WO2023181907A1

WO2023181907A1 - Compound, composition for forming anisotropic dye film, anisotropic dye film, and optical element

Info

Publication number: WO2023181907A1
Application number: PCT/JP2023/008490
Authority: WO
Inventors: 良輔朝戸; 靖志賀; 芳恵 ▲高▼見; 誠治秋山; 輝恒大澤; 奏也小島; 淳一大泉
Original assignee: 三菱ケミカル株式会社
Priority date: 2022-03-22
Filing date: 2023-03-07
Publication date: 2023-09-28
Also published as: TW202338062A

Abstract

A compound represented by formula (1). (In formula (1), -X¹ represents a monovalent organic group. -R¹¹ represents an alkyl group substituted by one or more fluorine atoms. -R¹² represents a hydrogen atom, an alkyl group, or an alkyl group substituted by one or more fluorine atoms. -R¹¹ and -R¹² may together form a ring. -A¹¹-, -A¹²-, -A¹³-, and -A¹⁴- each independently represent a 1,4-phenylene group that may have a substituent.)

Description

Compound, composition for forming an anisotropic pigment film, anisotropic pigment film and optical element

The present invention relates to compounds useful for polarizing films and the like included in display elements such as light control elements, liquid crystal elements (LCDs), and organic electroluminescent elements (OLEDs). The present invention also relates to a composition for forming an anisotropic dye film, an anisotropic dye film, and an optical element.

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 a low concentration of iodine (iodine-PVA polarizing films) (Patent Document 1). However, depending on the usage environment, iodine-PVA polarizing plates with low concentrations have problems such as the iodine sublimating or deteriorating, resulting in a change in color, and warping due to the relaxation of PVA stretching. There are problems that occur.

On the other hand, it is also known that an anisotropic dye film formed by coating a liquid crystal composition containing a dye functions as a polarizing film (Patent Document 2).

Japanese Unexamined Patent Publication No. 1-105204 JP2013-210624A

In a polarizing film formed by applying a liquid crystal composition containing a dye, it is desired that even a thin film has high light absorption selection performance and that there is no light leakage in the wavelength region of 350 nm to 800 nm. For this purpose, a plurality of dyes with good dichroic ratios are used, but in this case, it is necessary to adjust the absorption wavelength of the dye used so that it absorbs comprehensively in the wavelength region of 350 nm to 800 nm.

The present invention is directed to a compound that can shorten the maximum absorption wavelength in accordance with the absorption wavelength, and in which the resulting anisotropic dye film exhibits high dichroism even in a short wavelength region, and a compound containing the same. The present invention aims to provide a composition for forming an anisotropic dye film, an anisotropic dye film, and an optical element.

The present inventors have discovered that a compound having a specific structure can solve the above problems.
The present invention has the following aspects.

[1] A compound represented by the following formula (1).

(In formula (1),
-X ¹ represents a monovalent organic group.
-R ¹¹ represents an alkyl group substituted with one or more fluorine atoms.
-R ¹² represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
The alkyl group substituted with one or more fluorine atoms in -R ¹¹ , the alkyl group substituted with one or more fluorine atoms in -R ¹² , and the alkyl group substituted with one or more fluorine atoms may further have a substituent.
In addition, one or more methylene groups contained in the alkyl group substituted with one or more fluorine atoms in -R ¹¹ , the alkyl group in -R ¹² , and the alkyl group substituted with one or more fluorine atoms are , -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHCl-, or -CCl ₂ - The structure may be replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
-R ¹¹ and -R ¹² may be combined to form a ring, and the ring may have a substituent.
-A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ - each independently represent a 1,4-phenylene group which may have a substituent. )

[2] The compound according to [1], wherein -R ¹¹ in the formula (1) is an alkyl group substituted with one or more and five or less fluorine atoms.

[3] The compound according to [1], wherein -R ¹¹ in the formula (1) is an alkyl group having 1 to 10 carbon atoms and substituted with one or more fluorine atoms.

[4] -X ¹ in the above formula (1) is a hydrogen atom, -R ^a , -O-R ^a , -NH-R ^a , -C(=O)-R ^a , -C(=O)- O-R ^a , -C(=O)-NH-R ^a , -C(=O)-N(-R ^b )-R ^a , -O-C(=O)-R ^a , -NH-C (=O)-R ^a , -N(-R ^b )-C(=O)-R ^a , or -S-R ^a (-R ^a and -R ^b each independently have a branch. represents an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms.The alkyl group, The cycloalkyl group and the aryl group may each have a substituent. Also, -R ^a and -R ^b may be combined to form a ring having 2 to 15 carbon atoms, and The ring may have a substituent.Also, one or more methylene groups contained in the ring formed by combining the alkyl group, cycloalkyl group, aryl group, and R ^a and R ^b . -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF ₂ - , -CHCl-, or -CCl ₂ -, or a structure replaced with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group. ), the compound according to any one of [1] to [3].

[5] A composition for forming an anisotropic dye film containing a compound represented by the following formula (2) and a polymerizable liquid crystal compound.

(In formula (2),
-X represents a monovalent organic group.
-R ¹ represents an alkyl group substituted with one or more fluorine atoms.
-R ² represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
The alkyl group substituted with one or more fluorine atoms in -R ¹ , the alkyl group substituted with one or more fluorine atoms in -R ² , and the alkyl group substituted with one or more fluorine atoms may further have a substituent.
In addition, one or more methylene groups contained in the alkyl group substituted with one or more fluorine atoms in -R ¹ , the alkyl group in -R ² , and the alkyl group substituted with one or more fluorine atoms are - Replaced by O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHCl-, or -CCl ₂ - The structure may be replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
-R ¹ and -R ² may be combined to form a ring, and the ring may have a substituent.
-A ¹ -, -A ² - and -A ³ - each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent.
n represents 1, 2 or 3.
When n is 2 or 3, the plurality of -A ² -s may be the same or different. )

[6] The composition for forming an anisotropic dye film according to [5], wherein -A ³ - in the formula (2) is a 1,4-phenylene group which may have a substituent.

[7] For forming an anisotropic dye film according to [5] or [6], wherein -A ² - in the formula (2) is a 1,4-phenylene group which may have a substituent. Composition.

[8] The anisotropic dye according to any one of [5] to [7], wherein -A ¹ - in the formula (2) is a 1,4-phenylene group which may have a substituent. Composition for film formation.

[9] The composition for forming an anisotropic dye film according to any one of [5] to [8], wherein n in the formula (2) is 2.

[10] The anisotropic dye film according to any one of [5] to [9], wherein -R ¹ in the formula (2) is an alkyl group substituted with one or more and five or less fluorine atoms. Forming composition.

[11] Any one of [5] to [9], wherein -R ¹ in formula (2) is an alkyl group having 1 to 10 carbon atoms and substituted with one or more fluorine atoms. A composition for forming an anisotropic pigment film.

[12] X in the formula (2) is a hydrogen atom, -R ^a , -O-R ^a , -NH-R ^a , -C(=O)-R ^a , -C(=O)-O- R ^a , -C(=O)-NH-R ^a , -C(=O)-N(-R ^b )-R ^a , -OC(=O)-R ^a , -NH-C(= O) -R ^a , -N(-R ^b )-C(=O)-R ^a , or -S-R ^a (-R ^a and -R ^b may each independently have a branch) Represents an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms.The above alkyl group, cycloalkyl The group and the aryl group may each have a substituent. Also, -R ^a and -R ^b may be combined to form a ring having 2 to 15 carbon atoms, and the ring is It may have a substituent.In addition, one or more methylene groups contained in the ring formed by the alkyl group, cycloalkyl group, aryl group, and R ^a and R ^b are: -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF ₂ -, - It may be a structure in which it is replaced by CHCl- or -CCl ₂ -, or it may be a structure in which it is replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.) The composition for forming an anisotropic dye film according to any one of [5] to [11].

[13] The composition for forming an anisotropic dye film according to any one of [5] to [12], wherein the polymerizable liquid crystal compound is a low molecular weight polymerizable liquid crystal compound that does not have a repeating unit structure.

[14] An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of [5] to [13].

[15] An optical element comprising the anisotropic dye film according to [14].

The compound of the present invention can shorten the absorption maximum wavelength by adjusting the absorption wavelength, and also exhibits high dichroism.
The composition for forming an anisotropic dye film of the present invention contains the above compound and can realize a high dichroic ratio.
According to the anisotropic dye film and optical element using the composition for forming an anisotropic dye film of the present invention, excellent optical performance, particularly a sufficient dichroic ratio, can be achieved.

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

The anisotropic dye film 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.

The composition for forming an anisotropic dye film in the present invention includes a dye and a polymerizable liquid crystal compound.
The composition for forming an anisotropic dye 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 composition for forming an anisotropic dye film is preferably a solution from the viewpoint of ease of application to a substrate. 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 state of liquid crystal phase specifically refers to the state of the liquid crystal phase, as described on pages 1 to 16 of "Fundamentals and Applications of Liquid Crystals" (Shoichi Matsumoto, Ichiyoshi Tsunoda, 1991). 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.

In the present invention, a dye is a substance or compound that absorbs at least a portion of wavelengths in the visible light region (350 nm to 800 nm). Examples of dyes that can be used in the present invention include dichroic dyes.
A dichroic dye 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.
The dye may or may not have liquid crystallinity. Having liquid crystallinity means exhibiting a liquid crystal phase at any temperature.

[Compound]
The compound of the present invention is a compound represented by the following formula (1).

In formula (1),
-X ¹ represents a monovalent organic group.
-R ¹¹ represents an alkyl group substituted with one or more fluorine atoms.
-R ¹² represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
The alkyl group substituted with one or more fluorine atoms in -R ¹¹ , the alkyl group substituted with one or more fluorine atoms in -R ¹² , and the alkyl group substituted with one or more fluorine atoms may further have a substituent.
In addition, one or more methylene groups contained in the alkyl group substituted with one or more fluorine atoms in -R ¹¹ , the alkyl group in -R ¹² , and the alkyl group substituted with one or more fluorine atoms are , -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHCl-, or -CCl ₂ - The structure may be replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
-R ¹¹ and -R ¹² may be combined to form a ring, and the ring may have a substituent.
-A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ - each independently represent a 1,4-phenylene group which may have a substituent.

The composition for forming an anisotropic dye film of the present invention contains a compound represented by the following formula (2) and a polymerizable liquid crystal compound.

In formula (2),
-X represents a monovalent organic group.
-R ¹ represents an alkyl group substituted with one or more fluorine atoms.
-R ² represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
The alkyl group substituted with one or more fluorine atoms in -R ¹ , the alkyl group substituted with one or more fluorine atoms in -R ² , and the alkyl group substituted with one or more fluorine atoms may further have a substituent.
In addition, one or more methylene groups contained in the alkyl group substituted with one or more fluorine atoms in -R ¹ , the alkyl group in -R ² , and the alkyl group substituted with one or more fluorine atoms are - Replaced by O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHCl-, or -CCl ₂ - The structure may be replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
-R ¹ and -R ² may be combined to form a ring, and the ring may have a substituent.
-A ¹ -, -A ² - and -A ³ - each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent.
n represents 1, 2 or 3.
When n is 2 or 3, the plurality of -A ² -s may be the same or different.

Hereinafter, the compound represented by formula (1) may be referred to as "compound (1)". The compound represented by formula (2) is sometimes referred to as "compound (2)." Moreover, compound (1) and compound (2) may be collectively referred to as "the compound of the present invention."

(-X ¹ , -X)
In formula (1), -X ¹ represents a monovalent organic group.

In formula (2), -X represents a monovalent organic group.

Examples of the monovalent organic group in -X ¹ and -X include a hydrogen atom, a hydroxy group, an amino group, a cyano group, a carbamoyl group, a nitro group, a halogen atom, -R ^a , -O-R ^a , -NH -R ^a , -C(=O)-R ^a , -C(=O)-O-R ^a , -C(=O)-NH-R ^a , -C(=O)-N(-R ^b )-R ^a , -OC(=O)-R ^a , -NH-C(=O)-R ^a , -N(-R ^b )-C(=O)-R ^a , -S-R Examples include ^a . Since a high dichroic ratio tends to be obtained, hydrogen atoms, -R ^a , -O-R ^a , -NH-R ^a , -C(=O)-R ^a , -C(=O)-O-R ^a , -C(=O)-NH-R ^a , -C(=O)-N(-R ^b )-R ^a , -OC(=O)-R ^a , -NH-C(=O) -R ^a , -N(-R ^b )-C(=O)-R ^a , -SR ^a are preferred, -R ^a , -O-R ^a , -C(=O)-R ^a , - C(=O)-O-R ^a and -OC(=O)-R ^a are more preferred.

Here, -R ^a and -R ^b each independently constitute an optionally branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, or a ring. It represents a cycloalkyl group having 5 to 14 atoms, preferably 5 to 10 atoms, or an aryl group having 5 to 14 ring atoms, preferably 5 to 10 atoms.
The alkyl group, cycloalkyl group, and aryl group may each have a substituent.
Furthermore, -R ^a and -R ^b may be combined to form a ring having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, and the ring may have a substituent.

