferred because they can have a high molecular alignment in an anisotropic dye film.
Azo dye refers to a dye that has at least one azo group (-N=N-), and the number of azo groups in one molecule is determined by its solubility in solvents, compatibility with liquid crystal compounds, and color tone. From the viewpoint of ease of manufacture, the number is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

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

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

In formula (A),
D ¹ , D ² and D ³ each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent group which may have a substituent. represents a heterocyclic group;
p represents an integer from 0 to 4;
When p is an integer of 2 or more, the 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 group which may have a substituent. represents a heterocyclic group.
As the substitution position of the phenylene group, a 1,4-phenylene group is preferable because the molecule has high linearity.
As the substitution position of the naphthylene group, a 1,4-naphthylene group or a 2,6-naphthylene group is preferable because the linearity of the molecule is high.

From the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production, the divalent heterocyclic group preferably has 3 or more carbon atoms and 14 or less carbon atoms, more preferably 3 or more and 14 or less carbon atoms. It is 10 or less. In particular, a monocyclic or bicyclic heterocyclic group is preferable because the molecular long-short axis ratio tends to be large.
Examples of atoms other than carbon constituting the divalent heterocyclic group include at least one selected from nitrogen atoms, sulfur atoms, and oxygen atoms. When a heterocyclic group has a plurality of atoms constituting a ring other than carbon, these may be the same or different.
Specifically, pyridinediyl group, quinolinediyl group, isoquinolinediyl group, thiazolediyl group, benzthiazolediyl group, thienothiazolediyl group, thienothiophenediyl group, benzimidazolidinonediyl group, benzofurandiyl group, phthalimidodiyl group, Examples include oxazolediyl group and benzoxazolediyl group.

The optional substituents of the phenylene group, naphthylene group, and divalent heterocyclic group in D ¹ , D ² and D ³ include alkyl groups having 1 to 4 carbon atoms; methoxy groups, ethoxy groups, and butoxy groups; Alkoxy group having 1 to 4 carbon atoms; fluorinated alkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; cyano group; nitro group; hydroxyl group; halogen atom; substituted or substituted amino group, diethylamino group, pyrrolidino group, etc. Examples include unsubstituted amino groups.
The above-mentioned substituted amino group refers to an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or two substituted alkyl groups bonding to each other to form an alkanediyl group having 2 to 8 carbon atoms. refers to an amino group that contains The unsubstituted amino group is _-NH2 . Note that examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and a butyl group. Examples of alkanediyl groups having 2 to 8 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. , hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, and the like.
From the viewpoint of high molecular linearity, unsubstituted or substituted with a methyl group, methoxy group, hydroxyl group, fluorine atom, chlorine atom, dimethylamino group, pyrrolidinyl group, or piperidinyl group. is preferred.

p represents an integer from 0 to 4. From the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of production, the number is preferably 1 or more, preferably 4 or less, and more preferably 3 or less.

R ¹¹ and R ¹² represent the same or different monovalent organic groups.
Monovalent organic groups for R ¹¹ and R ¹² include a hydrogen atom, an optionally branched alkyl group having 1 to 15 carbon atoms; an alicyclic alkyl group having 1 to 15 carbon atoms; a methoxy group; Alkoxy group having 1 to 15 carbon atoms which may have a branch such as ethoxy group and butoxy group; Fluorinated alkyl group having 1 to 15 carbon atoms which may have a branch such as trifluoromethyl group; Cyano group; nitro group; hydroxyl group; halogen atom; substituted or unsubstituted amino group such as amino group, diethylamino group, and pyrrolidino group; carboxy group; Alkyloxycarbonyl group; Alkylphenylalkenyl group such as 2-(4-butylphenyl)ethenyl group; Carbamoyl group; Alkylcarbamoyl group having 1 to 15 carbon atoms which may have a branch such as butylcarbamoyl group; Sulfamoyl group ; an alkylsulfamoyl group having 1 to 15 carbon atoms which may have a branch such as a butylsulfamoyl group; an acylamino group having 1 to 15 carbon atoms which may have a branch such as a butylcarbonylamino group; ; an acyloxy group having 1 to 15 carbon atoms which may have a branch such as a butylcarbonyloxy group; a sulfanyl group; an alkylsulfanyl group having 1 to 15 carbon atoms such as a butylsulfanyl group; Examples include Q ¹ -R ¹ - and Q ² -R ² -.
The above-mentioned substituted amino group refers to an amino group having one or two optionally branched alkyl groups having 1 to 15 carbon atoms, or an amino group having 2 to 15 carbon atoms in which two substituted alkyl groups are bonded to each other. 15 means an amino group forming an alkanediyl group. The unsubstituted amino group is _-NH2 . Note that examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, and a butyl group. Examples of the alkanediyl group having 2 to 15 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. , hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, and the like.

R ¹¹ and R ¹² are hydrogen atoms, chain groups, aliphatic organic groups (“aliphatic organic groups” include chain and cyclic groups), carbon atoms partially containing nitrogen and/or Examples include aliphatic organic groups substituted with oxygen. In one embodiment, a hydrogen atom or a chain group is preferable, in another embodiment, a hydrogen atom or an aliphatic organic group is preferable, and in yet another embodiment, a hydrogen atom or a part of carbon is nitrogen and/or oxygen. Aliphatic organic groups substituted with are preferred.
Note that the above-mentioned "aliphatic organic group in which some of the carbon atoms are replaced with nitrogen and/or oxygen" includes chain-shaped and cyclic ones, and some methyl groups of the aliphatic organic group are hydroxyl groups, oxo groups. (=O), amino group, imino group, etc. are included.

As the chain group, the above-mentioned alkyl group having 1 to 15 carbon atoms which may have a branch; alkoxy group having 1 to 15 carbon atoms which may have a branch; Good fluorinated alkyl group having 1 to 15 carbon atoms; Substituted or unsubstituted amino group; Carboxy group; Alkyloxycarbonyl group having 1 to 15 carbon atoms which may have a branch; Carbamoyl group; an alkylcarbamoyl group having 1 to 15 carbon atoms; a sulfamoyl group; an alkylsulfamoyl group having 1 to 15 carbon atoms, which may have a branch; an acylamino group having 1 to 15 carbon atoms, which may have a branch; Groups; acyloxy groups having 1 to 15 carbon atoms which may have branches; sulfanyl groups; alkylsulfanyl groups having 1 to 15 carbon atoms; and the like.
Note that the above-mentioned substituted amino group means an amino group having one or two alkyl groups having 1 to 15 carbon atoms which may have a branch. The unsubstituted amino group is _-NH2 .

Examples of the aliphatic organic group include the above-mentioned optionally branched alkyl group having 1 to 15 carbon atoms, alicyclic alkyl group having 1 to 15 carbon atoms, and the like.
Examples of aliphatic organic groups in which some of the carbon atoms are replaced with nitrogen and/or oxygen include the above-mentioned alkoxy groups having 1 to 15 carbon atoms which may have branches; substituted or unsubstituted amino groups; carboxy groups ; Alkyloxycarbonyl group having 1 to 15 carbon atoms which may have a branch; Carbamoyl group; Alkylcarbamoyl group having 1 to 15 carbon atoms which may have a branch; Carbon which may have a branch Examples include an acylamino group having 1 to 15 carbon atoms; an acyloxy group having 1 to 15 carbon atoms which may have a branch.
The above-mentioned substituted amino group refers to an amino group having one or two optionally branched alkyl groups having 1 to 15 carbon atoms, or an amino group having 2 to 15 carbon atoms in which two substituted alkyl groups are bonded to each other. 15 means an amino group forming an alkanediyl group. The unsubstituted amino group is _-NH2 . Note that examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group, and a butyl group. Examples of the alkanediyl group having 2 to 15 carbon atoms include ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, and pentane-1,5-diyl group. , hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, and the like.

R ¹¹ and R ¹² are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms such as a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group; It is preferably substituted with an alkoxy group having 1 to 10 carbon atoms such as a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a diethylamino group, a pyrrolidino group, and a piperidinyl group. Furthermore, Q ¹ -R ¹ - and Q ² -R ² - in the polymerizable liquid crystal compound described below are also preferred.

Furthermore, the pigment other than the compound represented by formula (1) contained in the composition for forming an anisotropic pigment film of the present invention is not particularly limited, and known pigments can also be used.
Known pigments include, for example, the pigments ( (dichroic dyes, dichroic dyes).

Specifically, the dyes described below may be mentioned, but the dyes are not limited thereto.

In addition, the dye other than the compound represented by formula (1) contained in the anisotropic dye film-forming composition of the present invention has a wavelength showing a maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm. It is preferably a compound that is longer than the wavelength showing the maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm of the compound represented by formula (1) contained in the composition for forming an anisotropic dye film, and is preferably a compound represented by the formula (1). The wavelength showing the maximum value in the absorption curve in the wavelength range of 780 nm is the maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm of the compound represented by formula (1) contained in the composition for forming an anisotropic pigment film. It is more preferable that the compound is 5 nm or more longer than the wavelength showing the formula (1), and the wavelength showing the maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm is contained in the composition for forming an anisotropic dye film. More preferably, the compound is 10 nm or more longer than the wavelength showing the maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm. When the wavelength showing the maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm of a dye other than the compound represented by formula (1) is within the above range, color tone adjustment tends to be easier.

The molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention (in the case of using two or more types of dyes, the respective molecular weights) is preferably 300 or more, more preferably 350 or more, and 380 or more. The above is more preferable. Further, it is preferably 1,500 or less, more preferably 1,200 or less, and even more preferably 1,000 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, even more preferably from 380 to 1,000. Within the above range, the molecular major/minor axis ratio tends to increase.

The content occupied by the pigment (dichroic pigment) in the composition for forming an anisotropic pigment film (when two or more pigments are used together, the sum of their respective contents) is, for example, anisotropic pigment Based on the solid content (100 parts by mass) of the film-forming composition, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 30 parts by mass or less, and more preferably 10 parts by mass or less. . Specifically, the content of the dye (dichroic dye) in the composition for forming an anisotropic dye film is, for example, based on the solid content (100 parts by mass) of the composition for forming an anisotropic dye film. The amount is 0.01 to 30 parts by weight, preferably 0.05 to 10 parts by weight.
If the content of the dye (dichroic dye) is within the above range, the anisotropic dye of the present invention can be used without disturbing the orientation of the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention. It tends to be possible to polymerize the compounds contained in the film-forming composition. Moreover, if the content occupied by the dye (dichroic dye) is equal to or greater than the lower limit value, sufficient light absorption will be obtained and sufficient polarization performance will tend to be obtained. Moreover, if the content occupied by the dye (dichroic dye) is below the above-mentioned upper limit, inhibition of the alignment of liquid crystal molecules tends to be suppressed.

As the dye (dichroic dye), depending on the purpose, only the compound represented by formula (1) may be used, or the compound represented by formula (1) and other dyes may be used in combination. good. As mentioned above, the dye contained in the composition for forming an anisotropic dye film of the present invention includes a compound represented by formula (1) and a wavelength showing a maximum value in an absorption curve in a wavelength range of 380 nm to 780 nm. , one or more of the compounds contained in the composition for forming an anisotropic dye film and which are longer than the wavelength showing the maximum value in the absorption curve of the compound represented by formula (1) in the wavelength range of 380 nm to 780 nm. It is preferable to use them together. In particular, when forming a polarizing element such as a display using an anisotropic dye film-forming composition using the composition for forming an anisotropic dye film, it is preferable in that it exhibits polarization properties over a wide range of the visible region.

The dye contained in the composition for forming an anisotropic dye film of the present invention can be subjected to an alkylation reaction, an esterification reaction, an amidation reaction, an etherification reaction, an ipso-substitution reaction, a diazo coupling reaction, a coupling using a metal catalyst. It can be produced by combining known chemical reactions such as reactions.
For example, the dye contained in the composition for forming an anisotropic dye film of the present invention can be prepared by the method described in Examples or by the method described in "Shin Dye Kagaku" (written by Yutaka Hosoda, December 21, 1970, Gihodo). , "Overview of Synthetic Dyes" (Hiroshi Horiguchi, 1968, Sankyo Publishing) and "Theoretical Manufacturing Dye Chemistry" (Yutaka Hosoda, 1957, Gihodo).

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

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

In polymerizable liquid crystal compounds, the polymerizable group can be placed at any position within the liquid crystal compound molecule, but substituting it at the end of the liquid crystal compound molecule tends to facilitate intermolecular polymerization. It is preferable because there is.
In the polymerizable liquid crystal compound, one or more polymerizable groups can exist in the liquid crystal compound molecule, and when two or more polymerizable groups exist, it is preferable that they each exist at both ends of the liquid crystal compound molecule.

Further, the polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond within the liquid crystal compound molecule. In compounds with a carbon-carbon triple bond, the carbon-carbon triple bond is capable of rotational movement and can also serve as the core of a liquid crystal molecule. It has strong intermolecular interactions with compounds that have a π-conjugated system, such as molecules, and tends to have high molecular orientation.

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

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

(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 a partial structure represented by the following formula (3), a divalent organic group, or a single bond;
A ¹² represents a partial structure or a 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 or a divalent organic group represented by the following formula (3);
k is 1 or 2. )

-Cy-X ² -C≡C-X ¹ - ...(3)

(In the formula,
Cy represents a hydrocarbon ring group or a heterocyclic group;
-X ¹ - is -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 represents S- or -SCH ₂ -;
-X ² - is 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 -. )

Note that when A ¹¹ is a partial structure represented by formula (3), formula (2) is
Q ¹ -R ¹ -Cy-X ² -C≡C-X ¹ -Y ¹ -A ¹² -(Y ² -A ¹³ ) _k -R ² -Q ² ... (2A)
It may be,
Q ¹ -R ¹ -X ¹ -C≡C-X ² -Cy-Y ¹ -A ¹² -(Y ² -A ¹³ ) _k -R ² -Q ² ... (2B)
It may be.
Furthermore, when A ¹² is a partial structure represented by formula (3), formula (2) is
Q ¹ -R ¹ -A ¹¹ -Y ¹ -Cy-X ² -C≡C-X ¹ -(Y ² -A ¹³ ) _k -R ² -Q ² ...(2C)
It may be,
Q ¹ -R ¹ -A ¹¹ -Y ¹ -X ¹ -C≡C-X ² -Cy-(Y ² -A ¹³ ) _k -R ² -Q ² ... (2D)
It may be.
Furthermore, when A ¹³ is a partial structure represented by formula (3), formula (2) is
Q ¹ -R ¹ -A ¹¹ -Y ¹ -A ¹² -(Y ² -Cy-X ² -C≡C-X ¹ ) _k -R ² -Q ² ...(2E)
It may be,
Q ¹ -R ¹ -A ¹¹ -Y ¹ -A ¹² -(Y ² -X ¹ -C≡C-X ² -Cy) _k -R ² -Q ² ... (2F)
It may be.

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) is independent of each other. It may be reversed.

Furthermore, 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); in addition, A ¹¹ and A ¹³ are Although it may be a single bond, A ¹¹ and A ¹³ are not both single bonds.

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

The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.
The unlinked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms. Examples of aromatic hydrocarbon rings include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. .
The linked 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 has a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20. For example, a first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms are bonded together through a single bond, and 1 has a first bond on the atom constituting the ring of a monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms, and a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms It is a divalent group having a second bond on the atom constituting the group hydrocarbon ring. Examples of the linked aromatic hydrocarbon ring group include biphenyl-4,4'-diyl group.
As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable.
Among these, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring and a divalent group of a naphthalene ring are preferable, and a divalent group of a benzene ring (phenylene group) is more preferable. As the phenylene group, a 1,4-phenylene group is preferred. Having the above group tends to improve the molecular orientation of the liquid crystal compound.

The non-aromatic hydrocarbon ring group includes an unlinked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
The unlinked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms. Examples of non-aromatic hydrocarbon rings include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo [2 .2.2] octane ring, etc.
An unlinked non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the ring of a non-aromatic hydrocarbon ring, and a ring of a non-aromatic hydrocarbon ring. and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the unsaturated bond. As the unlinked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferable.
A linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and has a bond on the atom constituting the ring; One or more rings selected from the group consisting of an aromatic hydrocarbon ring, a fused aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a fused non-aromatic hydrocarbon ring, and a monocyclic or It is a divalent group that is bonded to a fused non-aromatic hydrocarbon ring through a single bond and has a bond on the atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded together through a single bond. , has a first bond on the atom constituting the first monocyclic ring having 3 to 20 carbon atoms or a fused non-aromatic hydrocarbon ring, and the second monocyclic ring having 3 to 20 carbon atoms or A divalent group having a second bond on the atom constituting the ring of a fused non-aromatic hydrocarbon ring, for example, a monocyclic ring having 3 to 20 carbon atoms or a fused aromatic hydrocarbon ring and a carbon number 3 to 20 monocyclic or fused non-aromatic hydrocarbon rings are bonded to each other by a single bond, and the first It is a divalent group having a bond and a second bond on an atom constituting a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Examples of the linked non-aromatic hydrocarbon ring group include bis(cyclohexane)-4,4'-diyl group and 1-cyclohexylbenzene-4,4'-diyl group.
As the non-aromatic hydrocarbon ring group, a non-linked non-aromatic hydrocarbon ring group is preferable from the viewpoint of molecular orientation of the liquid crystal compound.
Among these, the divalent group of cyclohexane (cyclohexanediyl group) is preferable as the non-aromatic hydrocarbon ring group. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferred. Having the above group tends to improve the solubility and molecular orientation of the liquid crystal compound.

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

The aromatic heterocyclic group includes an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.
The unlinked aromatic heterocyclic group is a monocyclic or fused aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms. Examples of aromatic heterocycles include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroimidazole ring, pyrrolopyrazole ring, and pyrrolopyrrole. ring, thienopyrrole ring, thienothiophene ring, furopyrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring , quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring, and the like.
A linked aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed aromatic heterocycles are bonded by a single bond and has a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms are bonded together through a single bond, and the first A monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms, with a first bond on an atom constituting the ring of a monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms; is a divalent group having a second bond on the atom constituting the ring.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
The unlinked non-aromatic heterocyclic group is a monocyclic or fused non-aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms. It is a divalent group of a monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms, and examples of the non-aromatic heterocycle include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, Pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydroxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine ring, etc. can be mentioned.
A linked non-aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed non-aromatic heterocycles are bonded by a single bond and has a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms are bonded together via a single bond; 1 has a first bond on an atom constituting a monocyclic ring having 4 to 20 carbon atoms or a fused non-aromatic heterocyclic ring, and a second monocyclic ring having 4 to 20 carbon atoms or a fused non-aromatic ring It is a divalent group having a second bond on the atom constituting the ring of an aromatic heterocycle.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy are R ^z , -OH, -O-R ^z , -O-C ( =O)-R ^z , -NH ₂ , -NH-R ^z , -N(R ^z' )-R ^z , -C(=O)-R ^z , -C(=O)-O-R ^z , -C(=O)-NH ₂ , -C(=O)-NH-R ^z , -C(=O)-N(R ^z' )-R ^z , -SH, -SR ^z , trifluoro It may be substituted with one or more groups selected from the group consisting of methyl group, sulfamoyl group, carboxy group, sulfo group, cyano group, nitro group, and halogen. Here, R ^z and R ^z' each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.
The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Cy have a highly linear molecular structure, and the molecules represented by formula (2) From the viewpoint of easy association and easy formation of a liquid crystal state, each independently is preferably unsubstituted or substituted with a methyl group, methoxy group, fluorine atom, chlorine atom, or bromine atom, and is unsubstituted. is more preferable.
The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group may be the same or different, and the aromatic hydrocarbon ring group, All of the non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be substituted, all may be unsubstituted, or some may be substituted and some may be substituted. It may be unsubstituted.

From the viewpoint of solubility and molecular orientation of the liquid crystal compound, Cy is preferably a hydrocarbon ring group, and more preferably a phenylene group or a cyclohexanediyl group. Moreover, as Cy, a 1,4-phenylene group and a cyclohexane-1,4-diyl group are more preferable, and a 1,4-phenylene group is particularly preferable, since the linearity of the molecular structure of the liquid crystal compound can be improved. .

Because of the linearity of liquid crystal compounds and the tendency for rotational movement around the short axis of the molecule, -X ¹ - is selected from -C(=O)O-, -OC(=O), which have small π bonding properties. -, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, - OCH ₂ -, -CH ₂ S-, -SCH ₂ - are preferred, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ - is more preferable. In one embodiment, -X ¹ - is -C(=O)O- or -OC(=O)-, and in another embodiment, -X ¹ - is -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ -.

-Cy- and -C≡C- are groups with high linearity from the viewpoint of enlarging the core of the liquid crystal compound and increasing the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film. -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 preferable, and a single bond is even more preferable because it has 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 necessary to ensure the polymerization function. The polymerizable group is preferably a photopolymerizable group from the viewpoint of producing an anisotropic dye film.
Specifically, the polymerizable group includes, for example, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a vinyloxy group, an ethynyl group, an ethynyloxy group, 1 , 3-butadienyl group, 1,3-butadienyloxy group, oxiranyl group, oxetanyl group, glycidyl group, glycidyloxy group, styryl group, styryloxy group and the like. Among these, acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, oxiranyl group, glycidyl group, glycidyloxy group are preferred; group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a glycidyl group, and a glycidyloxy group are more preferable, and an acryloyloxy group, a methacryloyloxy group, and a glycidyloxy group are even more preferable. By having the above-mentioned polymerizable group, polymerization tends to be easily controlled.