Examples of the optionally branched alkyl group having 1 to 15 carbon atoms in -R ^a and -R ^b include n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, 1-methylethyl group, 1,1-dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 2 , 2-dimethylpropyl group, 1,2,2-trimethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1, 3-dimethylbutyl group, 1,3,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 2,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 4-methylpentyl group group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 4,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,2-dimethylpentyl group, 3,4-dimethylpentyl group group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 3, 3,4-trimethylpentyl group, 2,3,3-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,2,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 1, 2,2-trimethylpentyl group, 2,3,4-trimethylpentyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1-methylhexyl group, 5, 5-dimethylhexyl group, 4,4-dimethylhexyl group, 3,3-dimethylhexyl group, 2,2-dimethylhexyl group, 4,5-dimethylhexyl group, 3,5-dimethylhexyl group, 2,5- Dimethylhexyl group, 1,5-dimethylhexyl group, 1,4-dimethylhexyl group, 4,5,5-trimethylhexyl group, 3,5,5-trimethylhexyl group, 2,5,5-trimethylhexyl group, 1,5,5-trimethylhexyl group, 6-methylheptyl group, 5-methylheptyl group, 6,6-dimethylheptyl group, 5,6-dimethylheptyl group, 4,6-dimethylheptyl group, 3,6- Examples include dimethylheptyl group, 2,6-dimethylheptyl group, 1,6-dimethylheptyl group, 6-methyloctyl group, 3-methyloctyl group, 1-methyloctyl group, and 1-methylnonyl group. From the viewpoint of good molecular alignment with the polymerizable liquid crystal compound used in the present invention, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-methylpropyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2,3,3-trimethylbutyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 4,4-dimethylpentyl group, 3 ,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 3,3,4-trimethylpentyl group, 2,3,3 -Trimethylpentyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 5,5-dimethylhexyl group, 4,4-dimethylhexyl group, 3,3-dimethyl Preferred are hexyl group, 3,5,5-trimethylhexyl group, 5-methylheptyl group, 6-methyloctyl group, 3-methyloctyl group, 1-methyloctyl group, and 1-methylnonyl group.

Examples of the cycloalkane ring in the cycloalkyl group having 5 to 14 ring atoms in -R ^a and -R ^b include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. , cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, bicyclo[2.2.2]octane ring, 4-methylcyclohexane ring, 4-ethylcyclohexane ring, 4-propylcyclohexane ring, A 4-butylcyclohexane ring is mentioned.

Examples of the aryl group having 5 to 14 ring atoms in -R ^a and -R ^b include a phenyl group and a naphthyl group.

When -R ^a and -R ^b combine to form a ring having 2 to 15 carbon atoms, the ring is, for example, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Examples thereof include an octane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetrahydronaphthalene ring, and a bicyclo[2.2.2]octane ring.

The alkyl group having 1 to 15 carbon atoms which may have a branch, the cycloalkyl group having 5 to 14 atoms forming the ring, and the aryl group having 5 to 14 atoms forming the ring. , one or more methylene groups contained in the ring having 2 to 15 carbon atoms formed by the combination of -R ^a and -R ^b are -O-, -S-, -NH-, -C (=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF ₂ -, -CHCl-, or -CCl ₂ - replaced ) structure, or a structure replaced with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.

Permissible substituents for the optionally branched alkyl group having 1 to 15 carbon atoms in -R ^a and -R ^b include -OH, -O-R ^f , -OC( =O)-R ^f , -NH ₂ , -NH-R ^f , -N(-R ^g )-R ^f , -C(=O)-R ^f , -C(=O)-O-R ^f , -C(=O)-NH ₂ , -C(=O)-NH-R ^f , -C(=O)-N(-R ^g )-R ^f , -SH, -SR ^f , sulfamoyl group , a carboxy group, a cyano group, a nitro group, a halogen, an acryloyloxy group, a methacryloyloxy group, a glycidyloxy group, and other polymerizable groups.
-R ^f and -R ^g each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.
One or more methylene groups contained in the linear or branched alkyl group having 1 to 15 carbon atoms, which are -R ^f and -R ^g , are -O-, -S-, -NH- , -N(-R ^h )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF ₂ -, -CHCl- , or a structure replaced by -CCl ₂ -, or a structure replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group. Here, -R ^h represents a linear or branched alkyl group having 1 to 6 carbon atoms.

The permissible substituents for the optionally branched alkyl group having 1 to 15 carbon atoms in -R ^a and -R ^b are preferably -O-R ^f . -O-R ^f includes, for example, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, acryloyloxy group, Examples include methacryloyloxy group and glycidyloxy group.

As substituents permissible for the cycloalkyl group having 5 to 14 ring atoms in R ^a and R ^b and the aryl group having 5 to 14 ring atoms, for example, - R ⁱ , -OH, -O-R ⁱ , -OC(=O)-R ⁱ , -NH ₂ , -NH-R ⁱ , -N(-R ^j )-R ⁱ , -C(=O )-R ⁱ , -C(=O)-O-R ⁱ , -C(=O)-NH ₂ , -C(=O)-NH-R ⁱ , -C(=O)-N(-R ^j ) -R ⁱ , -SH, -S-R ⁱ , trifluoromethyl group, sulfamoyl group, carboxy group, cyano group, nitro group, and halogen. Here, -R ⁱ and -R ^j each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
Permissible substituents for the cycloalkyl group having 5 to 14 ring atoms in -R ^a and -R ^b and the aryl group having 5 to 14 ring atoms include -R ⁱ , -O-R ⁱ are preferred. -R ⁱ and -O-R ⁱ include, for example, a methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, 2-ethylhexyloxy group, 5,5 -dimethyl-3-methylhexyloxy group.

When -R ^a and R ^b combine to form a ring having 2 to 15 carbon atoms, examples of permissible substituents on the ring include -R ⁱ , -OH, -O-R ⁱ , - OC(=O)-R ⁱ , -NH ₂ , -NH-R ⁱ , -N(-R ^j )-R ⁱ , -C(=O)-R ⁱ , -C(=O)-O -R ⁱ , -C(=O)-NH ₂ , -C(=O)-NH-R ⁱ , -C(=O)-N(-R ^j )-R ⁱ , -SH, -SR ⁱ , trifluoromethyl group, sulfamoyl group, carboxy group, cyano group, nitro group, and halogen. Here, -R ⁱ and -R ^j each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
When -R ^a and -R ^b combine to form a ring having 2 to 15 carbon atoms, -R ⁱ and -O-R ⁱ are preferred as the substituents allowed on the ring. -R ⁱ and -O-R ⁱ are, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexoxy group, n-heptoxy group, n-octoxy group, 2-ethylhexyloxy group, 5,5 -dimethyl-3-methylhexyloxy group.

The monovalent organic group in -X ¹ and -X preferably does not have a polymerizable group from the viewpoint of improving molecular alignment with the polymerizable liquid crystal compound. On the other hand, the monovalent organic group in -X ¹ and -X preferably has a polymerizable group from the viewpoint of improving the mechanical strength of the anisotropic dye film.

(-R ¹¹ , -R ¹² , -R ¹ , -R ² )
In formula (1), -R ¹¹ represents an alkyl group substituted with one or more fluorine atoms.
-R ¹² represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
-R ¹¹ and -R ¹² may be combined to form a ring.

In formula (2), -R ¹ represents an alkyl group substituted with one or more fluorine atoms.
-R ² represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
-R ¹ and -R ² may be combined to form a ring, and the ring may have a substituent.

The number of carbon atoms in the alkyl group substituted with one or more fluorine atoms in -R ¹¹ and -R ¹ is 1 or more and 10 or less, from the viewpoint of good molecular orientation with the polymerizable liquid crystal compound used in the present invention. It is preferably 1 or more and 6 or less, more preferably 2 or more and 4 or less. The alkyl group may be branched, linear, or cyclic cycloalkyl group.
Further, from the viewpoint of solubility, the number of fluorine atoms in the alkyl group is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.

-R ¹¹ and -R ¹ are, for example, 1-fluoromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 1,2-difluoroethyl group, 2,2-difluoroethyl group, 2,2, 2-trifluoroethyl group, 1,2,2,2-tetrafluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 1-fluoropropyl group, 2-fluoropropyl group, 3-fluoro Propyl group, 2,2-difluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 2,3,3,3-tetrafluoropropyl group, 2,2,3,3 , 3-pentafluoropropyl group, 1-fluorobutyl group, 2-fluorobutyl group, 3-fluorobutyl group, 4-fluorobutyl group, 1,1-difluorobutyl group, 2,2-difluorobutyl group, 3, 3-difluorobutyl group, 4,4-difluorobutyl group, 4,4,4-trifluorobutyl group, 3,4,4,4-tetrafluorobutyl group, 3,3,4,4,4-pentafluoro Butyl group, 1-fluoropentyl group, 2-fluoropentyl group, 3-fluoropentyl group, 4-fluoropentyl group, 5-fluoropentyl group, 1,1-difluoropentyl group, 2,2-difluoropentyl group, 3 , 3-difluoropentyl group, 4,4-difluoropentyl group, 5,5-difluoropentyl group, 5,5,5-trifluoropentyl group, 4,5,5,5-tetralifluoropentyl group, 4, 4,5,5,5-pentafluoropentyl group, 1-fluorohexyl group, 2-fluorohexyl group, 3-fluorohexyl group, 4-fluorohexyl group, 5-fluorohexyl group, 6-fluorohexyl group, 6 , 6-difluorohexyl group, 6,6,6-trifluorohexyl group, 2-fluoro-1-methylethyl group, 2,2-difluoro-1-methylethyl group, 2,2,2-trifluoro-1 -methylethyl group, 2-fluoro-1,1-dimethylethyl group, 2,2-difluoro-1,1-dimethylethyl group, 2,2,2-trifluoro-1,1-dimethylethyl group, 3- Fluoro-1-methylpropyl group, 3,3-difluoro-1-methylpropyl group, 3,3,3-trifluoro-1-methylpropyl group, 3-fluoro-2-methylpropyl group, 3,3-difluoro -2-methylpropyl group, 3,3,3-trifluoro-2-methylpropyl group, 3-fluoro-1,2-dimethylpropyl group, 3,3-difluoro-1,2-dimethylpropyl group, 3, 3,3-trifluoro-1,2-dimethylpropyl group, 3-fluoro-2,2-dimethylpropyl group, 3,3-difluoro-2,2-dimethylpropyl group, 3,3,3-trifluoro- 2,2-dimethylpropyl group, 3-fluoro-1,2,2-trimethylpropyl group, 3,3-difluoro-1,2,2-trimethylpropyl group, 3,3,3-trifluoro-1,2 , 2-trimethylpropyl group, 2-fluorocyclohexyl group, 3-fluorocyclohexyl group, 4-fluorocyclohexyl group, 2-fluoro-4-methylcyclohexyl group, 3-fluoro-4-methylcyclohexyl group, 2-fluoro-4 -Ethylcyclohexyl group, 3-fluoro-4-ethylcyclohexyl group, 2-fluoro-4-propylcyclohexyl group, 3-fluoro-4-propylcyclohexyl group, 2-fluoro-4-butylcyclohexyl group, 3-fluoro-4 -butylcyclohexyl group. Among them, from the viewpoint of balancing molecular orientation and solubility with the polymerizable liquid crystal compound, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoroethyl group, Propyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 4-fluorobutyl group, 4,4-difluorobutyl group, 4,4,4-trifluorobutyl group are preferred, and 2 -fluoroethyl group, 2,2-difluoroethyl group, and 2,2,2-trifluoroethyl group are more preferred.

The number of carbon atoms in the alkyl group of -R ¹² and -R ² and the alkyl group substituted with one or more fluorine atoms is 1 or more from the viewpoint of good molecular orientation with the polymerizable liquid crystal compound used in the present invention. It is preferably 10 or less, more preferably 1 or more and 6 or less, and even more preferably 2 or more and 4 or less. The alkyl group may be branched, linear, or cyclic cycloalkyl group. Furthermore, from the viewpoint of solubility, the number of fluorine atoms in the alkyl group substituted with fluorine atoms is preferably 5 or less, more preferably 3 or less, and even more preferably 2 or less.

Examples of the alkyl group for -R ¹² and -R ² include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, 1-methylethyl group, 1,1 -dimethylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2,2-trimethylpropyl group, 1-methylbutyl group, 2- Methylbutyl group, 3-methylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1,3,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 2,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group, 4-methylpentyl group, 3- Methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 4,4-dimethylpentyl group, 3,3-dimethylpentyl group, 2,2-dimethylpentyl group, 3,4-dimethylpentyl group, 2, 4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,4,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 3,3,4- Trimethylpentyl group, 2,3,3-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,2,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 1,2,2- Trimethylpentyl group, 1,1,2-trimethylpentyl group, 1,1,3-trimethylpentyl group, 1,1,4-trimethylpentyl group, 2,3,4-trimethylpentyl group, 1,2,3- Trimethylpentyl group, 1,3,4-trimethylpentyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1-methylhexyl group, 5,5-dimethylhexyl group group, 4,4-dimethylhexyl group, 3,3-dimethylhexyl group, 2,2-dimethylhexyl group, 4,5-dimethylhexyl group, 3,5-dimethylhexyl group, 2,5-dimethylhexyl group, 1,5-dimethylhexyl group, 1,4-dimethylhexyl group, 4,5,5-trimethylhexyl group, 3,5,5-trimethylhexyl group, 2,5,5-trimethylhexyl group, 1,5, 5-trimethylhexyl group, 6-methylheptyl group, 5-methylheptyl group, 6,6-dimethylheptyl group, 5,6-dimethylheptyl group, 4,6-dimethylheptyl group, 3,6-dimethylheptyl group, 2,6-dimethylheptyl group, 1,6-dimethylheptyl group, 7-methyloctyl group, 6-methyloctyl group, 5-methyloctyl group, 4-methyloctyl group, 3-methyloctyl group, 2-methyloctyl group group, 1-methyloctyl group, 8-methylnonyl group, 7-methylnonyl group, 6-methylnonyl group, 5-methylnonyl group, 4-methylnonyl group, 3-methylnonyl group, 2-methylnonyl group, 1-methylnonyl group, cyclohexyl group , 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, and 4-butylcyclohexyl group.

Examples of the alkyl group substituted with one or more fluorine atoms for -R ¹² and -R ² include the alkyl groups substituted with one or more fluorine atoms exemplified as -R ¹¹ and -R ¹ , and preferred Things are the same.

-R ¹² and -R ² include methyl group, ethyl group, n-propyl group, n-butyl group, 2-fluoroethyl group, 2, 2-difluoroethyl group, 2,2,2-trifluoroethyl group, 3-fluoropropyl group, 3,3-difluoropropyl group, 3,3,3-trifluoropropyl group, 4-fluorobutyl group, 4, 4-difluorobutyl group and 4,4,4-trifluorobutyl group are preferred.

Examples of the ring formed by combining -R ¹¹ and -R ¹² or -R ¹ and -R ² include a 2-fluoroaziridine ring, a 2,2-difluoroaziridine ring, a 2-fluoroazetidine ring, 2,2-difluoroazetidine ring, 3-fluoroazetidine ring, 3,3-difluoroazetidine ring, 2-fluoropyrrolidine ring, 2,2-difluoropyrrolidine ring, 3-fluoropyrrolidine ring, 3,3-fluoro Pyrrolidine ring, 3,4-difluoropyrrolidine ring, 2,5-difluoropyrrolidine ring, 3,3,4,4-tetrafluoropyrrolidine ring, 2-fluoropiperidine ring, 2,2-difluoropiperidine ring, 3-fluoropiperidine ring, 3,3-difluoropiperidine ring, 4,4-difluoropiperidine ring, 2,6-difluoropiperidine ring, 3,5-difluoropiperidine ring, and 3,3,5,5-tetrafluoropyrrolidine. Among them, from the viewpoint of good molecular orientation with the polymerizable liquid crystal compound, 2,2-difluoropyrrolidine ring, 3,3,4,4-tetrafluoropyrrolidine ring, 3,3-difluoropiperidine ring, 3, A 3,5,5-tetrafluoropyrrolidine ring is preferred. On the other hand, from the viewpoint of solubility, it is preferable that -R ¹¹ and -R ¹² and -R ¹ and -R ² do not form a ring together.

In the alkyl group substituted with one or more fluorine atoms in -R ¹¹ , -R ¹² , -R ¹ , -R ² , it is important from the viewpoint of solubility that the fluorine atom is substituted at the terminal carbon atom of the alkyl group. preferred. Furthermore, the total number of substituted fluorine atoms in -R ¹¹ and -R ¹² and the total number of substituted fluorine atoms in -R ¹ and -R ² are each preferably from 1 to 6, more preferably from 1 to 4. preferable. Within the above range, solubility tends to be good.

-R ¹¹ , -R ¹ alkyl group substituted with one or more fluorine atoms, -R ¹² , -R ² alkyl group, one or more alkyl groups substituted with one or more fluorine atoms The methylene group of is -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHCl-, or It may be a structure in which it is replaced by -CCl ₂ -, or it may be a structure in which it is replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.

The alkyl group substituted with one or more fluorine atoms in -R ¹¹ and -R ¹ , the alkyl group substituted with one or more fluorine atoms in -R ¹² and -R ² , each have a substituent. may have. Permissible substituents include, for example, -OH, -O-R ^p , -OC(=O)-R ^p , -NH ₂ , -NH-R ^p , -N(-R ^q )-R ^p , -C(=O)-R ^p , -C(=O)-O-R ^p , -C(=O)-NH ₂ , -C(=O)-NH-R ^p , -C(= O)-N(-R ^q )-R ^p , -SH, -S-R ^p , sulfamoyl group, carboxy group, cyano group, nitro group, halogen other than fluorine atom, acryloyloxy group, methacryloyloxy group, glycidyloxy Examples include polymerizable groups such as groups.
-R ^p and -R ^q each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms.

(-A ¹¹ -, -A ¹² -, -A ¹³ -, -A ¹⁴ -)
In formula (1), -A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ - each independently represent a 1,4-phenylene group which may have a substituent.

Permissible substituents for the 1,4-phenylene groups of -A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ - include -R ^A , -OH, -O-R ^A , -OC(=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- Examples include R ^A , 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. The number of carbon atoms in -R ^A and -R ^B is preferably 1 or more and 12 or less, more preferably 1 or more and 9 or less, from the viewpoint of good molecular alignment with the polymerizable liquid crystal compound used in the present invention. Note that the 1,4-phenylene group which may have a substituent does not include a divalent group of a naphthalene ring (naphthylene group).

One or more methylene groups contained in the linear or branched alkyl group in -R ^A and -R ^B include an ether oxygen atom, a thioether sulfur atom, an amine nitrogen atom (-NH-, -N(R ^z )-: Here, R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms), a carbonyl group, an ester bond, It may have a structure substituted by an amide bond, -CHF-, -CF ₂ -, -CHCl-, -CCl ₂ -, and a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group may be substituted. You can leave it there.

Permissible substituents for the 1,4-phenylene groups of -A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ - include - R ^A , -O-R ^A , trifluoromethyl group, and fluoro group are preferred. -R ^A is, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, 5,5-dimethyl-3-methylhexyl group. Can be mentioned.

-A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ - are preferably unsubstituted 1,4-phenylene groups from the viewpoint of dichroic ratio.

(-A ¹ -, -A ² -, -A ³ -)
In formula (2), -A ¹ -, -A ² - and -A ³ - each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent.

-A ¹ -, -A ² -, -A ³ - aromatic hydrocarbon rings include, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring. ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.

-A ¹ -, -A ² -, -A ³ - are divalent groups of aromatic hydrocarbon rings, and the absorption transition moment of compound (2) tends to coincide with the long axis direction of the dye. A divalent group of a benzene ring (phenylene group) and a divalent group of a naphthalene ring (naphthylene group), which may have a substituent, are preferred because they can increase the color ratio; ) is more preferable. In particular, 1,4-phenylene group, 1,4-naphthylene group, and 2,6-naphthylene group are more preferred, 1,4-phenylene group is even more preferred, and 1,4-phenylene group having no substituent is particularly preferred. preferable. With the above, the absorption transition moment of compound (2) tends to coincide with the long axis direction of compound (2), and the dichroic ratio can be increased. Note that the divalent group of the benzene ring (phenylene group) which may have a substituent does not include the divalent group of the naphthalene ring (naphthylene group).

Permissible substituents for the divalent group of the aromatic hydrocarbon ring -A ¹ -, -A ² -, -A ³ - include the above-mentioned -A ¹¹ -, -A ¹² -, -A ¹³ - and Permissible substituents for the 1,4-phenylene group of -A ¹⁴ - are listed, and preferred substituents are also the same as for -A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ -.

(n)
In formula (2), n represents 1, 2 or 3.
When n is 2 or 3, the plurality of -A ² -s may be the same or different.
In order to improve the molecular orientation with the polymerizable liquid crystal compound in the present invention and from the viewpoint of solubility, n is preferably 1 or 2, and more preferably 2.

(-N=N-)
-N=N- in formulas (1) and (2) is preferably trans-type from the viewpoint of improving the linearity of the compound of the present invention.

(Specific examples of compounds of the present invention)
Specific examples of the compounds of the present invention include, but are not limited to, the following compounds.

(absorption characteristics)
The compound of the present invention may have maximum absorption (λmax1) in the wavelength range of 350 to 800 nm, preferably in the wavelength range of 380 to 600 nm, in the anisotropic dye film prepared by the method described below. It has absorption, more preferably in the wavelength range of 400 to 560 nm, and still more preferably in the wavelength range of 420 to 550 nm. By having maximum absorption (λmax1) in this wavelength range, when combined with a dye having maximum absorption on the longer wavelength side, it tends to be possible to comprehensively absorb the wavelength range of 350 to 800 nm.

It is preferable that the compound of the present invention has a maximum absorption (λmax1 described above) in the anisotropic dye film at a longer wavelength than the maximum absorption (λmax2) measured after being dissolved in a solvent. This long wavelength shift is a phenomenon that occurs when the compound of the present invention is dispersed in a polymerizable liquid crystal compound and/or a polymer having units based on a polymerizable liquid crystal compound. This indicates that there is strong intermolecular interaction between the liquid crystal compound and/or the polymer having units based on the polymerizable liquid crystal compound. Long wavelength shift means that the difference in absorption maximum (λmax1-λmax2) becomes a positive value, and the difference is preferably 10 nm or more, more preferably 20 nm or more, and 30 nm or more. It is even more preferable that there be.

(solubility)
The solubility of the compound of the present invention is not particularly limited, but the solubility in cyclopentanone is preferably 0.4% by mass or more, more preferably 0.9% by mass or more, and 1.5% by mass or more. It is even more preferable that there be. When the solubility is at least the above lower limit, good coating film performance tends to be obtained. The upper limit of solubility is not particularly limited, but is 50% by mass or less.

[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, and contains at least compound (2) as the dye.
The composition for forming an anisotropic dye film of the present invention may contain only one type of compound (2), or may contain two or more types of compound (2).
In the composition for forming an anisotropic dye film of the present invention, -A ¹ -, -A ² -, -A ³ - in formula (2) are used as dyes from the viewpoint of suppressing precipitation in the composition. Those containing only one type of the same compound of the present invention are preferred, and those containing only one type of compound of the present invention are more preferred.

The composition for forming an anisotropic dye film of the present invention contains compound (2) as a dye, but may contain a dye other than compound (2).
Examples of dyes other than compound (2) contained in the composition for forming an anisotropic dye film of the present invention include azo dyes, quinone dyes (including naphthoquinone dyes, anthraquinone dyes, etc.), and stilbene dyes. Examples include dyes, cyanine dyes, phthalocyanine dyes, indigo dyes, and condensed polycyclic dyes (including perylene dyes, oxazine dyes, acridine dyes, etc.).
The composition for forming an anisotropic dye film of the present invention may contain only one type of dye other than compound (2) alone, or may contain two or more types in any combination and ratio. Good too.

Among the dyes other than the compound (2) exemplified above, azo dyes are preferable because they can have a high molecular alignment in an anisotropic dye film.
Hereinafter, azo dyes other than compound (2) are also referred to as "other azo dyes."

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, and preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

Examples of other azo dyes include compounds represented by the following formula (3).
R ³¹ -E ¹ -N=N-(E ² -N=N) _p -E ³ -R ³² ...(3)
(In formula (3),
-E ¹ -, -E ² - and -E ³ - each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a naphthylene group which may have a substituent. represents an optionally divalent heterocyclic group.
p represents an integer from 0 to 4.
When p is an integer of 2 or more, the plurality of -E ² -s may be the same or different.
-R ³¹ and -R ³² each independently represent a monovalent organic group. )

-E ¹ -, -E ² - and -E ³ - each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a naphthylene group which may have a substituent. represents an optionally divalent heterocyclic group.
As for the substitution position of the phenylene group, a 1,4-phenylene group is preferred 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.

As the divalent heterocyclic group, the number of carbon atoms forming the ring is preferably 3 or more and 14 or less, more preferably 3 or more and 10 or less. Particularly preferred are monocyclic or bicyclic heterocyclic groups.
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.
Examples of the divalent heterocyclic group include a pyridinediyl group, a quinolinediyl group, an isoquinolinediyl group, a thiazolediyl group, a benzothiazolediyl group, a thienothiazolediyl group, a thienothiophenediyl group, a benzimidazolidinonediyl group, and a benzofurandiyl group. group, phthalimidodiyl group, oxazolediyl group, and benzoxazolediyl group.