The chain organic group in R ¹ and R ² is a divalent organic group that does not contain a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, or non-aromatic heterocycle. be.
Such chain organic groups include -(alkylene group)-, -O-(alkylene group)-, -S-(alkylene group)-, -NH-(alkylene group)-, -N(alkyl group) -(alkylene group)-, -OC(=O)-(alkylene group)-, and -C(=O)O-(alkylene group)-.
The chain organic group in R ¹ and R ² is preferably -(alkylene group)- or -O-(alkylene group)-. In one embodiment, the chain organic group in R ¹ and R ² is -(alkylene group)-, and in another embodiment, the chain organic group is -O-(alkylene group)-. be.

Examples of the alkylene group in these chain organic groups include linear or branched alkylene groups having 1 to 25 carbon atoms. Some of the carbon-carbon bonds in the alkylene group may be unsaturated bonds, and one or more methylene groups contained in the alkylene group may include an ether oxygen atom, a thioether sulfur atom, an amine The structure may be replaced by a nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF ₂ -, -CHCl-, or -CCl ₂ -.
Note that examples of the aminic nitrogen atom include -NH- and -N(R ^z ), where R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.
Since the alkylene group in these chain organic groups has high molecular linearity, some of the carbon atoms in the alkylene group may be unsaturated bonds, and one or more carbon atoms contained in the alkylene group may be unsaturated bonds. It is preferably a linear alkylene group having 1 to 25 carbon atoms, which may have a structure in which the methylene group is replaced by the above-mentioned group.
The number of atoms in the main chain (meaning the longest chain part in the chain organic group) of the chain organic group is preferably 3 to 25, more preferably 5 to 20, even more preferably 6 to 20.

Examples of chain organic groups include -(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 - are preferable from the viewpoint of enhancing the molecular orientation of the liquid crystal compound. Note that n in these formulas is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and even more preferably an integer of 5 to 19. In addition, n1, n2, and n3 in these formulas each independently represent an integer, and the number of atoms in the main chain (meaning the longest chain part in the chain organic group) of the chain organic group is , preferably 3 to 25, more preferably 5 to 20, still more preferably 6 to 20.

R ¹ and R ² are each independently -(alkylene group)-, -O-(alkylene group)-, preferably -(alkylene group)-, -O-(alkylene group)- is more preferable. With the above molecular structure, the molecular orientation of the liquid crystal compound tends to be enhanced.
When X ¹ and R ¹ or X ¹ and R ² are bonded as in formula (2B) and formula (2E); For example, when A ¹³ is a single bond in formula (2B), When R ¹ or R ² is bonded ^to Y 1 or Y 2, as in the case where A ^{11 is} a single bond in (2E), R ¹ bonded to X ¹ or Y ¹ or Y ² Alternatively, R ² is preferably -(alkylene group)- from the viewpoint of enhancing the molecular orientation of the liquid crystal compound.
Further, as other than the above, R 1 ^or R ² that does not bond to X ¹ or Y ¹ or Y ² is preferably -O- (alkylene group)- from the viewpoint of enhancing the molecular orientation 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).

^-Q3 -...(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.

The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.
The unlinked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms. Examples of aromatic hydrocarbon rings include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. .
The linked 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 has a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20. For example, a first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms are bonded together through a single bond, and 1 has a first bond on the atom constituting the ring of a monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms, and a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms It is a divalent group having a second bond on the atom constituting the group hydrocarbon ring. Examples of the linked aromatic hydrocarbon ring group include biphenyl-4,4'-diyl group.
As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable.
Among these, as the aromatic hydrocarbon ring group, a divalent group of a benzene ring and a divalent group of a naphthalene ring are preferable, and a divalent group of a benzene ring (phenylene group) is more preferable. As the phenylene group, a 1,4-phenylene group is preferred. Having the above group tends to improve the molecular orientation of the liquid crystal compound.

The non-aromatic hydrocarbon ring group includes an unlinked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.
The unlinked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms. Examples of non-aromatic hydrocarbon rings include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo [2 .2.2] octane ring, etc.
An unlinked non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the ring of a non-aromatic hydrocarbon ring, and a ring of a non-aromatic hydrocarbon ring. and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the unsaturated bond. As the unlinked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferable.
A linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and has a bond on the atom constituting the ring; One or more rings selected from the group consisting of an aromatic hydrocarbon ring, a fused aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a fused non-aromatic hydrocarbon ring, and a monocyclic or It is a divalent group that is bonded to a fused non-aromatic hydrocarbon ring through a single bond and has a bond on the atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20. For example, a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded together through a single bond. , has a first bond on the atom constituting the first monocyclic ring having 3 to 20 carbon atoms or a fused non-aromatic hydrocarbon ring, and the second monocyclic ring having 3 to 20 carbon atoms or It is a divalent group having a second bond on the atom constituting the fused non-aromatic hydrocarbon ring. Further, for example, a monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, and The first bond is on the atom constituting 20 monocyclic or fused aromatic hydrocarbon rings, and the ring is a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. It is a divalent group having a second bond on the atom.
Examples of the linked non-aromatic hydrocarbon ring group include bis(cyclohexane)-4,4'-diyl group and 1-cyclohexylbenzene-4,4'-diyl group.
The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group.
Among these, the divalent group of cyclohexane (cyclohexanediyl group) is preferable as the non-aromatic hydrocarbon ring group. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferred 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 an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.
The unlinked aromatic heterocyclic group is a monocyclic or fused aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms. Examples of aromatic heterocycles include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroimidazole ring, pyrrolopyrazole ring, and pyrrolopyrrole. ring, thienopyrrole ring, thienothiophene ring, furopyrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring , quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, quinazoline ring, quinazolinone ring, azulene ring, and the like.
A linked aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed aromatic heterocycles are bonded by a single bond and has a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms are bonded together through a single bond, and the first A monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms, with a first bond on an atom constituting the ring of a monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms; is a divalent group having a second bond on the atom constituting the ring.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.
The unlinked non-aromatic heterocyclic group is a monocyclic or fused non-aromatic heterocyclic divalent group, and preferably has 4 to 20 carbon atoms. It is a divalent group of a monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms, and examples of the non-aromatic heterocycle include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, Pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydroxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzimidazole ring, quinuclidine ring, etc. can be mentioned.
The linked non-aromatic heterocyclic group is a divalent group in which a single ring or a plurality of condensed non-aromatic heterocycles are bonded by a single bond and has a bond on the atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. For example, a first monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms are bonded together through a single bond; 1 has a first bond on the atom constituting the ring of a monocyclic ring having 4 to 20 carbon atoms or a fused non-aromatic heterocyclic ring, and a second monocyclic ring having 4 to 20 carbon atoms or a fused non-aromatic ring. It is a divalent group having a second bond on the atom constituting the ring of an aromatic heterocycle.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in Q3 are R ^z , -OH, -O-R ^z , -O-C( =O)-R ^z , -NH ₂ , -NH-R ^z , -N(R ^z' )-R ^z , -C(=O)-R ^z , -C(=O)-O-R ^z , -C(=O)-NH ₂ , -C(=O)-NH-R ^z , -C(=O)-N(R ^z' )-R ^z , -SH, -SR ^z , trifluoro It may be substituted with one or more groups selected from the group consisting of methyl group, sulfamoyl group, carboxy group, sulfo group, cyano group, nitro group, and halogen. Here, R ^z and R ^z' each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.
The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in ^Q3 have high linearity in molecular structure, and the molecules represented by formula (2) It is preferable that each of them is independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and is unsubstituted. It is more preferable.
The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group may be the same or different, and the aromatic hydrocarbon ring group, All of the non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be substituted, all may be unsubstituted, or some may be substituted and some may be substituted. It may be unsubstituted.
Furthermore, the substituents possessed by the divalent organic groups in A ¹¹ , A ¹² , and A ¹³ may be the same or different, and all of the divalent organic groups in A ¹¹ , A ¹² , and A ¹³ are substituted. It may be completely unsubstituted, or it may be partly substituted and partly unsubstituted.

^Q3 is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. Further, as Q ³ , 1,4-phenylene group and cyclohexane-1,4-diyl group are more preferable since they can improve the linearity of the molecular structure of the liquid crystal compound.

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

In formula (2), one of A ¹¹ , A ¹² , and A ¹³ is a partial structure represented by formula (3), and the other two are each independently a divalent organic group. Among A ¹¹ , A ¹² , and A ¹³ , it is preferable that Cy in the partial structure represented by formula (3) is a hydrocarbon ring group, and the divalent organic group is a hydrocarbon ring group. It is particularly preferable that there be. Furthermore, the hydrocarbon ring group is preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group. Further, it is preferable that one of A ¹¹ and A ¹³ is a cyclohexane-1,4-diyl group.
Further, 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 divalent organic groups. In this case, one of A ¹¹ and A ¹³ , which is a divalent organic group, is preferably a cyclohexane-1,4-diyl group, and it is particularly preferable that A ¹² is a 1,4-phenylene group. With the above structure, the molecular orientation of the liquid crystal compound tends to be good.

Because of the linearity of liquid crystal compounds and the tendency for rotational movement around the short axis of the molecule, -Y ¹ - and -Y ² - are each independently composed of 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 - is preferable, and a single bond, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, and -OCH ₂ - are more preferable.

As in formula (2A), formula (2C), formula (2D), and formula (2F), when X ¹ and Y ¹ or X ¹ and Y ² are bonded, Y ¹ bonded to X ¹ Alternatively, Y ² bonded to X ¹ is preferably a single bond; -X ¹ - and the other of -Y ¹ - and -Y ² - are -C(=O)O- or -OC(= O)- is preferred.
Furthermore, as in formula (2B) and formula (2E), when X ¹ is not bonded to either Y ¹ or Y ² , -X ¹ - is -CH ₂ CH ₂ -, -CH ₂ It is preferably O- or -OCH ₂ -; both -Y ¹ - and -Y ² - are preferably -C(=O)O- or -OC(=O)-. With the above structure, the molecular orientation of the liquid crystal compound tends to be good.

As formula (2), the above formula (2A), the above formula (2B), the above (2E), and the above (2F) are preferable.
In addition, as another embodiment, in formula (2), one of A ¹¹ , A ¹² , and A ¹³ is a 1,4-phenylene group, and the other two are each independently a divalent group. An organic group is preferable, and it is particularly preferable that the divalent organic group is a hydrocarbon ring group. Furthermore, the hydrocarbon ring group is preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group. With the above structure, molecular linearity tends to be high.

k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2. When the above value is achieved, the molecular orientation of the liquid crystal compound tends to be good.
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, but are not limited to, the following polymerizable liquid crystal compounds. In the formula, C ₅ H ₁₁ means an n-pentyl group, and C ₆ H ₁₃ means an n-hexyl group.