Examples of optional substituents of the phenylene group, naphthylene group, and divalent heterocyclic group in -E ¹ -, -E ² -, and -E ³ - include an alkyl group having 1 to 4 carbon atoms; a methoxy group; , alkoxy groups having 1 to 4 carbon atoms such as ethoxy and butoxy groups; fluorinated alkyl groups having 1 to 4 carbon atoms such as trifluoromethyl groups; cyano groups; nitro groups; hydroxyl groups; halogen atoms; amino groups, diethylamino groups , and a substituted or unsubstituted amino group such as a pyrrolidino group. 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. means an amino group. The unsubstituted amino group is _-NH2 . Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group and butyl group. Examples of the alkanediyl group 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. 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, the phenylene group, naphthylene group, and divalent heterocyclic group in -E ¹ -, -E ² -, and -E ³ - are unsubstituted or substituted. In some cases, substitution is preferably performed with a methyl group, methoxy group, hydroxyl group, fluorine atom, chlorine atom, dimethylamino group, pyrrolidinyl group, or piperidinyl group.

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

-R ³¹ and -R ³² represent the same or different monovalent organic groups.
Examples of the monovalent organic group in -R ³¹ and -R ³² 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; ; Alkoxy group having 1 to 15 carbon atoms which may have a branch such as a methoxy group, ethoxy group and butoxy group; A fluoride having 1 to 15 carbon atoms which may have a branch such as a trifluoromethyl group Alkyl 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; number of carbon atoms that may have branches such as butoxycarbonyl group 1-15 alkyloxycarbonyl group; Alkylphenylalkenyl group such as 2-(4-butylphenyl)ethenyl group; Carbamoyl group; Alkylcarbamoyl having 1-15 carbon atoms which may have a branch such as butylcarbamoyl group. group; sulfamoyl group; alkylsulfamoyl group having 1 to 15 carbon atoms which may have a branch such as a butylsulfamoyl group; an alkylsulfamoyl group having 1 to 15 carbon atoms which may have a branch such as a butylcarbonylamino group; 15 acylamino group; optionally branched acyloxy group with 1 to 15 carbon atoms such as butylcarbonyloxy group; sulfanyl group; alkylsulfanyl group with 1 to 15 carbon atoms such as butylsulfanyl group; liquid crystal compound described below Examples include -R ⁴¹ and -R ⁴² . The above 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 in which two substituted alkyl groups are bonded to each other and having 2 to 15 carbon atoms. means an amino group forming an alkanediyl group. The unsubstituted amino group is _-NH2 . Examples of the alkyl group having 1 to 15 carbon atoms include methyl group, ethyl group, and 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. group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, and the like.

-R ³¹ and -R ³² include hydrogen atoms, chain groups, aliphatic organic groups ("aliphatic organic groups" include chain and cyclic groups), and carbon atoms in which some of the carbon atoms are nitrogen. Aliphatic organic groups substituted with atoms and/or oxygen atoms (``aliphatic organic groups in which some of the carbon atoms are replaced with nitrogen atoms and/or oxygen atoms'') include chain-like and cyclic ones. , aliphatic organic groups in which some methyl groups are replaced with hydroxyl groups, oxo groups (=O), amino groups, imino groups, etc.), and in some embodiments, hydrogen atoms, A chain group is preferable, and in another embodiment, a hydrogen atom and an aliphatic organic group are preferable. In still another embodiment, a hydrogen atom and an aliphatic group in which some of the carbon atoms are replaced with nitrogen atoms and/or oxygen atoms are preferable. Group organic groups are preferred.

Examples of the chain group include 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; A fluorinated alkyl group having 1 to 15 carbon atoms which may optionally have a branch; a substituted or unsubstituted amino group (a substituted amino group refers to a fluorinated alkyl group having 1 to 15 carbon atoms which may have a branch) means an amino group. An unsubstituted amino group is -NH ₂ ); Carboxy group; Alkyloxycarbonyl group having 1 to 15 carbon atoms which may have a branch; Carbamoyl group; an optionally branched alkylcarbamoyl group having 1 to 15 carbon atoms; a sulfamoyl group; an optionally branched alkylsulfamoyl group having 1 to 15 carbon atoms; an optionally branched alkylsulfamoyl group having 1 to 15 carbon atoms; Examples include acylamino group; acyloxy group having 1 to 15 carbon atoms which may have a branch; sulfanyl group; alkylsulfanyl group having 1 to 15 carbon atoms. Note that the chain group and the aliphatic organic group partially overlap.

Examples of the aliphatic organic group include the above-mentioned optionally branched alkyl group having 1 to 15 carbon atoms and alicyclic alkyl group having 1 to 15 carbon atoms.
Examples of aliphatic organic groups in which some of the carbon atoms are replaced with nitrogen atoms and/or oxygen atoms include the above-mentioned alkoxy groups having 1 to 15 carbon atoms which may have a branch; substituted or unsubstituted Amino group; Carboxy group; 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; An optionally branched acylamino group having 1 to 15 carbon atoms; and an optionally branched acyloxy group having 1 to 15 carbon atoms. The above 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 in which two substituted alkyl groups are bonded to each other and having 2 to 15 carbon atoms. means an amino group forming an alkanediyl group. The unsubstituted amino group is _-NH2 . Examples of the alkyl group having 1 to 15 carbon atoms include methyl group, ethyl group, and 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. 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, -R ³¹ and -R ³² 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, etc. Group: Preferred are alkoxy groups having 1 to 10 carbon atoms such as butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, and octyloxy group, diethylamino group, pyrrolidino group, and piperidinyl group. Also preferred are -R ⁴¹ and -R ⁴² in the liquid crystal compounds described below.

Other azo dyes that may be included in the composition for forming an anisotropic dye film of the present invention are not particularly limited, and known azo dyes can also be used.
Known azo dyes include, for example, the dyes (dichroic dyes, dichroic dyes, dyes).

Other azo dyes include, but are not limited to, the following azo dyes.

The dye other than compound (2) contained in the composition for forming an anisotropic dye film of the present invention has a wavelength showing a maximum value in the absorption curve in the wavelength range of 350 to 800 nm. It is preferable to use a dye having a wavelength longer than the maximum value in the absorption curve of compound (2) in the wavelength range of 350 to 800 nm, which is contained in the composition, and an azo dye is preferable. Further, the difference in wavelength is preferably 5 nm or more, and preferably 10 nm or more. With the above, when an anisotropic dye film formed using the composition for forming an anisotropic dye film of the present invention is applied to a polarizing element such as a display, it exhibits polarizing properties in a wide range of the visible region. can do.

(Molecular weight of the compound and dye of the present invention)
The molecular weight of the compound of the present invention (when two or more compounds of the present invention are used together, the respective molecular weights) is preferably 300 or more, more preferably 350 or more, even more preferably 380 or more, and preferably 1500 or less, Moreover, 1200 or less is more preferable, and 1000 or less is even more preferable. Specifically, the molecular weight of the compound 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. Since the molecular length and bulk are appropriate within the above range, the molecular orientation of the compound of the present invention tends to be good.

The molecular weight of the dye other than compound (2) 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 molecular weight of each dye) is preferably 300 or more, and 350 or more. is more preferable, 380 or more is still more preferable, 1500 or less is preferable, 1200 or less is more preferable, and even more preferably 1000 or less. Specifically, the molecular weight of the dye other than compound (2) is preferably from 300 to 1,500, more preferably from 350 to 1,200, even more preferably from 380 to 1,000. Since the molecular length and bulkiness are appropriate within the above range, the molecular orientation of dyes other than compound (2) tends to be favorable.

The molecular weight of the compound of the present invention and dyes other than compound (2) is the sum of the atomic weights contained in the dyes.

(Pigment content)
The content occupied by pigments such as dichroic pigments in the anisotropic pigment film-forming composition of the present invention (when two or more pigments are used together, the sum of their contents) is, for example, anisotropic pigment film-forming composition. It is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably less than 30% by mass, more preferably less than 25% by mass, based on the solid content of the pigment film-forming composition. It is more preferably less than 20% by weight, particularly preferably less than 10% by weight. 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% by mass) of the composition for forming an anisotropic dye film. The content is 0.01% by mass or more and less than 30% by mass, preferably 0.05% by mass or more and less than 20% by mass, and more preferably 0.05% by mass or more and less than 10% by mass.

If the content occupied by the dye is within the above range, the composition for forming an anisotropic dye film of the present invention can be used without disturbing the orientation of the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention. It tends to be possible to polymerize polymerizable liquid crystal compounds contained in objects. Moreover, if the content occupied by the dye is equal to or higher 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 is below the above-mentioned upper limit, inhibition of the alignment of liquid crystal molecules tends to be suppressed.
Here, the solid content of the composition for forming an anisotropic pigment film corresponds to the total of all components other than the solvent in the composition for forming an anisotropic pigment film.

The composition for forming an anisotropic pigment film of the present invention only needs to contain the compound of the present invention as an essential component as a pigment, and may not contain a pigment other than the above-mentioned compound (2) together with compound (2). However, if the composition for forming an anisotropic dye film of the present invention contains a dye other than compound (2), from the viewpoint of more effectively obtaining the effects of the present invention by using compound (2). The content of compound (2) in 100% by mass of the total amount of dyes in the composition for forming an anisotropic dye film of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more. On the other hand, it is more preferably 15% by mass or more, and particularly preferably 20% by mass or more. On the other hand, from the viewpoint of exhibiting polarization characteristics over a wide visible range, this proportion is preferably 80% by mass or less, more preferably 60% by mass or less, and preferably 50% by mass or less. More preferably, the content is particularly preferably 40% by mass or less.

(Method for producing pigment)
Pigments other than the compound (2) contained in the compound of the present invention or the composition for forming an anisotropic dye film of the present invention can be used for alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipsosubstitution reaction, diazolysis reaction, etc. It can be produced by combining known chemical reactions such as coupling reactions and coupling reactions using metal catalysts.
For example, the compounds of the present invention can be prepared using the methods described in the examples below, "New Dye Chemistry" (authored by Yutaka Hosoda, published by Gihodo, December 21, 1972), "Overview of Synthetic Dyes" (authored by Hiroshi Horiguchi, published by Gihodo), It can be synthesized according to the method described in ``Theoretical Manufacturing Dye Chemistry'' (by Yutaka Hosoda, 1957, Gihodo) (Sankyo Publishing, 1968).

<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 the polymerizable liquid crystal compound, the polymerizable group can be placed at any position within the liquid crystal compound molecule, but it is preferable from the viewpoint of ease of polymerization that the polymerizable group is substituted at the end of the liquid crystal compound molecule. .
In a polymerizable liquid crystal compound, one or more polymerizable groups can exist in the liquid crystal compound molecule, but if two or more polymerizable groups exist, it is important that they are present at both ends of the liquid crystal compound molecule to facilitate polymerization. It is preferable from the viewpoint of quality.

Furthermore, the polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond within the liquid crystal compound molecule. When the compound has a carbon-carbon triple bond, the carbon-carbon triple bond is capable of rotational movement and can serve as the core of the liquid crystal molecule, and the molecules have high mobility and the liquid crystal molecules do not interact with each other. They have strong intermolecular interactions with compounds that have a π-conjugated system, such as pigment molecules, and tend 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. A low-molecular polymerizable liquid crystal compound having no repeating unit structure is preferred because it tends to provide a high dichroic ratio.
The molecular weight of the low-molecular polymerizable compound having no repeating unit structure is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 1,000 or less. The lower limit of the molecular weight of the polymerizable liquid crystal compound is not particularly limited, but is preferably 400 or more, more preferably 500 or more. If the molecular weight is below the above upper limit, the liquid crystal compound tends to have good mobility during film formation for orientation, and the molecular orientation tends to be good; if the molecular weight is above the above lower limit, the molecules of the liquid crystal compound Higher linearity tends to improve molecular orientation.
The above upper and lower limits can be arbitrarily combined. The molecular weight of the polymerizable liquid crystal compound may be, for example, 400 or more and 2000 or less, 400 or more and 1500 or less, or 500 or more and 1000 or less.

For example, the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is a compound represented by the following formula (4) (hereinafter referred to as "polymerizable liquid crystal compound (4)"). ).