The polymerizable liquid crystal compounds 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.

The polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention preferably has an isotropic phase appearance temperature of 160°C or lower, more preferably 140°C or lower, from the viewpoint of the process. The temperature is more preferably 115°C or lower, even more preferably 110°C or lower, and particularly preferably 105°C or lower.
Note that the isotropic phase appearance temperature herein means a phase transition temperature from liquid crystal to liquid and a phase transition temperature from liquid to liquid crystal. In the present invention, it is preferable that at least one of these phase transition temperatures is within the above range, and it is more preferable that both of these phase transition temperatures are within the above range.

The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be used in a known manner such as an alkylation reaction, an esterification reaction, an amidation reaction, an etherification reaction, an ipsosubstitution reaction, a coupling reaction using a metal catalyst, etc. It can be produced by combining the following chemical reactions.
For example, the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention can be used by the method described in Examples or from 449 to It can be synthesized according to the method described on page 468.

(Relationship between the polymerizable liquid crystal compound and the compound represented by formula (1))
From the viewpoint of easily improving the orientation of the anisotropic dye film formed using the composition for forming an anisotropic dye film, in the composition for forming an anisotropic dye film, the molecular length of the liquid crystal compound and It is preferable that the difference between the dye molecular length and the dye molecule length is smaller because the intermolecular interaction between the liquid crystal molecules and the dye molecules is stronger and the dye molecules are less likely to inhibit the association between the liquid crystal molecules.

Therefore, in the composition for forming an anisotropic pigment 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 an anisotropic pigment film, The ratio (r _n1 /r _n2 ) to the number of ring structures (r _n2 ) possessed by the compound represented by formula (1) contained in the forming composition is preferably 0.7 to 1.5. .
Note that a condensed ring in which two or more rings are condensed is counted as one ring structure.

Here, the number of ring structures (r _n2 ) that the compound represented by formula (1) has is the sum of A ¹ , A ² , and A ³ in the formula, and specifically, when n is 1 If _n is 2, r _n2 is 4; if n is 3, r _n2 is 5.
Note that 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 of ring structures (r _n2 ) possessed by the compound represented by formula (1). do not have.

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 if r _n1 is 4, 5, 6, or 7, the polymerizable composition contained in the composition for forming an anisotropic dye film _The ratio ( _{r n1} /r _n2 ) is preferably 0.7 to 1.5.

The number of ring structures (r _n1 ) included in the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film includes ring structures contained in the polymerizable groups in the polymerizable liquid crystal compound (for example, oxirane rings and Oxetane rings, etc.) are not included.

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

Examples of usable polymerization initiators include titanocene derivatives; biimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-s-triazine derivatives; alkylphenone derivatives; oxime ester derivatives; benzoins; Examples include benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; acetophenone derivatives; thioxanthone derivatives; benzoic acid ester derivatives; acridine derivatives; phenazine derivatives; anthrone derivatives.
Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferred.

Specifically, the titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl). 1-yl), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl-1-yl) dicyclopentadienyl titanium di(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium di(2,4-difluorophenyl-1-yl), di(methylcyclopentadienyl) ) titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl), dicyclopentadi enyltitanium [2,6-di-fluoro-3-(pyrro-1-yl)-pheny-1-yl] and the like.

In addition, as biimidazole derivatives, 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 and the like.

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

Further, as halomethyl-s-triazine derivatives, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.

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

In addition, oxime ester derivatives include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl-1-[6-(2-methylbenzoyl)-9 -ethyl-9H-carbazol-3-yl]ethanone oxime, oxime esters described in Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2006-36750, International Publication No. WO 2009/131189, etc. Examples include derivatives.

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

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

In addition, examples of acylphosphine oxide derivatives include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and bis(2,4, Examples include 6-trimethylbenzoyl) phenylphosphine oxide.

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

In addition, examples of sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, and diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate. , 4,4'-bis[diphenylsulfonio]diphenylsulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluoroantimonate, 4,4 '-Bis[di(β-hydroxyethoxy)phenylsulfonio]diphenylsulfide bishexafluorophosphate, 7-[di(p-tolyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7-[di( p-tolyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-tolyl)sulfonio-diphenylsulfide tetrakis(pentafluorophenyl)borate, etc. can be mentioned.

Further, examples of anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

In addition, as acetophenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy -1-methylethyl-(p-isopropylphenyl)ketone, 1-hydroxy-1-(p-dodecylphenyl)ketone, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, 1, Examples include 1,1-trichloromethyl-(p-butylphenyl)ketone.

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

Further, benzoic acid ester derivatives; ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, etc. can be mentioned.

Further, examples of acridine derivatives include 9-phenylacridine and 9-(p-methoxyphenyl)acridine.

Furthermore, examples of phenazine derivatives include 9,10-dimethylbenzphenazine and the like.

Furthermore, examples of anthrone derivatives include benzanthrone and the like.

One type of polymerization initiator may be used alone, or two or more types may be used in combination.

A commercially available product can also be used as the polymerization initiator.
Commercially available products include, for example, IRGACURE (registered trademark) 250, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, IRGACURE 819, IRGACURE 784 , OXE-01, OXE-02 (all manufactured by BASF); Sequal (registered trademark) BZ, Z, and BEE (manufactured by Seiko Kagaku Co., Ltd.); kayacure (registered trademark) BP100, and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); ADEKA Optomer SP-152, and SP-170 (manufactured by ADEKA Co., Ltd.); TAZ-A, and TAZ-PP (manufactured by Nippon Siberhegner Co., Ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (CHANGZHOU TRONLY NEW ELECTRONIC) MATERIALS CO., LTD) ).

When the composition of the present invention contains a polymerization initiator, the content of the polymerization initiator in the composition of the present invention is set to 100 parts by mass of the polymerizable liquid crystal compound from the viewpoint of not easily disturbing the orientation of the polymerizable liquid crystal compound. On the other hand, it is usually 0.1 to 30 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 0.5 to 8 parts by weight.

If necessary, a polymerization accelerator may be used in combination with the polymerization initiator. Examples of the polymerization accelerator used include N,N-dialkylaminobenzoic acid alkyl esters such as N,N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzoic acid. Examples include mercapto compounds having a heterocycle such as imidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds;

Furthermore, a sensitizing dye may be used in combination for the purpose of increasing the sensitivity, if necessary. Appropriate sensitizing dyes are used depending on the wavelength of the exposure light source; for example, xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Publication No. 4-219756; Coumarin dyes having heterocycles as described in Japanese Patent Application Laid-open No. 3-239703, Japanese Patent Application Publication No. 5-289335, etc.; 3-ketocoumarin dyes described in Japanese Unexamined Patent Publication No. 6-19240, etc.; pyrromethene dyes described in Japanese Unexamined Patent Publication No. 47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japan Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Application Publication No. 52-112681, Japanese Patent Application Publication No. 58-15503, Japanese Publication No. 60-88005 Publication, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-69, Unexamined Japanese Patent Application No. 168088-1988, Unexamined Japanese Patent Publication No. 107761-1982, Unexamined Japanese Patent Application No. 1987-10776, Unexamined Japanese Patent Publication No. 5-107761. Examples include dyes having a dialkylaminobenzene skeleton described in JP-A No. 210240, Japanese Patent Application Laid-Open No. 4-288818, and the like.
The sensitizing dyes may also be used alone or in combination of two or more.

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

The solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound and the dye, and more preferably a solvent that can completely dissolve the polymerizable liquid crystal compound and the dye. Further, it is preferable that the solvent is inert to the polymerization reaction. Furthermore, from the viewpoint of coating the composition for forming an anisotropic dye film of the present invention, which will be described later, a solvent having a boiling point in the range of 50 to 200°C is preferable.

When the composition for forming an anisotropic pigment film of the present invention contains a solvent, the content ratio of the solvent in the composition for forming an anisotropic pigment film is based on the total amount (100% by mass) of the composition of the present invention. The amount is 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 to 50% by mass.
If the solid content in the composition for forming an anisotropic pigment film is below the above-mentioned upper limit, the viscosity of the composition for forming an anisotropic pigment film will not become too high, and the thickness of the polarizing film obtained will be uniform. , the polarizing film tends to be less likely to have unevenness.
Such solid content can be determined in consideration of the thickness of the polarizing film to be manufactured.
The viscosity of the composition for an anisotropic dye film of the present invention is not particularly limited as long as a uniform film without uneven thickness can be produced by the coating method described below, but it is From the viewpoint of obtaining productivity and in-plane uniformity of optical properties, the pressure is preferably 0.1 mPa·s or more, preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

(Other additives)
The composition for forming an anisotropic dye film of the present invention may further contain a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersion agent, a It may also contain other additives such as additives, antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, and metal oxides. By including additives, the coating properties and stability of the composition for forming an anisotropic pigment film can be improved, and the stability of the anisotropic pigment film formed from the composition for forming an anisotropic pigment film can be improved. It may be possible to improve it.

[Method for producing composition for forming anisotropic pigment film]
The method for producing the composition for an anisotropic dye film of the present invention is not particularly limited. For example, a dye, a polymerizable liquid crystal compound, and if necessary a solvent and other additives are mixed, and the mixture is stirred and shaken at 0 to 80° C. to dissolve the dye. If it is poorly soluble, a homogenizer, bead mill disperser, etc. may be used.
The method for producing the composition for an anisotropic dye film of the present invention may include a filtration step for the purpose of removing foreign substances in the composition.

In the composition for forming an anisotropic pigment film of the present invention, the composition obtained by removing the solvent from the composition for forming an anisotropic pigment film may or may not be a liquid crystal at any temperature; It is preferable that the material exhibits liquid crystallinity. The composition from which the solvent has been removed from the composition for forming an anisotropic dye film preferably has an isotropic phase appearance temperature of less than 160°C, more preferably less than 140°C, from the viewpoint of the coating process described below. Preferably, the temperature is less than 115°C, more preferably less than 110°C, even more 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 and one or both of a polymerizable liquid crystal compound and a polymer having a unit based on the polymerizable liquid crystal compound, and the dye is represented by formula (1). Contains compounds.
The anisotropic dye film of the present invention comprises a non-polymerizable liquid crystal compound, a polymerization initiator, a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, a non-polymerizable non-liquid crystal compound, a surfactant, a leveling agent, and a coupling agent. It may also contain agents, pH adjusters, dispersants, antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, metal oxides, and the like.

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 dye film of the present invention can function as a polarizing film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption. By selecting a composition containing (or transparent material), it is possible to functionalize it as a dye film with various anisotropies such as refractive anisotropy and conduction anisotropy.

When the anisotropic dye film of the present invention is used as a polarizing element for a liquid crystal display or an antireflection film for an OLED, the orientation characteristics of the anisotropic dye film can be expressed using a dichroic ratio. If the dichroic ratio is 8 or more, it functions as a polarizing element, but it is preferably 15 or more, more preferably 20 or more, even more preferably 25 or more, particularly preferably 30 or more, and even more preferably 40 or more. Further, the higher the dichroic ratio is, the more preferable it is. When the dichroic ratio is equal to or higher than the lower limit, it is useful as an optical element, particularly a polarizing element, which will be described later.
When used as a polarizing element in an antireflection film for OLED, even if the performance of peripheral materials such as a retardation film is low, if the performance of the polarizing element is high, the properties as an antireflection film will improve. Therefore, if the performance of the polarizing element is high, it will be easier to simplify the layer structure, it will be easier to exhibit sufficient functionality even with a thin film structure, and it will be suitable for use in applications where it is deformed, including folding and bending. Furthermore, costs can also be kept low.

The dichroic ratio (D) referred to in the present invention is expressed by the following formula when the dye is uniformly oriented.
D= _Az / _Ay
Here, A _z is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye, and A _y is the absorbance of the light incident on the anisotropic dye film. This is the absorbance observed when the polarization direction of is perpendicular.
There is no particular restriction on the respective absorbances (A _z , A _y ) as long as they have the same wavelength, and any wavelength may be selected depending on the purpose, but when expressing the degree of orientation of the anisotropic dye film, It is preferable to use a value corrected by visibility in the specific wavelength range of 380 nm to 780 nm of the anisotropic pigment film, or a value at the maximum absorption wavelength in the visible range.

Further, the transmittance of the anisotropic dye film of the present invention is preferably 25% or more, more preferably 35% or more, particularly preferably 40% or more at the intended wavelength of use. Further, the transmittance may be at an upper limit depending on the application.
When the anisotropic dye film of the present invention is used as a dye film having anisotropy in the entire visible light wavelength range, the transmittance of the anisotropic dye film in the visible light wavelength range is preferably 25% or more. , more preferably 35% or more, particularly preferably 40% or more. Further, the transmittance may be at an upper limit depending on the application. For example, when increasing the degree of polarization, the transmittance is preferably 50% or less. Since the transmittance is within the above range, it is useful as an optical element, which will be described later, and especially as an optical element for liquid crystal displays used for color display, and for antireflection films that combine an anisotropic dye film and a retardation film. Useful.

The dry film thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 100 nm or more, and still more preferably 500 nm or more. On the other hand, the thickness is preferably 30 μm or less, more preferably 10 μm or less, even more preferably 5 μm or less, particularly preferably 3 μm or less. When the thickness of the anisotropic dye film is within the above range, uniform orientation of the dye and uniform film thickness tend to be obtained within the film.

[Method for producing anisotropic dye 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 wet film forming method referred to in the present invention is a method of applying and orienting a composition for an anisotropic dye film onto a substrate by some method. Therefore, the composition for an anisotropic dye film only needs to have fluidity and may or may not contain a solvent. From the viewpoint of viscosity and film uniformity during coating, it is more preferable that a solvent is included.

The liquid crystals and dyes in the anisotropic dye film may be oriented by shearing during the coating process, or may be oriented during the drying process of the solvent. Alternatively, the liquid crystal, dye, etc. may be aligned and laminated on the substrate through a process of heating after coating and drying to realign the liquid crystal, dye, etc. In the wet film forming method, when the anisotropic dye film composition is applied onto the substrate, the anisotropic dye film composition is already in the anisotropic dye film composition, or in the process of drying the solvent, or after the solvent is completely removed. When the dye or liquid crystal compound self-associates (a state of molecular association such as a liquid crystal state), alignment occurs in a minute area. By applying an external field to this state, it is possible to align the dye in a certain direction in a macroscopic region and obtain an anisotropic dye film having desired performance. In this respect, it differs from a method based on the principle of dyeing a polyvinyl alcohol (PVA) film or the like with a solution containing a dye and stretching it, and orienting the dye only in the stretching process. Note that the external field here includes the influence of an alignment treatment layer applied in advance on the substrate, shear force, magnetic field, electric field, heat, etc., and these may be used alone or in combination. good. If necessary, a heating step may be performed.
The process of applying the composition for an anisotropic dye film on a substrate to form a film, the process of applying an external field to orient it, and the process of drying the solvent may be performed sequentially or simultaneously.

Examples of the method for applying the composition for forming an anisotropic dye film onto the substrate in the wet film forming method include a coating method, a dip coating method, an LB film forming method, and a known printing method. 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 onto the substrate using a coating method.
The orientation direction of the anisotropic dye film may be different from the coating direction. In the present invention, the orientation direction of an anisotropic dye film means, for example, the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, and the fast axis in the case of a retardation film. Or the slow axis.

The method of applying a composition for an anisotropic dye film to obtain an anisotropic dye film is not particularly limited, but for example, the method described in "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., published March 20, 1971) ), the method described on pages 253-277, the method described on pages 118-149 of "Creation and Application of Molecular Cooperative Materials" (CMC Publishing Co., Ltd., March 3, 1998) supervised by Kunihiro Ichimura, steps A slot die coating method, a spin coating method, a spray coating method, a bar coating method, a roll coating method, a blade coating method, a curtain coating method, a fountain method, a dip method, etc. on a substrate having a structure (which may be subjected to orientation treatment in advance) An example of this method is to apply it with. Among these, it is preferable to employ the slot die coating method or the bar coating method because a highly uniform anisotropic dye film can be obtained.

A die coater used in the slot die coating method is generally equipped with a coating machine that discharges a coating liquid, a so-called slit die. Slit dies are used, for example, in Japanese Unexamined Patent Publication No. 2-164480, Japanese Unexamined Patent Publication No. 6-154687, Japanese Unexamined Patent Application No. 9-131559, "Basics and Applications of Dispersion, Coating, and Drying" (2014). , Technosyste Co., Ltd., ISBN 9784924728707 C 305), "Wet coating technology for displays and optical components" (2007, Information Corporation, ISBN 9784901677752), "Precision coating and drying technology in the electronics field" (2007, Technical Information Association, ISBN 9784861041389) ) etc. These known slit dies can coat even flexible members such as films and tapes, and hard members such as glass substrates.

Substrates used for forming the anisotropic dye film of the present invention include glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, and triacetyl. Examples include cellulose or urethane films. In addition, in order to control the orientation direction of the dye, the surface of this substrate is coated with a known method (rubbing) described in "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000), pages 226 to 239. method, method of forming grooves (fine groove structure) on the surface of alignment film, method using polarized ultraviolet light/polarized laser (photoalignment method), alignment method by LB film formation, alignment method by oblique vapor deposition of inorganic material, etc.) Accordingly, an alignment treatment (alignment film) may be performed. Particularly preferred are alignment treatments using a rubbing method and a photoalignment method. Examples of materials used in the rubbing method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, and acrylic resin. Examples of materials used in the photo-alignment method include polycinnamate-based materials, polyamic acid/polyimide-based materials, and azobenzene-based materials. When an alignment treatment layer is provided, it is thought that the liquid crystal compound and the dye are oriented due to the influence of the alignment treatment of the alignment treatment layer and the shear force applied to the anisotropic dye film composition during coating.

When applying the composition for an anisotropic pigment film, the feeding method and feeding interval of the composition for an anisotropic pigment film are not particularly limited. If the anisotropic dye film is thin, the anisotropic dye film may be continuously anisotropic. It is desirable to apply the pigmented film composition while supplying it.

The speed at which the anisotropic dye film composition is applied is usually 0.001 m/min or more, preferably 0.01 m/min or more, more preferably 0.1 m/min or more, and even more preferably is 1.0 m/min or more, particularly preferably 5.0 m/min or more. Moreover, 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. When the coating speed is within the above range, the anisotropic dye film tends to have anisotropy and can be coated uniformly.
The coating temperature of the anisotropic dye film composition is generally 0°C or higher and 100°C or lower, preferably 80°C or lower, and more preferably 60°C or lower.
The humidity during application of the anisotropic dye film composition is preferably 10% RH or more, and preferably 80 RH% or less.

The anisotropic dye film may be subjected to insolubilization treatment. Insolubilization refers to a treatment that controls the elution of a compound from an anisotropic dye film and increases the stability of the film by reducing the solubility of the compound in the anisotropic dye film.
Specifically, film polymerization, overcoating, etc. are preferable from the viewpoints of ease of post-processing, durability of the anisotropic dye film, and the like.

When polymerizing a film, the film in which liquid crystal molecules and dye molecules are aligned is polymerized using light, heat, and/or radiation.

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

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

Although polymerization may be carried out using light, heat, and/or radiation, it is preferable to use photopolymerization or a combination of photopolymerization and thermal polymerization because the film forming process takes less time and the equipment is simpler. preferred.

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

The optical element in the present invention has functions such as a polarizing element, a retardation element, and a refractive anisotropy and conduction anisotropy that obtain linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption. Represents an element. These functions can be adjusted as appropriate by the anisotropic dye film forming process and the selection of the composition containing the substrate and organic compound (dye and transparent material).

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

The optical element may be provided with other layers in order to maintain and improve the function of the anisotropic dye film. For example, layers that have the function of blocking specific wavelengths and layers that have the function of blocking specific substances (oxygen blocking film, water vapor blocking film) are used to improve durability such as light resistance, heat resistance, water resistance, etc. etc.); wavelength cut filters used to change the color gamut or improve optical properties; and 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, polarizing elements are not limited to anisotropic dye films, but can also be used as overcoat layers, which have functions such as improving polarization performance and mechanical strength; adhesive layers or antireflection layers; alignment films; and retardation films. It may be used in combination with a layer having optical functions such as a function as a brightness-enhancing film, a function as a reflection or anti-reflection film, a function as a transflective film, a function as a diffusion film, etc. . Specifically, layers having the various functions described above may be laminated by coating, laminating, etc., and used as a laminate.
These layers can be provided as appropriate depending on the manufacturing process, characteristics, and functions, and the position, order, etc. of stacking them are not particularly limited. For example, 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. Further, the order in which each layer is formed may be before or after forming the anisotropic dye film.

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

The layer having a function as a retardation film can be formed by applying or bonding the retardation film to other layers constituting the polarizing element. The retardation film may be subjected to stretching treatment as described in, for example, Japanese Unexamined Patent Publication No. 2-59703, Japanese Unexamined Patent Publication No. 4-230704, etc., or stretching treatment described in Japanese Unexamined Patent Publication No. 7-230007, etc. It can be formed by processing.