Q ¹ -R ⁴¹ -A ⁴¹ -Y ¹ -A ⁴² -(Y ² -A ⁴³ ) _k -R ⁴² -Q ² ...(4)

(In formula (4),
-Q ¹ represents a hydrogen atom or a polymerizable group.
-Q ² represents a polymerizable group.
-R ⁴¹ - and -R ⁴² - each independently represent a chain organic group.
-A ⁴¹ - and -A ⁴³ - each independently represent a partial structure represented by the following formula (5), a divalent organic group, or a single bond.
-A ⁴² - represents a partial structure represented by the following formula (5) or a divalent organic group.
-Y ¹ - and -Y ² - each independently represent a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S) -, -C(=O)S-, -SC(=O)-, -CH ₂ CH ₂ -, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC( =O)-, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, or -SCH ₂ -.
One of -A ⁴¹ - and -A ⁴³ - is a partial structure or a divalent organic group represented by the following formula (5).
k is 1 or 2.
When k is 2, the two -Y ² -A ⁴³ - may be the same or different. )

-C ^y -X ⁵² -C≡C-X ⁵¹ -...(5)
(In formula (5),
-C ^y - represents a hydrocarbon ring group or a heterocyclic group.
-X ⁵¹ - 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 S- or -SCH ₂ -.
-X ⁵² - 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 ⁴¹ - is a partial structure represented by formula (5), formula (4) may be the following formula (4A) or the following formula (4B).
Q ¹ -R ⁴¹ -C ^y -X ⁵² -C≡C-X ⁵¹ -Y ¹ -A ⁴² -(Y ² -A ⁴³ ) _k -R ⁴² -Q ² ...(4A)
Q ¹ -R ⁴¹ -X ⁵¹ -C≡C-X ⁵² -C ^y -Y ¹ -A ⁴² -(Y ² -A ⁴³ ) _k -R ⁴² -Q ² ...(4B)

Further, when -A ⁴² - is a partial structure represented by formula (5), formula (4) may be the following formula (4C) or the following formula (4D).
Q ¹ -R ⁴¹ -A ⁴¹ -Y ¹ -C ^y -X ⁵² -C≡C-X ⁵¹ -(Y ² -A ⁴³ ) _k -R ⁴² -Q ² ...(4C)
Q ¹ -R ⁴¹ -A ⁴¹ -Y ¹ -X ⁵¹ -C≡C-X ⁵² -C ^y -(Y ² -A ⁴³ ) _k -R ⁴² -Q ² ...(4D)

Further, when -A ⁴³ - is a partial structure represented by formula (5), formula (4) may be the following formula (4E) or the following formula (4F).
Q ¹ -R ⁴¹ -A ⁴¹ -Y ¹ -A ⁴² -(Y ² -C ^y -X ⁵² -C≡C-X ⁵¹ ) _k -R ⁴² -Q ² ... (4E)
Q ¹ -R ⁴¹ -A ⁴¹ -Y ¹ -A ⁴² -(Y ² -X ⁵¹ -C≡C-X ⁵² -C ^y ) _k -R ⁴² -Q ² ... (4F)

Similarly, when two or more of -A ⁴¹ -, -A ⁴² -, and -A ⁴³ - are partial structures represented by formula (5), each independently represents a partial structure represented by formula (5). The orientation of the substructure may be reversed.

Furthermore, as described above, -A ⁴¹ -, -A ⁴² -, and -A ⁴³ - are each independently a partial structure or a divalent organic group represented by formula (5), and in addition, - A ⁴¹ - and -A ⁴³ - may be single bonds, but -A ⁴¹ - and -A ⁴³ - are not both single bonds.

(-C ^y -)
The hydrocarbon ring group in -C ^y - 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 monocyclic or fused aromatic hydrocarbon ring divalent group, and the number of carbon atoms is 6 to 20, and the molecular orientation can be controlled by an appropriate core size. It is preferable because it is good. The number of carbon atoms in the unlinked aromatic hydrocarbon ring group is more preferably 6 to 15. 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. Can be mentioned.

A 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 the atom constituting the ring. It is preferable that the single ring or condensed ring has 6 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The number of carbon atoms in the monocyclic or condensed ring is more preferably 6 to 15. Examples of the linked aromatic hydrocarbon ring group include 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. is bonded to the ring by a single bond, has a first bond on an atom constituting the first monocyclic ring or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms, and has a second bond having a carbon number of 6 to 20. Examples include divalent groups having a second bond on atoms constituting 6 to 20 monocyclic or fused aromatic hydrocarbon rings. A specific example of the linked aromatic hydrocarbon ring group is a biphenyl-4,4'-diyl group.

As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable because it optimizes the intermolecular interaction between the liquid crystal compounds and improves the molecular orientation.
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. When -C ^y - is one of these groups, the linearity of the liquid crystal molecules increases, and the effect of improving molecular orientation tends to be obtained.

The non-aromatic hydrocarbon ring group includes a non-linked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

The unlinked non-aromatic hydrocarbon ring group is a monocyclic or fused non-aromatic hydrocarbon ring divalent group, and the number of carbon atoms is 3 to 20, depending on the molecular orientation depending on the appropriate core size. This is preferable because it provides good properties. The number of carbon atoms in the unlinked non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetrahydronaphthalene ring, and a bicyclo [2.2.2] Octane ring etc. are mentioned.

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 from the viewpoint of productivity.

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 single ring or condensed ring is preferably 3 to 20 because an appropriate core size improves molecular orientation.
Examples of the connected non-aromatic hydrocarbon ring group include a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or fused non-aromatic ring having 3 to 20 carbon atoms. The hydrocarbon ring is bonded with a single bond, the first bond is on the atom constituting the first monocyclic ring or the fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and the second Examples include a divalent group having a second bond on an atom constituting a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Furthermore, 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 together through 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. Examples include divalent groups having a second bond on the atom.
Specific 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 because the molecular orientation is improved by optimizing the intermolecular interaction between the liquid crystal compounds.

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

The heterocyclic group in -C ^y - 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 the number of carbon atoms is 4 to 20, so that good molecular orientation can be achieved by an appropriate core size. It is preferable for the following reasons. The number of carbon atoms in the unlinked aromatic heterocyclic group is more preferably 4 to 15.
Examples of aromatic heterocycles include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, oxadiazole ring, and thiadiazole ring. ring, triazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole 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, quinazoline ring, quinazolinone ring, and azulene ring.

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. It is preferable that the single ring or condensed ring has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.
As the linked aromatic heterocyclic group, for example, a first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms are used. bonded with a single bond, has a first bond on an atom constituting a first monocyclic ring having 4 to 20 carbon atoms or a fused aromatic heterocyclic ring, and a second bond having 4 to 20 carbon atoms. A divalent group having a second bond on an atom constituting a monocyclic ring or a condensed aromatic heterocycle can be mentioned.

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 the number of carbon atoms is 4 to 20, and the molecular orientation can be controlled by an appropriate core size. It is preferable because it is good. The number of carbon atoms in the unlinked non-aromatic heterocyclic group is more preferably 4 to 15.
Examples of the non-aromatic heterocycle of a divalent group of a monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, and a 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. It will be done.

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. It is preferable that the single ring or condensed ring has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.
Examples of the linked aromatic heterocyclic group include a first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms. are bonded to each other by a single bond, the first bond is on an atom constituting a monocyclic ring having 4 to 20 carbon atoms or a fused non-aromatic heterocyclic ring, and the second bond is bonded to a ring having 4 to 20 carbon atoms. A divalent group having a second bond on an atom constituting a ring of ~20 monocyclic or fused non-aromatic heterocycles can be mentioned.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -C ^y - are respectively -R ^k , -OH, -O-R ^k , - OC(=O)-R ^k , -NH ₂ , -NH-R ^k , -N(-R ^k' )-R ^k , -C(=O)-R ^k , -C(=O)- OR ^k , -C(=O)-NH ₂ , -C(=O)-NH-R ^k , -C(=O)-N(-R ^k' )-R ^k , -SH, -S -R ^k , a trifluoromethyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, and a halogen group, which may be substituted with one or more groups. -R ^k and -R ^k' 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 -C ^y - have high linearity in molecular structure, and the polymerizable liquid crystal compound (4) 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, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -C ^y - may be the same or different; All of the hydrocarbon ring group, 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. may be partially unsubstituted.

-C ^y - is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group, since the molecular orientation of the polymerizable liquid crystal compound (4) is improved. Since the linearity of the molecular structure of the polymerizable liquid crystal compound (4) can be increased, -C ^y - is more preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group; -phenylene group is particularly preferred.

(-X ⁵¹ -)
-X ⁵¹ - 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 S- or -SCH ₂ -, but among these, -X ⁵¹ - is π because of the linearity of the polymerizable liquid crystal compound (4) and the tendency for rotational movement around the short axis of the molecule. Low bonding, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC Preferred examples include (=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -CH ₂ S-, and -SCH ₂ -. Among these, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ - are more preferred, and -X ⁵¹ - is -C(=O)O- or -OC(=O)-. In another embodiment, -X ⁵¹ - is preferably -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -.

(-X ⁵² -)
-X ⁵² - 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 -.
-C ^y - is a group with high linearity from the viewpoint of enlarging the core of the polymerizable liquid crystal compound (4) and increasing the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film. and -C≡C- are preferably connected. Specifically, -X ⁵² - includes 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)-, A single bond is more preferable because it has higher linearity.

(-Q ¹ and -Q ² )
The polymerizable groups in -Q ¹ and -Q ² are groups that have a partial structure that can be polymerized by light, heat, and/or radiation, and include functional groups or atoms necessary to ensure the polymerization function. It is a group. The polymerizable group is preferably a photopolymerizable group from the viewpoint of producing an anisotropic dye film.

Examples of the polymerizable group include acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, vinyl group, vinyloxy group, ethynyl group, ethynyloxy group, 1,3-butadienyl group, Examples include 1,3-butadienyloxy group, oxiranyl group, oxetanyl group, glycidyl group, glycidyloxy group, styryl group, and styryloxy group. Acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, oxiranyl group, glycidyl group, glycidyloxy group are preferred, and acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylamino group A methacryloyloxy 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.

(-R ⁴¹ - and -R ⁴² -)
The chain organic group in -R ⁴¹ - and -R ⁴² - is a divalent 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. is an organic group.
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)-.

Examples of the alkylene group in these chain organic groups include linear or branched alkylene groups having 1 to 25 carbon atoms. A portion of the carbon-carbon bonds of the alkylene group may be unsaturated bonds. One or more methylene groups contained in the alkylene group are -O-, -S-, -NH-, -N(R ^m )-, -C(=O)-, -C(=O)- The structure may be replaced by O-, -C(=O)-NH-, -CHF-, -CF ₂ -, -CHCl-, or -CCl ₂ -. R ^m 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 of the alkylene group may be unsaturated bonds, and one or more carbon atoms contained in the alkylene group may be It is preferable that the methylene group is 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 ) _r -CH ₂ -, -O-(CH ₂ ) _r -CH ₂ -, -(O) _r1 -(CH ₂ CH ₂ O) _r2 -(CH ₂ ) _r3 -, -(O) _r1 -(CH ₂ ) _r2 -(CH ₂ CH ₂ O) _r3 - are preferred. r 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, even more preferably an integer of 5 to 19. In addition, r1, r2, and r3 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, even more preferably 6 to 20.

-R ⁴¹ - and -R ⁴² - are each independently preferably -(alkylene group)-, -O-(alkylene group)-, -(alkylene group)-, -O-(alkylene group) - is more preferable. In one embodiment, the chain organic group in -R ⁴¹ - and -R ⁴² - is -(alkylene group)-, and in another embodiment, it is -O-(alkylene group)-.

When -X ⁵¹ - and -R ⁴¹ - or -X ⁵¹ - and -R ⁴² - are bonded as in the above formula (4B) and formula (4E); in the above formula (4B), -A ⁴³ - is a single bond, or in the formula (4E), -A ⁴¹ - is a single bond, and -R ⁴¹ - or -R ⁴² - is bonded to -Y ¹ - or -Y ² - In case;, -R ⁴¹ - or -R ⁴² - directly bonded to -X ⁵¹ -, -Y ¹ - or -Y ¹ - is preferably -(alkylene group) -.

Other than the above, -R ⁴¹ - or -R ⁴² - which does not directly bond to -X ⁵¹ -, -Y ¹ - or -Y ² - is preferably -O- (alkylene group)-.

(Divalent organic group in -A ⁴¹ -, -A ⁴² -, and -A ⁴³ -)
The divalent organic group in -A ⁴¹ -, -A ⁴² -, and -A ⁴³ - is preferably a group represented by the following formula (6).

-Q ³ -...(6)
(In formula (6), ^Q3 represents a hydrocarbon ring group or a heterocyclic group.)

The hydrocarbon ring group represented by -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 the number of carbon atoms is preferably 6 to 20.The core size provides good molecular orientation. This is preferable for the following reasons. The number of carbon atoms in the unlinked aromatic hydrocarbon ring group is more preferably 6 to 15. 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. .

A 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 the atom constituting the ring. It is preferable that the single ring or condensed ring has 6 to 20 carbon atoms because an appropriate core size provides good orientation. The number of carbon atoms in the linked aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of the linked aromatic hydrocarbon ring group include 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. is bonded to the ring by a single bond, has a first bond on an atom constituting the first monocyclic ring or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms, and has a second bond having a carbon number of 6 to 20. Examples include divalent groups having a second bond on atoms constituting 6 to 20 monocyclic or fused aromatic hydrocarbon rings. A specific example of the linked aromatic hydrocarbon ring group is a biphenyl-4,4'-diyl group.

As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable because it optimizes the intermolecular interaction between the liquid crystal compounds and improves the molecular orientation.
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. When -Q ³ - is one of these groups, the linearity of the liquid crystal molecules increases, and the effect of improving molecular orientation tends to be obtained.

The unlinked non-aromatic hydrocarbon ring group is a monocyclic or fused non-aromatic hydrocarbon ring divalent group, and the number of carbon atoms is 3 to 20, depending on the molecular orientation depending on the appropriate core size. This is preferable because it provides good properties. The number of carbon atoms in the unlinked non-aromatic hydrocarbon ring group is more preferably 3 to 15. 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.

The unlinked non-aromatic hydrocarbon ring group is preferably a divalent cyclohexane group (cyclohexanediyl group), and the cyclohexanediyl group is preferably a cyclohexane-1,4-diyl group.

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

The unlinked aromatic heterocyclic group is a monocyclic or fused aromatic heterocyclic divalent group, and the number of carbon atoms is 4 to 20, so that good molecular orientation can be achieved by an appropriate core size. It is preferable for the following reasons. The number of carbon atoms in the unlinked aromatic heterocyclic group is more preferably 4 to 15.
Examples of aromatic heterocycles include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, and pyrrolo ring. Pyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, thienothiazole ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, Examples include a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a shinoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

The unlinked non-aromatic heterocyclic group is a monocyclic or fused non-aromatic heterocyclic divalent group, and the number of carbon atoms is 4 to 20, and the molecular orientation can be controlled by an appropriate core size. It is preferable because it is good. The number of carbon atoms in the unlinked non-aromatic heterocyclic group is more preferably 4 to 15.
Examples of the non-aromatic heterocycle of a divalent group of a monocyclic or condensed non-aromatic heterocycle having 4 to 20 carbon atoms include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, 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 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. It is preferable that the single ring or condensed ring has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.
Examples of the linked aromatic heterocyclic group include a first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms. are bonded to each other by a single bond, the first bond is on an atom constituting a monocyclic ring or a condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second bond is 4 to 20 carbon atoms. A divalent group having a second bond on an atom constituting a ring of ~20 monocyclic or fused non-aromatic heterocycles can be mentioned.

The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Q ³ - are respectively -R ⁿ , -OH, -O-R ⁿ , - OC(=O)-R ⁿ , -NH ₂ , -NH-R ⁿ , -N(-R ^n' )-R ⁿ , -C(=O)-R ⁿ , -C(=O)- O-R ⁿ , -C(=O)-NH ₂ , -C(=O)-NH-R ⁿ , -C(=O)-N(-R ^n' )-R ⁿ , -SH, -S -R ⁿ may be substituted with one or more groups selected from the group consisting of a trifluoromethyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, and a halogen. -R ⁿ and -R ^n' 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 -Q ³ - have high linearity in molecular structure, and the polymerizable liquid crystal compound (4) 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 possessed by the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Q ³ - may be the same or different; All of the hydrocarbon ring group, 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. may be partially unsubstituted.
-A ⁴¹ -, -A ⁴² - and -A ⁴³ - may have the same or different substituents, and -A ⁴¹ -, -A ⁴² - and -A ⁴³ - have divalent organic groups. All of the organic groups may be substituted, all of them may be unsubstituted, or some of them may be substituted and some of them may be unsubstituted.

-Q ³ - is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. -Q ³ - is more preferably a 1,4-phenylene group or a cyclohexane-1,4-diyl group, since they can improve the linearity of the molecular structure of the polymerizable liquid crystal compound (4).

-A ⁴¹ -, -A ⁴² - and -A ⁴³ - are divalent organic groups, -Q ³ - is a hydrocarbon ring group, that is, the divalent organic group is a hydrocarbon ring group. preferable. 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 polymerizable liquid crystal compound (4), 1,4-phenylene group and cyclohexane-1,4 -diyl group is more preferred.

In the polymerizable liquid crystal compound (4), one of -A ⁴¹ -, -A ⁴² - and -A ⁴³ - is a partial structure represented by formula (5), and the other two are each a partial structure represented by formula (5). Independently, it is preferably a divalent organic group, and among -A ⁴¹ -, -A ⁴² - and -A ⁴³ -, -C ^y - in the partial structure represented by formula (5) is a hydrocarbon ring group. It is more 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. Further, it is preferable that one of -A ⁴¹ - and -A ⁴³ - is a cyclohexane-1,4-diyl group.
Furthermore, it is preferable that one of -A ⁴¹ - and -A ⁴³ - is a partial structure represented by formula (5), and the other one and -A ⁴² - are divalent organic groups. preferable. In this case, one of -A ⁴¹ - and -A ⁴³ -, which is a divalent organic group, is preferably a cyclohexane-1,4-diyl group, and -A ⁴² - is a 1,4-phenylene group. It is particularly preferable that there be.

(-Y ¹ - and -Y ² -)
-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 -. Because of the linearity of the polymerizable liquid crystal compound (4) and the tendency for rotational movement around the short axis of the molecule, -Y ¹ - and -Y ² - are each independently selected from monomers with small π bonding properties. 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 preferred, and a single bond, -C(=O)O-, -OC(=O)-, -CH ₂ CH ₂ -, -CH ₂ O-, and -OCH ₂ - are more preferred.

When -X ⁵¹ - and -Y ¹ - or -X ⁵¹ - and -Y ² - are bonded as in the above formula (4A), formula (4C), formula (4D), and formula (4F), It is preferable that -Y ¹ - bonded to -X ⁵¹ - or -Y ² - bonded to -X ⁵¹ - be a single bond. The other of -X ⁵¹ - and -Y ¹ - and -Y ² - is preferably -C(=O)O- or -OC(=O)-.
As in formula (4B) and formula (4E), when -X ⁵¹ - is not bonded to either -Y ¹ - or -Y ² -, -X ⁵¹ - is -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ - is preferable, and -Y ¹ - and -Y ² - are both -C(=O)O- or -OC(=O)- It is preferable.

(k)
k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2.
When k is 2, each -Y ² - may be the same or different from each other, and each -A ⁴³ - may be the same or different from each other.

(preferred structure)
The polymerizable liquid crystal compound (4) is a compound represented by the above formula (4A), (4B), (4E) or (4F), which optimizes the intermolecular interaction between the liquid crystal compounds, It is preferable because it has an appropriate core size and good molecular orientation.

(Specific example of polymerizable liquid crystal compound)
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 following exemplary formula, -C ₆ H ₁₃ means n-hexyl group, and -C ₅ H ₁₁ means n-pentyl group.

(Content of liquid crystal compound)
The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention preferably consists of a polymerizable liquid crystal compound (4). The composition for forming an anisotropic dye film of the present invention may contain only one type of polymerizable liquid crystal compound, or may contain two or more types in any combination and ratio.

The content of the liquid crystal compound in the composition for forming an anisotropic pigment film of the present invention (when two or more liquid crystal compounds are used together, the sum of their respective contents) is the content of the liquid crystal compound in the composition for forming an anisotropic pigment film of the present invention. Based on the solid content (100 parts by mass), the amount is preferably 35 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, preferably 99 parts by mass or less, and more preferably 98 parts by mass or less. If the content of the liquid crystal compound in the composition for forming an anisotropic dye film is greater than or equal to the above lower limit and less than or equal to the upper limit, the orientation of liquid crystal molecules tends to be high.

The composition for forming an anisotropic dye film of the present invention may contain one or more polymerizable or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (4). , from the viewpoint of more effectively obtaining the effects of the present invention by using the polymerizable liquid crystal compound (4), polymerization in 100% by mass of the total amount of liquid crystal compounds contained in the composition for forming an anisotropic dye film of the present invention. The proportion of the liquid crystal compound (4) is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15 to 100% by mass.

In addition, the composition for forming an anisotropic dye film of the present invention contains a polymerizable liquid crystal compound whose mass concentration in the composition for forming an anisotropic dye film is as described below with respect to the concentration of the compound of the present invention. It is preferable to contain it so as to have a mass concentration.

(Isotropic phase appearance temperature)
From the viewpoint of the process, 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. , more preferably 115°C or less, even more preferably 110°C or less, particularly preferably 105°C or less.
Here, the isotropic phase appearance temperature means the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid to liquid crystal. In the present invention, it is preferable that at least one of these phase transition temperatures is below the above upper limit, and it is more preferable that both of these phase transition temperatures are below the above upper limit.

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

(Relationship between polymerizable liquid crystal compound and compound of the present invention)
From the viewpoint of easily improving the orientation of the anisotropic dye film formed using the composition for forming an anisotropic dye film, molecules of a polymerizable liquid crystal compound are used in the composition for forming an anisotropic dye film. The smaller the difference between the length and the molecular length of the dye, the stronger the intermolecular interaction between the liquid crystal molecules and the dye molecules, and the dye molecules are less likely to inhibit the association between the liquid crystal molecules, which is preferable.

Therefore, in the composition for forming an anisotropic dye film of the present invention, the number of ring structures (r _n1 ) possessed by the polymerizable liquid crystal compound contained in the composition for forming an anisotropic dye film, The ratio (r _n1 /r _n2 ) to the number of ring structures (r n2 ) possessed by the compound of the present invention 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 ) possessed by the compound of the present invention, for example, compound (1), means -A ¹¹ -, -A ¹² -, -A ¹³ - and -A ¹⁴ - in formula (1). , and r _n2 is 4.
Even if -X ¹ in formula (1) is a cyclic functional group such as a pyrrolidinyl group or piperidinyl group, the ring structure contained in -X ¹ is determined by the number of ring structures (r _n2 ) possessed by the compound of the present invention. are not included.
Furthermore, the number of ring structures (r _n2 ) possessed by the compound of the present invention, for example, compound (2), is the sum of -A ¹ -, -A ² -, and -A ³ - in formula (2). Specifically, when n is 1, r _n2 is 3; when n is 2, r _n2 is 4; when n is 3, r _n2 is 5.
Even if -X in formula (2) is a cyclic functional group such as a pyrrolidinyl group or piperidinyl group, the ring structure contained in -X is not included in the number of ring structures (r _n2 ) possessed by the compound of the present invention. do not have.

More specifically, if r _n2 is 3, r _n1 is 3 or 4; if r _n2 is 4, r _n1 is 3, 4, 5, or 6; r _n2 is 5. If r _n1 is 4, 5, 6, or 7, the number of ring structures (r _n1 ) of the polymerizable liquid crystal compound contained in the composition for forming an anisotropic pigment film and the anisotropic pigment film This is preferable because the ratio (r _n1 /r _n2 ) to the number of ring structures (r _n2 ) possessed by the compound of the present invention contained in the forming composition is 0.7 to 1.5.

The number of ring structures (r _n1 ) possessed by 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.

It is preferable that the composition for forming an anisotropic dye film of the present invention contains the polymerizable liquid crystal compound in such a manner that the mass concentration of the polymerizable liquid crystal compound is at least 1 times the mass concentration of the compound of the present invention. If the mass concentration of the polymerizable liquid crystal compound is one or more times the mass concentration of the compound of the present invention, a high dichroic ratio tends to be obtained, which is preferable from the viewpoint of improving the mechanical strength of the anisotropic dye film. The mass concentration of the polymerizable liquid crystal compound in the composition for forming an anisotropic dye film of the present invention is more preferably 1.5 times or more, and more preferably 2 times or more, the mass concentration of the compound of the present invention. It is preferably 3 times or more, particularly preferably 7 times or more, and even more preferably 7 times or more. On the other hand, if the amount of the polymerizable liquid crystal compound is too large relative to the compound of the present invention, the absorbance as an anisotropic dye film tends to decrease. The mass concentration of the liquid crystal compound is preferably 1000 times or less, more preferably 700 times or less, and even more preferably 500 times or less than the mass concentration of the compound of the present invention.

<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 polymerization initiators that can be used 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; and anthrone derivatives.
Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferred.

Specifically, examples of titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluoro phenyl-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(methylcyclopenta dienyl) titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl-1-yl), dicyclo Pentadienyl titanium [2,6-di-fluoro-3-(pyrro-1-yl)-pheny-1-yl] is mentioned.

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

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

Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.

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-(4-diethylaminobenzoyl)coumarin and 4-(diethylamino)chalcone.

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

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

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

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 iodonium salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, and di(4-nonylphenyl)iodonium hexafluorophosphate. can be mentioned.

Examples of the 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 Can be mentioned.

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

Examples of acetophenone derivatives include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 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.

Examples of benzoic acid ester derivatives include ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

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

Examples of phenazine derivatives include 9,10-dimethylbenzphenazine.

Examples of anthrone derivatives include benzanthrone.

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 Chemical Co., Ltd.); kayacure (registered trademark) BP100, and UVI-6992 (manufactured by Dow Chemical Co., Ltd.); ADEKA Optomer SP-152, and SP-170 (manufactured by ADEKA Co., Ltd.); TAZ-A, and TAZ-PP (manufactured by Nippon Siberhegner Co., Ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (CHANGZHOU TRONLY NEW ELECTRONIC) MATERIALS CO.,LTD) (manufactured by).

When the composition for forming an anisotropic pigment film of the present invention contains a polymerization initiator, the content of the polymerization initiator in the composition for forming an anisotropic pigment film of the present invention does not disturb the orientation of the polymerizable liquid crystal compound. From the viewpoint of difficulty, the amount is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the polymerizable liquid crystal compound. Department.

Moreover, a polymerization accelerator may be used in combination with the polymerization initiator, if necessary. 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; and mercapto compounds such as aliphatic polyfunctional mercapto compounds.
One type of polymerization accelerator may be used alone, or two or more types may be used in combination.