The layer having a function as a brightness-enhancing film can be formed by applying or bonding the brightness-enhancing film to other layers constituting the polarizing element. The brightness enhancement film can be produced by forming micropores by the method described in Japanese Unexamined Patent Publication No. 2002-169025 and Japanese Unexamined Patent Publication No. 2003-29030, or by forming fine pores with a center wavelength of selective reflection. It can be formed by overlapping two or more different cholesteric liquid crystal layers.

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

The layer that functions as a retardation film or an optical compensation film contains a liquid crystal compound such as a discotic liquid crystal compound, a nematic liquid crystal compound, a smectic liquid crystal compound, or a cholesteric liquid crystal compound, in addition to other layers constituting the polarizing element. It can be formed by coating and orienting it. At that time, an alignment film may be provided on the substrate, and a retardation film or an optical compensation film may 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 in various display devices such as liquid crystal devices (LCDs) and organic electroluminescent devices (OLEDs), the electrodes constituting these display devices The anisotropic dye film of the present invention may be directly formed on the surface of a substrate or the like, or the substrate on which the anisotropic dye film of the present invention is formed may be used as a component of these display elements.

The present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
In the following description, "part" means "part by weight".

[Method for identifying liquid crystal phase]
The liquid crystallinity of the obtained composition for forming an anisotropic dye film was determined by differential scanning calorimetry (Seiko Instruments "DSC220CU"), X-ray structural analysis (Rigaku Co., Ltd. "NANO-Viewer"), and hot stage (Rigaku Co., Ltd. "NANO-Viewer"). 9 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000). It was identified as a liquid crystal according to the method described on pages 117 to 176 and pages 117 to 176.

[Measurement of transmittance and dichroic ratio for polarized light in the absorption axis/polarization axis direction of anisotropic dye film]
The transmittance of the obtained anisotropic dye film for polarized light in the absorption axis/polarization axis direction was measured using a spectrophotometer equipped with a Glan-Thompson polarizer (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100"). It was measured.
Linearly polarized measurement light is incident on the anisotropic dye film, and the transmittance for polarized light in the direction of the absorption axis of the anisotropic dye film and the transmittance for light polarized in the direction of the polarization axis of the anisotropic dye film are measured, and the transmittance is calculated using the following formula. The dichroic ratio (D) was calculated.
D= _Az / _Ay
(In the formula,
A _y =-log(T _y );
A _z =-log(T _z );
_Tz is the transmittance of the anisotropic dye film to polarized light in the absorption axis direction;
T _y is the transmittance of the anisotropic dye film to polarized light in the direction of the polarization axis. )

Specifically, we used a sandwich cell (cell gap: 8.0 μm, 10.0 μm) in which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, Inc.) was formed on glass as a base material. A composition for an anisotropic pigment film was injected in an isotropic phase into a material (preliminarily rubbed with a cloth) and cooled to 80 °C at a rate of 5 °C/min to obtain an anisotropic pigment film. The dichroic ratio was measured at each temperature while cooling down to 0°C at a rate of °C/min. Among them, the dichroic ratio at the temperature and wavelength that showed the maximum dichroic ratio was determined as the dichroic ratio of the anisotropic dye film. In addition, in the measurement at that temperature, the dichroic ratio at the wavelength at which the absorbance in the orthogonal position (absorption axis direction) showed the maximum value in the anisotropic dye film (the dichroic ratio at the wavelength at which the absorbance showed the maximum value in the film) Color ratio) was also measured.

[Synthesis of polymerizable liquid crystal compound]

<Liquid crystal compound (I-1)>
Lub et al. , Recl. Trav. Chim. Liquid crystal compound (I-1) was synthesized by a method similar to the compound described in 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 = 6.8Hz), 4.04 (t, 2H, J = 6 .8Hz), 4.15 (t, 2H, J = 6.8Hz), 5.82 (d, 2H, J = 10.4Hz), 6.12 (dd, 2H, J = 10.4, 17. 4Hz), 6.40 (d, 2H, J = 17.4Hz), 6.97 (d, 2H, J = 9.2Hz), 7.11 (d, 2H, J = 9.2Hz), 7. 21 (d, 2H, J = 9.0Hz), 8.13 (d, 2H, J = 9.0Hz)

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

Synthesis of (I-2-a):
Ethyl propiolate (9.7 g, 99 mmol) and copper(I) oxide (7.5 g, 94 mmol) were added to a solution of p-iodophenol (11.0 g, 50 mmol) in N,N-dimethylformamide (150 mL). The mixture was stirred at 110° C. for 9 hours and allowed to cool to room temperature. After filtering the precipitate, ethyl acetate was added, and the mixture was washed with water and then 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):
(I-2-a) (4.20g, 22.1mmol), 11-bromo-1-undecanol (5.55g, 22.1mmol), potassium carbonate (6.10g, 44.2mmol), N,N- Dimethylformamide (30 mL) was mixed and stirred at 80° C. for 4 hours. After filtering the precipitate, diethyl ether was added, and the mixture was washed with water and then 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 precipitate that had separated out 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) and tetrahydrofuran (20 mL) were mixed, followed by N,N-dimethylaniline (1.02 g, 8.4 mmol), 2,5-di-t -Butylphenol (54mg) was added. After cooling in an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was slowly added. After stirring in an ice bath for 6 hours, methylene chloride was added, and the mixture was washed successively with 1 mol/L hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine. 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):
(I-2-e) was synthesized by the synthesis method described in Japanese Patent Application Publication No. 2014-262884.

Synthesis of (I-2-f):
(I-2-d) (2.00 g, 5.17 mmol), (I-2-e) (1.01 g, 5.17 mmol), N,N-dimethylamino-4-pyridine (0.13 g, 1 .03 mmol), 2,5-di-t-butylphenol (58 mg), and methylene chloride (30 mL) were mixed, and after cooling in an ice bath, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride ( 1.09 g, 5.69 mmol) was added. After standing overnight, it was washed with a saturated ammonium chloride aqueous solution and then with a saturated saline solution. Purification was performed by silica gel column chromatography (hexane/ethyl acetate) to obtain 1.9 g of a white solid (I-2-f).

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

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

Lub et al. , Recl. Trav. ChIm. (I-2-i) was synthesized by a method similar to the compound described in Pays-Bas, 115, 321-328 (1996).
Next, (I-2-i) (trans form only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol), and ethanol (430 mL) were mixed, Stirred at 78°C for 2 hours. The solvent was distilled off, the residue was dissolved in ethyl acetate (150 mL), hexane (750 mL) was added, and the mixture was cooled. The precipitate was separated by filtration, washed with hexane, and dried to obtain 29.2 g of white solid (I-2-j).
(I-2-j) (37.2g, 118.3mmol), N,N-dimethylaniline (21.5g, 177.5mmol), 2,5-di-t-butylphenol (0.24g), tetrahydrofuran ( 380 mL) were mixed. After cooling in an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was slowly added. After the dropwise addition, the mixture was stirred at 50° C. for 2 hours, and then the solvent was distilled off until the liquid volume became 190 mL, and the mixture was poured 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).

Synthesis of (I-2):
(I-2-g) (494 mg, 1.03 mmol), (I-2-h) (400 mg, 1.09 mmol), N,N-dimethylamino-4-pyridine (27 mg, 0.22 mmol), 2, 5-di-t-butylphenol (2 mg) and methylene chloride (10 mL) were mixed and cooled in an ice bath, followed by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (230 mg, 1.19 mmol). was added. After stirring in an ice bath for 4 hours, the mixture was washed with a saturated aqueous ammonium chloride solution and then with a saturated saline solution. 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 of this compound are shown 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 = 6.8Hz), 3.99 (t, 2H, J = 6 .8Hz), 4.15 (t, 4H, J=6.8Hz), 5.80 (d, 2H, J=10.4Hz), 6.12 (dd, 2H, J=17.2, 10.
4Hz), 6.39 (d, 2H, J = 17.2Hz), 6.89 (d, 2H, J = 6.8Hz), 7.10 (d, 2H, J = 6.8Hz), 7. 19 (d, 2H, J = 6.8Hz), 7.55 (d, 2H, J = 6.8Hz)

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

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

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

Synthesis of (I-3-b):
4-iodophenol (3.62g, 16.5mmol), (I-3-a) (6.43g, 16.1mmol), N,N-dimethylamino-4-pyridine (0.39g, 3.20mmol) , methylene chloride (80 mL) were mixed, and after cooling in an ice bath, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) (3.39 g, 17.7 mmol) was added. Stir for a minute. Thereafter, the mixture was stirred at room temperature for 2 hours, and washed with a saturated ammonium chloride aqueous solution and then with a saturated saline solution. 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):
After (I-3-b) (5.00 g, 8.33 mmol) was completely dissolved in diisopropylamine (70 mL), dichlorobis(triphenylphosphine)palladium(II) (58 mg, 0.08 mmol) and iodide were added. Copper(I) (48 mg, 0.25 mmol) was mixed and trimethylsilylacetylene (0.98 g, 9.99 mmol) was added. After stirring at room temperature for 30 minutes, the mixture was extracted with water and ethyl acetate, and then 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):
(I-3-c) (4.30 g, 7.53 mmol) and chloroform (100 mL) were mixed, cooled in an ice bath, and then tetra-n-butylammonium fluoride (TBAF) tetrahydrofuran solution (1 mol/L, 9 mL) was added. After stirring for 20 minutes, the mixture 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):
(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 ( 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 at room temperature for 1 hour, the mixture was extracted with water and 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):
(I-3-e) obtained in the above operation and tetrahydrofuran (60 mL) were mixed, and after completely dissolving at 50° C., ethanol (60 mL) was added. P-toluenesulfonic acid pyridinium salt (PPTS) (0.54 g, 2.13 mmol) was added to this slurry solution, heated at 60° C. for 2 hours, and then left overnight. The next day, the mixture was heated again to 60° C. to completely dissolve it, and then the reaction solution was added to ice water. After extraction with chloroform and concentration of the solution, the obtained solid was suspended and washed with hexane to obtain 4.02 g of a white solid (I-3-f).

Synthesis of (I-3):
(I-3-f) (4.00g, 4.98mmol), acrylic acid (0.72g, 9.96mmol), N,N-dimethyl-4-aminopyridine (0.12g, 0.10mmol), dichloromethane ( After cooling in 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, and after 18 hours, acrylic acid (0.36 g, 4.98 mmol), EDC (1.05 g, 5.5 g, 5 mmol) and stirred for 5 hours.The reaction solution was washed with a saturated aqueous ammonium chloride solution and then with saturated brine, and purified by silica gel column chromatography (hexane/ethyl acetate) to obtain a white solid (I-3). 2.30g was obtained.

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. 2Hz), 6.12 (dd, 2H, J = 10.4, 17.2Hz), 5.81 (d, 2H, J = 10.4Hz), 4.15 (t, 4H, J = 6.8Hz) ), 3.46 (t, 4H, J=9.2Hz), 3.30-3.20 (m, 2H), 2.60-2.45 (m, 2H), 2.22-2.10 (m, 8H), 1.70-1.50 (m, 8H), 1.45-1.25 (m, 36H)

The fact that compound (I-3) exhibits liquid crystallinity means that 0.2 parts by weight of 4-methoxyphenol as a polymerization inhibitor is added to 100 parts by weight of the liquid crystal compound, and polarized light with a hot stage is attached. This was confirmed by observing birefringence at 70°C using a microscope.

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

Synthesis of (II-1-a):
Tetrahydrofuran (100 mL) and sodium hydride (purity 60%, 6.7 g, 168.0 mmol) were added to an ice-cooled reactor, and diethyl (4-nitrobenzyl)phosphonate (18.0 g, 65.9 mmol) was added. , 4-butylbenzaldehyde (9.1 g, 56.1 mmol), and tetrahydrofuran (50 mL) were added dropwise over 10 minutes, washed with tetrahydrofuran (30 mL), and stirred at 50° C. for 0.5 hour. The reaction solution was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was dissolved in ethyl acetate (20 mL) by heating, then hexane (50 mL) was added and cooled, and the precipitate precipitated was filtered, washed with hexane, and dried under reduced pressure to obtain (II-1- 15.0g of a) was obtained.

Synthesis of (II-1-b):
(II-1-a) (15.0 g, 53.3 mmol), tetrahydrofuran (150 mL), and iron powder (13.9 g, 248.9 mmol) were mixed, and ammonium chloride (13.3 g) was dissolved in water (30 mL). , 248.6 mmol) was added dropwise, and the mixture was stirred at 50°C for 3 hours. The mixture was filtered through Celite, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was suspended in hexane, and the precipitate was filtered, washed with hexane, and dried to obtain 10.9 g of (II-1-b).

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

The maximum absorption wavelength (λ _max ) of this compound in a 10 ppm chloroform solution was 459 nm, and the gram extinction coefficient was 107.6 Lg ⁻¹ cm ⁻¹ .
In addition, the structure was confirmed by NMR. The results are shown below.
^1H -NMR (CDCl ₃ , 400MHz) δ0.94 (t, 3H, J=7.2Hz), 1.32-1.43 (m, 2H), 1.55-1.68 (m, 2H) , 2.00-2.12 (m, 4H), 2.62 (t, 2H, J = 7.6Hz), 3.41 (t, 4H, J = 6.4Hz), 6.63 (d, 2H, J = 8.8Hz), 7.14 (d, 2H, J = 8.8Hz), 7.19 (d, 2H, J = 8.0Hz), 7.45 (d, 2H, J = 8 .0Hz), 7.60 (d, 2H, J = 8.4Hz), 7.84 (d, 2H, J = 8.4Hz), 7.88 (d, 2H, J = 9.2Hz)

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

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

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

The maximum absorption wavelength (λ _max ) of this compound in a 10 ppm chloroform solution was 458 nm, and the gram extinction coefficient was 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 = 7.2Hz), 1.24 (t, 6H, J = 7.2Hz), 1.33-1.44 (m, 2H), 1.57-1.67 (m, 2H), 2.64 (t, 2H, J = 7.2Hz), 3.47 (q, 4H, J = 7.2Hz), 6.74 ( d, 2H, J = 9.2Hz), 7.15 (d, 2H, J = 8.0Hz), 7.20 (d, 2H, J = 8.0Hz), 7.47 (d, 2H, J = 8.0Hz), 7.61 (d, 2H, J = 8.8Hz), 7.85 (d, 2H, J = 8.0Hz), 7.88 (d, 2H, J = 8.8Hz)
The solubility of this compound in cyclopentanone was measured in the same manner as for dye (II-1) (detection absorption wavelength: 254 nm) and was found to be 3.0% or more.

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

Synthesis of (II-3-a):
Tetrahydrofuran (200 mL) and sodium hydride (purity 60%, 10.1 g, 252.6 mmol) were added to an ice-cooled reactor, and diethyl (4-nitrobenzyl)phosphonate (23.0 g, 84.2 mmol) was added. , 4-heptyloxybenzaldehyde (18.6 g, 84.2 mmol), and tetrahydrofuran (200 mL) was added dropwise over 10 minutes, washed with tetrahydrofuran (30 mL), and stirred at 50° C. for 2 hours. The reaction solution was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was heated and dissolved in ethyl acetate (35 mL), hexane (80 mL) was added thereto, and the precipitate was filtered, washed with hexane, and dried under reduced pressure to obtain (II-3- 23.1g of a) was obtained.

Synthesis of (II-3-b):
(II-3-a) (23.1 g, 68.1 mmol), tetrahydrofuran (200 mL), and iron powder (19.0 g, 340.5 mmol) were mixed, and ammonium chloride (18.2 g) was dissolved in water (50 mL). , 340.5 mmol) was added dropwise, and the mixture was stirred at 50°C for 5 hours. The mixture was filtered through Celite, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (hexane/ethyl acetate), suspended in hexane, and the precipitate was filtered and washed with hexane. It was dried under reduced pressure to obtain 10.7 g of (II-3-b).

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

The maximum absorption wavelength (λ _max ) of this compound in a 10 ppm chloroform solution was 459 nm, and the gram extinction coefficient was 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 = 7.0Hz), 1.30 (t, 6H, J = 7.0Hz), 1.28-1.41 (m, 6H), 1.42-1.52 (m, 2H), 1.74-1.86 (m, 2H), 3.45 (q, 4H, J = 7.2Hz), 3.98 (t, 2H, J = 6.6Hz), 6.73 (d, 2H, J = 9.6Hz), 6.90 (d, 2H, J = 8.8Hz), 7.01 (d, 1H, J = 16 .4Hz), 7.13 (d, 1H, J = 16.4Hz), 7.46 (d, 2H, J = 8.8Hz), 7.58 (d, 2H, J = 8.4Hz), 7 .80-7.87 (m, 4H)
The solubility of this compound in cyclopentanone was measured in the same manner as for dye (II-1) (detection absorption wavelength: 254 nm) and was found to be 3.0% or more.

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

Synthesis of (II-4):
(II-1-b) (1.0 g, 4.0 mmol) and N-methylpyrrolidone (13 mL) were mixed, concentrated hydrochloric acid (1.0 g, 10.0 mmol) was added, and after cooling in an ice bath, water was added. Sodium nitrite (0.3 g, 4.4 mmol) dissolved in (1.3 mL) was added and stirred for 1 hour. The reaction solution was coupled with 1-phenylpiperidine (0.6 g, 4.0 mnmol) dissolved in methanol (25 mL) and water (6.5 mL) at pH = 7, and the precipitate was filtered and diluted with water. Washed and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane/methylene chloride) to obtain 760 mg of an orange solid (II-4).

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

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

The maximum absorption wavelength (λ _max ) of this compound in a 10 ppm chloroform solution was 459 nm, and the gram extinction coefficient was 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 = 7.2Hz), 1.16 (t, 6H, J = 7.2Hz), 1.39-1.45 (m, 2H), 1.67-1.71 (m, 2H), 2.74 (t, 2H, J = 7.6Hz), 3.38 (q, 4H, J = 7.2Hz), 7.20 ( d, 1H, J = 8.4Hz), 7.37 (d, 2H, J = 8.4Hz), 7.57-7.61 (m, 1H), 7.65-7.70 (m, 1H ), 7.90-7.95 (m, 3H), 8.10 (d, 2H, J = 8.8Hz), 8.17 (d, 2H, J = 8.8Hz), 8.31 (d , 1H, J=8.4Hz), 9.05(d, 1H, J=8.0Hz)
The solubility of this compound in cyclopentanone was measured in the same manner as for dye (II-1) (detection absorption wavelength: 254 nm) and found to be 2.2%.

The chemical structures of the liquid crystal compound and dye synthesized above are shown below. In the formula, C ₁₁ H ₂₂ means that 11 methylene chains are linearly bonded.

The solubility of dye (III-1) in cyclopentanone was measured in the same manner as dye (II-1) (detection absorption wavelength: 254 nm) and found to be 0.7%.
Further, the solubility of dye (III-2) in cyclopentanone was measured in the same manner as dye (II-1) (detection absorption wavelength: 254 nm) and found to be 0.8%.

Example 1
By adding 20.00 parts of liquid crystal compound (I-1) and 0.40 parts of dye (II-1) to 399.6 parts of chloroform, stirring to make them compatible, and removing the solvent, Composition 1 for forming an anisotropic dye film was obtained.
It was confirmed that the anisotropic dye film-forming composition 1 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
In order to determine the dichroic ratio using the obtained composition 1 for forming an anisotropic dye film, an anisotropic dye film 1 was prepared using a sandwich cell with a cell gap of 8.0 μm. , the dichroic ratio of the anisotropic dye film 1 was determined.
The results are shown in Table 2.

Example 2
Anisotropic pigment film forming composition 2 and anisotropic pigment film forming composition 2 were prepared in the same manner as in Example 1 except that 0.30 parts of pigment (II-2) was used instead of 0.40 parts of pigment (II-1). A pigment film 2 was obtained.
It was confirmed that the anisotropic dye film-forming composition 2 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
Regarding the anisotropic pigment film 2, the dichroic ratio of the anisotropic pigment film 2 was determined.
The results are shown in Table 2.

Example 3
Anisotropic pigment film forming composition 3 and anisotropic dye film forming composition 3 were prepared in the same manner as in Example 1 except that 0.30 parts of pigment (II-3) was used instead of 0.40 parts of pigment (II-1). A pigment film 3 was obtained.
It was confirmed that the anisotropic dye film-forming composition 3 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
Regarding the anisotropic pigment film 3, the dichroic ratio of the anisotropic pigment film 3 was determined.
The results are shown in Table 2.

Example 4
In place of 20.00 parts of liquid crystal compound (I-1), 20.00 parts of liquid crystal compound (I-2) was used, and in place of 0.40 part of dye (II-1), 0 part of dye (II-1) was used. Composition 4 for forming an anisotropic dye film and Anisotropic dye film 4 were obtained in the same manner as in Example 1, except that .28 parts were used.
It was confirmed that the anisotropic dye film-forming composition 4 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
Regarding the anisotropic pigment film 4, the dichroic ratio of the anisotropic pigment film 4 was determined.
The results are shown in Table 2.

Example 5
In place of 20.00 parts of liquid crystal compound (I-1), 20.00 parts of liquid crystal compound (I-2) was used, and in place of 0.40 part of dye (II-1), 0 part of dye (II-4) was used. Anisotropic dye film forming composition 5 and An anisotropic dye film 5 was obtained.
It was confirmed that the anisotropic dye film-forming composition 5 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
Regarding the anisotropic pigment film 5, the dichroic ratio of the anisotropic pigment film 5 was determined.
The results are shown in Table 2.