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, such as xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; Coumarin dyes having a heterocycle as described in JP-A-239703, JP-A-5-289335, etc.; 3-ketocoumarin-based dyes as described in JP-A-3-239703, JP-A-5-289335, etc.; Pyrromethene dyes described in JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A-48-84183; 112681/1981, 15503/1983, 88005/1980, 56403/1983, 69/1991, 168088/1987 , JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like.
The sensitizing dyes may 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 in the composition for forming an anisotropic dye film of the present invention is not particularly limited as long as it can sufficiently disperse or dissolve the dye or other additives in the polymerizable liquid crystal compound.
Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, and γ. - Ester solvents such as butyrolactone, propylene glycol methyl ether acetate, ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, etc. ; Aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; Perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, hexa Examples include fluorine-containing solvents such as fluoro-2-propanol; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene.
These solvents may be used alone or in combination of two or more.

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

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 of the present invention is the total amount of the composition for forming an anisotropic pigment film of the present invention. (100% by mass), preferably 50% by mass or more and 98% by mass or less. In other words, the solid content in the composition for forming an anisotropic dye film of the present invention is preferably 2% by mass or more and 50% by mass or less.
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. Moreover, if it is more than the said lower limit, it tends to become easy to obtain a polarizing film with an appropriate thickness.
Such solid content can be determined in consideration of the thickness of the polarizing film to be manufactured.

The viscosity of the composition for forming 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. From the viewpoint of achieving thickness uniformity over a large area, productivity such as coating speed, and in-plane uniformity of optical properties, the viscosity of the composition for forming an anisotropic dye film of the present invention is 0.1 mPa·s or more. is preferable, 500 mPa·s or less is preferable, 100 mPa·s or less is more preferable, 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 include, as necessary, components other than the dye and the polymerizable liquid crystal compound, such as a polymerization inhibitor, a polymerization aid, and a polymerization initiator in addition to the above-mentioned polymerization initiator. Non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic/inorganic fillers, organic/inorganic nanosheets, organic/inorganic nanofibers, metal oxides, etc. It may also contain additives. By containing these additives, the coating properties, stability, etc. of the composition for forming an anisotropic pigment film of the present invention can be improved, and the composition for forming an anisotropic pigment film of the present invention can be formed from the composition for forming an anisotropic pigment film. In some cases, the stability of the anisotropic dye film can be improved.

<Method for producing composition for forming anisotropic pigment film>
The method for producing the composition for forming 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 forming 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 obtained by removing the solvent from the composition for forming an anisotropic dye film of the present invention preferably has an isotropic phase appearance temperature of less than 160°C, preferably 140°C, from the viewpoint of the coating process described below. It is more preferably less than 115°C, even more preferably less than 110°C, and particularly preferably less than 105°C.

[Anisotropic pigment film]
The anisotropic dye film of the present invention is formed using the composition for forming an anisotropic dye film of the present invention. Therefore, the anisotropic dye film of the present invention includes a dye and one or both of a polymerizable liquid crystal compound and a polymer having a structural unit based on the polymerizable liquid crystal compound, and the dye includes the compound of the present invention.

The anisotropic dye film of the present invention formed using the composition for forming an anisotropic dye film of the present invention preferably has a total mass of a polymerizable liquid crystal compound and a polymer having structural units based on the polymerizable liquid crystal compound. The concentration is 1 times or more, more preferably 1.5 times or more, even more preferably 2 times or more, particularly preferably 3 times or more, and preferably 1000 times or less, more preferably 700 times or more, the mass concentration of the compound of the present invention. It is contained in an amount not more than 500 times, more preferably not more than 500 times.

The anisotropic dye film of the present invention may optionally contain 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, It may also contain surfactants, leveling agents, coupling 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 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 of the anisotropic dye film 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 particularly preferably 40 or more. The higher the dichroic ratio, the better. 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. Furthermore, from the viewpoint of exhibiting polarizing performance in a wide range of wavelengths from 350 nm to 800 nm, if the dichroic ratio at a wavelength of 450 nm is 8 or more, it will function as a polarizing element, but this dichroic ratio is also preferably 12 or more, and 15 or more. More preferably, 20 or more is even more preferable.

When used as a polarizing element in an anti-reflection 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 anti-reflection 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, Az is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye. Ay is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is perpendicular.

There is no particular restriction on the respective absorbances (Az, Ay) as long as they have the same wavelength, and any wavelength may be selected depending on the purpose. When expressing the degree of orientation of the anisotropic dye film, it is preferable to use a value corrected by visibility in a specific wavelength range of 350 nm to 800 nm of the anisotropic dye film, or a value at the maximum absorption wavelength in the visible range.

Furthermore, the transmittance of the anisotropic dye film of the present invention is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more at the intended wavelength of use. 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. The transmittance of the anisotropic dye film of the present invention 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, even more preferably 500 nm or more, and preferably 30 μm or less, more preferably 10 μm or less, and still 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 an anisotropic dye film-forming composition onto a substrate by some method. Therefore, the composition for forming 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 composition for forming an anisotropic dye film is applied onto the substrate, the composition is already in the composition for forming an anisotropic dye film, or in the process of drying the solvent, or the solvent is completely removed. After that, the dye or liquid crystal compound self-associates (in a state of molecular association such as a liquid crystal state), thereby causing alignment 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. Here, the external field includes the influence of an alignment layer applied in advance on the substrate, shear force, magnetic field, electric field, heat, etc., and these may be used alone or in combination. If necessary, a heating step may be performed.

The process of applying the composition for forming 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 refers to the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, and the fast axis or slow axis in the case of a retardation film. It refers to the phase axis.

The method of applying an anisotropic pigment film-forming composition to obtain an anisotropic pigment film is not particularly limited, but for example, the method described in "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., March 20, 1971) The method described on pages 253-277 of ``Creation and Application of Molecular Cooperative Materials'' (CMC Publishing Co., Ltd., published March 3, 1998) supervised by Kunihiro Ichimura, Slot die coating method, spin coating method, spray coating method, bar coating method, roll coating method, blade coating method, curtain coating method, fountain method, dip method on a substrate having a step structure (orientation treatment may be performed in advance) An example of this method is to apply it using a method such as 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.

The 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 described, for example, in JP-A-2-164480, JP-A-6-154687, JP-A-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 Technology Corporation, ISBN 9784901677752), and "Precision coating and drying technology in the electronics field" (2007, Technical Information Association, ISBN 9784861041389). . These known slit dies can coat even flexible members such as films and tapes, and hard members such as glass substrates.

Examples of the substrate 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, Examples include triacetylcellulose or urethane-based films.

In order to control the orientation direction of the dye, the surface of the substrate is coated with a known method (rubbing method, orientation Orientation can be achieved by methods such as forming grooves (fine groove structures) on the film surface, using polarized ultraviolet light/polarized laser (photoalignment method), orientation method using LB film formation, orientation method using oblique vapor deposition of inorganic materials, etc. A treatment (alignment film) may be applied. 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 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 layer and the shear force applied to the composition for forming an anisotropic dye film during coating.

When applying the composition for forming an anisotropic pigment film, the method and interval for supplying the composition for forming 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-forming composition while supplying it.

The speed at which the composition for forming an anisotropic dye film is applied is preferably 0.001 m/min or more, more preferably 0.01 m/min or more, and still more preferably 0.1 m/min or more, Even more preferably it is 1.0 m/min or more, particularly preferably 5.0 m/min or more. Further, the speed is preferably 400 m/min or less, more preferably 200 m/min or less, even more preferably 100 m/min or less, even 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 composition for forming an anisotropic dye film is preferably 0°C or higher and 100°C or lower, more preferably 80°C or lower, and still more preferably 60°C or lower.
The humidity during application of the composition for forming an anisotropic dye film 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 the liquid crystal compound and the dye are oriented 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 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. Other layers include, for example, layers that have the function of blocking specific wavelengths and layers that have the function of blocking specific substances (oxygen (barrier films such as barrier films, water vapor blocking films, etc.); wavelength cut filters used to change the color gamut or improve optical properties; and layers containing materials that absorb specific wavelengths. .

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

Polarizing elements are not limited to anisotropic dye films, but also function as overcoat layers that improve polarization performance and mechanical strength; adhesive layers or antireflection layers; alignment films; and retardation films. , a layer having an optical function 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 on the opposite side 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.

A 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 the stretching treatment described in, for example, JP-A-2-59703, JP-A-4-230704, etc., or the treatment described in JP-A-7-230007, etc. It can be formed by

A 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 JP-A-2002-169025 and JP-A-2003-29030, or by forming two or more layers with different center wavelengths of selective reflection. It can be formed by overlapping cholesteric liquid crystal layers.

A layer having a function as a reflective film or a semi-transparent reflective film can be formed by, for example, 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 below with reference to Examples. The present invention is not limited to the following examples unless it exceeds the gist thereof.
In the following description, "parts" means "parts by mass."

[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 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.
Further, the wavelength at which the absorption of polarized light in the absorption axis direction is maximum was defined as the maximum absorption wavelength of the anisotropic dye film.
D=Az/Ay
(In the formula,
Ay=-log(Ty);
Az=-log(Tz);
Tz is the transmittance of the anisotropic dye film to polarized light in the absorption axis direction;
Ty is the transmittance of the anisotropic dye film to polarized light in the direction of the polarization axis. )

Specifically, a sandwich cell (cell gap: 8.0 μm or 10.0 μm) in which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, Inc.) was formed on glass as a substrate (cell gap: 8.0 μm or 10.0 μm), A composition for forming an anisotropic pigment film is injected in an isotropic phase into a material (previously rubbed with a cloth), and an anisotropic pigment film is obtained by cooling to 80 °C at a rate of 10 °C/min. The dichroic ratio was measured at each temperature while cooling to 40°C at a rate of 10°C/min. Among them, the dichroic ratio at a wavelength of 450 nm at the temperature showing the maximum dichroic ratio was determined as the dichroic ratio at a wavelength of 450 nm of the anisotropic dye film.

The dichroic ratio of the anisotropic dye film measured above is preferably 12 or more at a wavelength of 450 nm, which is sufficient for practical use, more preferably 15 or more, and even more preferably 20 or more.

[Synthesis of polymerizable liquid crystal compound]
<Polymerizable liquid crystal compound (I-1)>
A polymerizable liquid crystal compound (I-1) represented by the following structural formula was synthesized according to the description in JP-A-2020-042305. In the following formula, C ₁₁ H ₂₂ means that 11 methylene chains are linearly bonded.

Regarding the polymerizable liquid crystal compound (I-1), 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. For differential scanning calorimetry, 0.2 parts by mass of 4-methoxyphenol was added as a polymerization inhibitor to 100 parts by mass of polymerizable liquid crystal compound (I-1).
The phase transition temperature from liquid crystal to liquid crystal of polymerizable liquid crystal compound (I-1) was 111.0°C, and the phase transition temperature from liquid crystal to liquid crystal was 109.4°C.
It was confirmed by polarizing microscope observation and X-ray structure analysis that this temperature was the isotropic phase appearance temperature.

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

Synthesis of (II-1-a):
3,5,5-triethyl-1-hexanol (76.8 g, 532 mmol), 47% aqueous hydrogen bromide (HBr) solution (100.8 g, 586 mmol), and concentrated sulfuric acid (16.6 g, 185 mmol) were mixed, and 120 Stirred at ℃ for 5 hours. After cooling to 25°C, it was added to hexane (1200 mL) and washed with purified water (2400 mL x 3). After concentrating the organic layer, it was purified by silica gel chromatography (hexane) to obtain 71.0 g of (II-1-a).

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

Synthesis of (II-1-c):
Under an argon stream, (II-1-b) (113.5 g, 427.7 mmol) and ethyl acetate (1100 mL) were mixed, followed by palladium on carbon (5% Pd/C, water content 55% by mass, 11.4 g). was added and stirred at 25° C. for 60 hours under a hydrogen atmosphere. After purging the inside of the container with argon, the catalyst was filtered off. The catalyst was extracted with dichloromethane, the organic layers were combined, concentrated, and purified by silica gel chromatography (dichloromethane) to obtain 99.5 g of (II-1-c).

Synthesis of (II-1-d):
At room temperature under a nitrogen stream, (II-1-c) (43.3 g, 0.184 mol) and acetic acid (1.3 L) were added, stirred and dissolved, and 1-nitroso-4-nitrobenzene (28.0 g, 1 .0eq.) was added in portions. After stirring for 4 hours, 1-nitroso-4-nitrobenzene (8.4 g, 0.3 eq.) was further added, and stirring was continued at room temperature overnight. Dichloromethane (3.9 L) and purified water (1.3 L) were poured into the mixture, and after stirring for a while, the oil and water were separated. After extracting the aqueous layer with dichloromethane (1.3 L), it was combined with the original organic layer, washed sequentially with purified water (1.3 L), saturated sodium bicarbonate solution (1.3 L), and saturated brine (500 mL), then anhydrous. Drying with magnesium sulfate, filtration, and concentration of the filtrate gave a reddish brown solid. This crude product was purified by silica gel column chromatography (hexane/dichloromethane = 3/1) to obtain 52.08 g of (II-1-d).