Comparative example 1
Anisotropic pigment film forming composition 7 and anisotropic pigment film forming composition 7 were prepared in the same manner as in Example 1 except that 0.2 parts of pigment (II-5) was used instead of 0.40 parts of pigment (II-1). A pigment film 7 was obtained.
It was confirmed that the anisotropic dye film-forming composition 7 exhibited liquid crystallinity by observing birefringence at 60° C. using a polarizing microscope equipped with a hot stage.
Regarding the anisotropic pigment film 7, the dichroic ratio of the anisotropic pigment film 7 was determined.
The results are shown in Table 2.

Example 6
399.6 parts of chloroform, 34.28 parts of liquid crystal compound (I-2), 0.34 parts of azo dye of formula (III-1) (manufactured by Hayashibara Co., Ltd.), and azo dye of formula (III-2) (manufactured by Showa Kako Co., Ltd.), 0.28 parts of azo dye of formula (II-1), and 0.21 parts of azo dye of color (II-4) were added, and the mixture was mixed by stirring. After that, the solvent was removed to obtain an anisotropic dye film-forming composition 8.
It was confirmed that the anisotropic dye film-forming composition 8 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
In order to determine the dichroic ratio by the method described above using the obtained composition 8 for forming an anisotropic pigment film, an anisotropic pigment film 8 was prepared, and the dichroic ratio of the anisotropic pigment film 8 was determined. Decided.
The maximum dichroic ratio of this anisotropic dye film 8 was 48.7 at 40° C. and a wavelength of 675 nm. The dichroic ratio at a wavelength of 495 nm at which the absorbance of the azo dye of formula (II-1) showed a maximum value in liquid crystal compound (I-2) was 31.7.

Example 7
717.9 parts of cyclopentanone, 243.6 parts of liquid crystal compound (I-2), 4.35 parts of azo dye of formula (II-1), and IRGACURE (registered trademark) 369 (product of BASF). After adding 5.58 parts and 3.62 parts of BYK-361N (manufactured by BYK-Chemie) and stirring at 80°C, a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm) was used. Composition 9 for anisotropic dye film was obtained by filtration.
Composition 9 for anisotropic dye film was formed into a film by spin coating on a substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, Inc., alignment film was formed by rubbing method) was formed on glass. After heating and drying at 120° C. for 2 minutes, the mixture was cooled to a liquid crystal phase and polymerized at an exposure dose of 500 mj/cm ² (based on 365 nm) to obtain an anisotropic dye film 9. When the obtained anisotropic dye film 9 was held over a commercially available polarizing plate and rotated, it became bright and dark, and it was confirmed that it exhibited good performance that could be used as a polarizing film.

Example 8
2615.7 parts of chloroform, 19.65 parts of liquid crystal compound (I-2), 0.06 parts of azo dye of formula (III-1) (manufactured by Hayashibara Co., Ltd.), and azo dye of formula (III-2) (manufactured by Showa Kako Co., Ltd.) and 0.05 part of dye (II-2) were added, stirred to make them compatible, and the solvent was removed to form an anisotropic dye film. Composition 10 was obtained.
It was confirmed that the anisotropic dye film-forming composition 10 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
In order to determine the dichroic ratio by the method described above using the obtained composition 10 for forming an anisotropic pigment film, an anisotropic pigment film 10 was prepared, and the dichroic ratio of the anisotropic pigment film 10 was determined. Decided.
The maximum dichroic ratio of this anisotropic dye film 10 was 31.0 at 40° C. and a wavelength of 595 nm. The dichroic ratio at a wavelength of 485 nm at which the absorbance of dye (II-2) reached its maximum value in liquid crystal compound (I-2) was 20.4.

Example 9
79.67 parts of chloroform, 20.00 parts of liquid crystal compound (I-2), 0.18 parts of azo dye of formula (III-2) (manufactured by Showa Kako Co., Ltd.), and 0 parts of dye (II-1). After adding .14 parts and stirring to make them compatible, the solvent was removed to obtain an anisotropic dye film-forming composition 11.
It was confirmed that the anisotropic dye film-forming composition 11 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
In order to determine the dichroic ratio by the method described above using the obtained composition 11 for forming an anisotropic pigment film, an anisotropic pigment film 11 was prepared, and the dichroic ratio of the anisotropic pigment film 11 was determined. Decided.
The maximum dichroic ratio of this anisotropic dye film 11 was 34.2 at 40° C. and a wavelength of 515 nm. The dichroic ratio at a wavelength of 470 nm, where the absorbance of dye (II-1) reached its maximum value in liquid crystal compound (I-2), was 28.7.

Example 10
Anisotropic dye film forming composition 12 and An anisotropic dye film 12 was obtained.
It was confirmed that the anisotropic dye film-forming composition 12 exhibited liquid crystallinity by observing birefringence at 70° C. using a polarizing microscope equipped with a hot stage.
In order to determine the dichroic ratio using the obtained composition 12 for forming an anisotropic pigment film, an anisotropic pigment film 12 was prepared, and the dichroic ratio of the anisotropic pigment film 12 was determined by the method described above. Decided.
The maximum dichroic ratio of this anisotropic dye film 12 was 28.8 at 70° C. and a wavelength of 515 nm. The dichroic ratio at a wavelength of 470 nm at which the absorbance of dye (II-1) reached its maximum value in liquid crystal compound (I-3) was 25.5.

Comparative example 2
Composition 13 for forming an anisotropic dye film was obtained in the same manner as in Example 1 except that 0.2 parts of dye (II-6) was used instead of 0.40 parts of dye (II-1). .
The solubility of dye (II-6) in cyclopentanone was measured in the same manner as dye (II-1) (detection absorption wavelength: 254 nm) and found to be 0.0%.
In composition 13 for forming an anisotropic dye film, precipitates were observed at 60° C. using a polarizing microscope equipped with a hot stage. This is thought to be due to the low solubility of the dye (II-6), and it is difficult to show a sufficient dichroic ratio even when forming an anisotropic dye film from Composition 13 for forming an anisotropic dye film. .

Comparative example 3
To 79.66 parts of chloroform, 20.00 parts of liquid crystal compound (I-2), 0.18 parts of azo dye of formula (III-2) (manufactured by Showa Kako Co., Ltd.), and 0 parts of dye (II-5). After adding .15 parts and stirring to make them compatible, the solvent was removed to obtain an anisotropic dye film-forming composition 14.
It was confirmed that the anisotropic dye film-forming composition 14 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
In order to determine the dichroic ratio by the method described above using the obtained composition 14 for forming an anisotropic pigment film, an anisotropic pigment film 14 was prepared, and the dichroic ratio of the anisotropic pigment film 14 was determined. Decided.
The maximum dichroic ratio of this anisotropic dye film 14 was 6.6 at 40° C. and a wavelength of 485 nm. The dichroic ratio at a wavelength of 465 nm, at which the absorbance of dye (II-5) reached its maximum value in liquid crystal compound (I-2), was 6.6.

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

The composition for forming an anisotropic dye film of the present invention can realize excellent optical performance, particularly a sufficient dichroic ratio. In particular, a sufficient dichroic ratio can be achieved in the wavelength range of 430 nm to 550 nm.
Since the anisotropic dye film of the present invention is formed using the composition for forming an anisotropic dye film of the present invention, it is possible to achieve excellent optical performance, particularly a sufficient dichroic ratio.
Since the optical element of the present invention includes the anisotropic dye film of the present invention, it can achieve excellent optical performance, particularly a sufficient dichroic ratio.

Claims (13)

Contains a dye and a polymerizable liquid crystal compound,
A composition for forming an anisotropic dye film, wherein the dye contains 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 phenyl group that may have a substituent (excluding a sulfo group);
A ² and A ³ each independently represent a phenylene group that may have a substituent (excluding a sulfo group);
X represents a monovalent organic group;
n represents 1, 2, or 3. ) Contains a dye and a polymerizable liquid crystal compound,
A composition for forming an anisotropic dye film, wherein the dye contains 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 phenyl group that may have a substituent (excluding a sulfo group),
The permissible substituents for the phenyl group are -R ^A or -O-R ^A , and R ^A each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms;
A ² represents a phenylene group which may have a substituent (excluding a sulfo group);
A ³ represents a phenylene group without a substituent;
X represents a monovalent organic group;
n represents 1, 2, or 3. ) Contains a dye and a polymerizable liquid crystal compound,
A composition for forming an anisotropic dye film, wherein the dye contains 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 phenyl group that may have a substituent (excluding a sulfo group),
The permissible substituents for the phenyl group are -R ^A or -O-R ^A , and R ^A each independently represents a linear or branched alkyl group having 1 to 15 carbon atoms;
A ² and A ³ each independently represent a phenylene group without a substituent;
X is -N(-R ^y )-R ^x , and R ^x and R ^y are each independently an optionally branched alkyl group having 1 to 3 carbon atoms, or R ^x and R ^y together represent an alkylene group having 2 to 6 carbon atoms which may have a branch;
n represents 1, 2, or 3. ) The composition for forming an anisotropic dye film according to claim 1, wherein n is 1. The composition for forming an anisotropic dye film according to claim 2, wherein n is 1. The composition for forming an anisotropic dye film according to claim 3, wherein n is 1. X is -O-(R ^x ) or -N(-R ^x )-R ^y ; R ^x and R ^y are each independently an optionally branched alkyl group having 1 to 15 carbon atoms; or represents an aryl group having 5 to 14 ring atoms; R ^x and R ^y together represent an alkylene group having 2 to 15 carbon atoms, which may have a branch; The alkyl group having 1 to 15 carbon atoms which may have a branch and the aryl group having 5 to 14 atoms constituting the ring may each have a substituent; One or more methylene groups contained in the alkylene group having 2 to 15 carbon atoms which may have an etheric oxygen atom, a thioetheric sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide The structure may be replaced by a bond, -CHF-, _-CF2- , -CHCl-, _-CCl2- ; the aminic nitrogen atom is -NH- or -N( ^Rz )-; The composition for forming an anisotropic dye film according to claim 1 or 4, wherein R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms. The ratio (r _n1 /r _n2 ) of the number of ring structures (r _n1 ) possessed by the polymerizable liquid crystal compound to the number (r _n2 ) possessed by the compound represented by the formula (1) is 0. The composition for forming an anisotropic dye film according to any one of claims 1 to 7 , which has a molecular weight of 7 to 1.5. The composition for forming an anisotropic dye film according to any one of claims 1 to 8 , 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 9 , further comprising a polymerization initiator. The wavelength at which the dye exhibits a maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm is greater than the wavelength at which the maximum value in the absorption curve in the wavelength range of 380 nm to 780 nm of the compound represented by formula (1) The composition for forming an anisotropic dye film according to any one of claims 1 to 10 , which contains one or more long compounds. An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of claims 1 to 11 . An optical element comprising the anisotropic dye film according to claim 12 .