Synthesis of (II-1-e):
(II-1-d) (52.0 g, 0.141 mol), ethanol (520 mL), purified water (52 mL), and sodium sulfide pentahydrate (Na ₂ S.5H ₂ O) (47.4 g, 2. 0 equiv.) was added and stirred at an external temperature of 80°C for 6 hours. After cooling to room temperature, the reaction solution was poured into purified water (500 mL), stirred for a while, collected by suction filtration, and rinsed with purified water (250 mL). The obtained solid was purified by silica gel column chromatography (dichloromethane) to obtain 34.40 g of (II-1-e).

Synthesis of (II-1-f):
At room temperature under a nitrogen stream, (II-1-e) (34.4 g, 0.101 mol) and acetic acid (1.0 L) were added, stirred and dissolved, and 1-nitroso-4-nitrobenzene (20.0 g, 1 .3 eq.) was added in portions, and stirring was continued at room temperature overnight. The reaction solution was poured into purified water and stirred at room temperature for a while, then collected by suction filtration and rinsed with purified water. This solid was purified by silica gel column chromatography (chloroform) to obtain 38.6 g of (II-1-f).

Synthesis of (II-1-g):
At room temperature under nitrogen atmosphere, (II-1-f) (38.6 g, 81.5 mmol), ethanol (386 mL), purified water (39 mL) and Na ₂ S 5H ₂ O (27.4 g, 2.0 equiv) ) was added and stirred at an external temperature of 80°C for 6 hours. After cooling to room temperature, the reaction solution was poured into purified water (400 mL), stirred for a while, collected by suction filtration, and rinsed with purified water (200 mL). The obtained solid was purified by silica gel column chromatography (hexane/dichloromethane = 1/1) to obtain 30.20 g of (II-1-g).

Synthesis of (II-1-h):
N-ethylaniline (2.71 g, 22.3 mmol), 1,1,1-trifluoro-3-iodopropane (9.98 g, 2.0 eq.), acetonitrile (15 mL), potassium carbonate (6.45 g, 2.3 eq.) was charged, and the mixture was heated and stirred at 90° C. for 24 hours under a nitrogen atmosphere. After cooling to room temperature, purified water (50 mL) was added and extracted with ethyl acetate/hexane (=10/40 mL). After concentrating the organic layer, it was purified by silica gel column chromatography (dichloromethane/hexane = 1/9) to obtain 865 mg of (II-1-h).

Synthesis of dye (II-1):
(II-1-g) (750 mg, 1.69 mmol) was dissolved in acetic acid (20 mL) and propionic acid (10 mL) in a reactor at room temperature under a nitrogen atmosphere, and then cooled to an internal temperature of 0°C. A nitrosyl sulfuric acid/sulfuric acid solution (40% by mass, 698 mg, 1.3 eq.) was added dropwise, and the mixture was stirred at an internal temperature of 0 to 2°C for 1 hour.
In another reactor, (II-1-h) (515 mg, 1.5 eq.) was dissolved in methanol (6 mL) and tetrahydrofuran (THF) (6 mL) at room temperature under nitrogen atmosphere, and then acetic acid was added. Sodium (361 mg, 2.6 eq.) was added, and the mixture was cooled to an internal temperature of 0°C.
The above solution (II-1-g) was added thereto over 20 minutes at an internal temperature of 0 to 3°C, and stirring was continued for 2 hours at an internal temperature of 0°C and for 5 hours while returning to room temperature. Purified water (20 mL) was added dropwise, and the precipitate was collected by suction filtration and washed with purified water (30 mL) to obtain a red wet solid (1.02 g). This crude product was separated and purified by silica gel column chromatography (dichloromethane/hexane = 1/3) to obtain 404 mg of dye (II-1).

The maximum absorption wavelength (λmax2) of dye (II-1) in a 10 ppm chloroform solution was 482 nm.
In addition, the structure was confirmed by nuclear magnetic resonance (NMR) spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ0.92 (s, 9H), δ1.02 (d, 3H, J=6.8Hz), δ1.14-1.33 (m, 5H), δ1.65 -1.87 (m, 3H), δ2.48 (m, 2H), δ3.51 (q, 2H, J = 6.8Hz), δ3.69 (t, 2H, J = 8.0Hz), δ4 .08 (t, 2H, J = 6.8Hz), δ6.76 (d, 2H, J = 9.2Hz), δ7.03 (d, 2H, J = 9.2Hz), δ7.92-8. 10 (m, 12H)

The solubility of dye (II-1) in cyclopentanone was measured.
3 mg of dye (II-1) was added to 103 mg of cyclopentanone, and the mixture was stirred at 80°C for 5 minutes. Thereafter, the dye (II-1) was left to stand at room temperature for 1 hour, and the resulting mixture was filtered using a syringe equipped with a syringe filter (manufactured by ADVANTEC, DISMIC 03JP050AN 39102251, diameter 0.5 μm). A saturated solution of cyclopentanone was obtained. This solution was diluted with 746 mg of tetrahydrofuran, and the concentration was determined using a liquid chromatograph (HPLC) (L-2300 series manufactured by Hitachi High Technologies). A solution of 0.1% by mass 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. The results are shown in Table 1.

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

Synthesis of (II-2-a):
At room temperature under a nitrogen stream, molecular sieve 4A (2.0 g), tripotasium phosphite (1.17 g, 0.1 equiv.), 18-crown 6-ether (2.90 g, 0.2 equiv.), THF ( 330 mL), N-ethylaniline (6.65 g, 50.8 mmol), trifluoroacetic acid (28.8 g, 4.6 equiv.), and phenylsilane (23.7 g, 4.0 equiv.) were added. The mixture was stirred at 80° C. for 6 hours under heating and reflux. After cooling, purified water (200 mL) was added, and the solid was filtered off. The filtrate was extracted with dichloromethane (100 mL x 2) and concentrated under reduced pressure to obtain a crude pale yellow oil (44.0 g). This was purified by silica gel column chromatography (dichloromethane/hexane = 20/1) to obtain 5.85 g of (II-2-a).

Synthesis of dye (II-2):
(II-1-g) (750 mg, 1.69 mmol) was dissolved in acetic acid (20 mL) and propionic acid (10 mL) at room temperature under a nitrogen atmosphere, and then cooled to an internal temperature of 0°C. A nitrosyl sulfuric acid/sulfuric acid solution (40% by mass, 698 mg, 1.3 eq.) was added dropwise at an internal temperature of 0 to 3°C, and the mixture was stirred for 1 hour at an internal temperature of 0 to 2°C.
In another reactor, (II-2-a) (482 mg, 1.5 eq.) was dissolved in methanol (6 mL) and THF (6 mL) at room temperature under nitrogen atmosphere, and then sodium acetate (361 mg, 2 .6 eq.) was added, and the mixture was cooled to an internal temperature of 0°C.
The above solution (II-1-g) was added thereto over 20 minutes at an internal temperature of 0 to 5°C, and the mixture was stirred for 2 hours at an internal temperature of 0 to 5°C and for 6 hours while returning to room temperature. Purified water (20 mL) was added dropwise and the precipitate was collected by suction filtration, and the obtained solid was separated and purified by silica gel column chromatography (dichloromethane/hexane = 1/3) to obtain 249 mg of dye (II-2).

The maximum absorption wavelength (λmax2) of dye (II-2) in a 10 ppm chloroform solution was 446 nm.
In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ0.92 (s, 9H), δ1.02 (d, 3H, J=6.8Hz), δ1.14-1.34 (m, 5H), δ1.65 -1.87 (m, 3H), δ3.62 (q, 2H, J = 6.8Hz), δ3.98 (q, 2H, J = 8.8Hz), δ4.09 (t, 2H, J = 6.8Hz), δ6.90 (d, 2H, J = 9.2Hz), δ7.03 (d, 2H, J = 9.2Hz), δ7.92-8.10 (m, 12H)

For dye (II-2), the concentration of the cyclopentanone saturated solution was measured in the same manner as for dye (II-1). The results are shown in Table 1.

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

Synthesis of (II-3-a):
At room temperature under a nitrogen stream, molecular sieve 4A (2.0 g), tripotasium phosphite (1.08 g, 0.1 equiv.), 18-crown 6-ether (2.68 g, 0.2 equiv.), THF ( 300 mL), N-ethylaniline (6.16 g, 50.8 mmol), difluoroacetic acid (11.2 g, 2.3 equiv.), and phenylsilane (22.0 g, 4.0 equiv.) were added, and the temperature was raised to 80 ml. The mixture was stirred for 6 hours under heating at reflux. After cooling, purified water (200 mL) was added, and the solid was filtered off. The filtrate was extracted with dichloromethane (100 mL x 2) and concentrated under reduced pressure to obtain a crude pale yellow oil (40.0 g). This was purified by silica gel column chromatography (dichloromethane/hexane = 20/1) to obtain 5.73 g of (II-3-a).

Synthesis of dye (II-3):
(II-1-g) (750 mg, 1.69 mmol) was dissolved in acetic acid (20 mL) and propionic acid (10 mL) at room temperature under a nitrogen atmosphere, and then cooled to an internal temperature of 0°C. A nitrosyl sulfuric acid/sulfuric acid solution (40% by mass, 698 mg, 1.3 eq.) was added dropwise at an internal temperature of 0 to 3°C, and the mixture was stirred for 1 hour at an internal temperature of 0 to 2°C.
In another reactor, (II-3-a) (470 mg, 1.5 eq.) was dissolved in methanol (6 mL) and THF (6 mL) at room temperature under nitrogen atmosphere, and then sodium acetate (361 mg, 2 .6 eq.) was added, and the mixture was cooled to an internal temperature of 0°C.
The above solution (II-1-g) was added thereto over 22 minutes at an internal temperature of 0 to 5°C, and stirring was continued for 1 hour and 40 minutes at an internal temperature of 0 to 5°C for 6 hours while returning to room temperature. Purified water (20 mL) was added dropwise and the precipitate was collected by suction filtration to obtain a red wet solid (1.04 g). This crude product was purified by silica gel column chromatography (dichloromethane/hexane = 1/3) to obtain 299 mg of dye (II-3).

The maximum absorption wavelength (λmax2) of dye (II-3) in a 10 ppm chloroform solution was 465 nm.
In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ0.92 (s, 9H), δ1.02 (d, 3H, J=6.8Hz), δ1.16-1.34 (m, 5H), δ1.65 -1.87 (m, 3H), δ3.62 (q, 2H, J = 6.8Hz), δ3.98 (q, 2H, J = 8.8Hz), δ4.09 (t, 2H, J = 6.8Hz), δ6.90 (d, 2H, J = 9.2Hz), δ7.03 (d, 2H, J = 9.2Hz), δ7.92-8.10 (m, 12H)

The concentration of the cyclopentanone saturated solution for dye (II-3) was also measured in the same manner as for dye (II-1). The results are shown in Table 1.

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

Synthesis of (II-4-a):
In a reaction vessel, aniline (670 mg, 7.19 mmol), 1-fluoro-2-iodoethane (2.50 g, 2.0 eq.), dimethylformamide (DMF) (25 mL), potassium carbonate (3.98 g, 4.0 eq. ) and heated and stirred at 85° C. for 17 hours under a nitrogen atmosphere. After cooling to room temperature, it was quenched with purified water (50 mL) and extracted with ethyl acetate/hexane (=10/40 mL). The organic layer was washed successively with purified water (25 mL x 3) and saturated brine (10 mL), filtered, and the filtrate was concentrated to obtain a crude yellow oil (1.31 g). This crude product was separated and purified by silica gel column chromatography (dichloromethane/hexane = 1/9) to obtain 202 mg of (II-4-a).

Synthesis of dye (II-4):
(II-1-g) (3.0 g, 6.76 mmol) was dissolved in acetic acid (80 mL) and propionic acid (40 mL) at room temperature under a nitrogen atmosphere, and then cooled to an internal temperature of 0°C. A nitrosyl sulfuric acid/sulfuric acid solution (40% by mass, 2.8 g, 1.3 eq.) was added dropwise at an internal temperature of 0 to 3°C, and the mixture was stirred for 1 hour at an internal temperature of 0 to 2°C.
In another reactor, (II-4-a) (1.87 g, 1.5 eq.) was dissolved in methanol (24 mL) and THF (24 mL) at room temperature under nitrogen atmosphere, and then sodium acetate (1 .44 g, 2.6 eq.) was added thereto, and the mixture was cooled to an internal temperature of 0°C.
The above solution (II-1-g) was added thereto over 30 minutes at an internal temperature of 0 to 5°C, and the mixture was stirred for 2 hours at an internal temperature of 0 to 5°C and for 6 hours while returning to room temperature. Purified water (80 mL) was added dropwise and the precipitate was collected by suction filtration to obtain a red wet solid (2.74 g). This crude product was purified by silica gel column chromatography (dichloromethane/hexane = 1/3 and toluene) to obtain dye (II-4) (856 mg).

The maximum absorption wavelength (λmax2) of dye (II-4) in a 10 ppm chloroform solution was 465 nm.
In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ1.00 (t, 3H, J=7.8Hz), δ1.47-1.56 (m, 4H), δ1.76-1.83 (m, 2H) , δ2.67 (s, 1H, J=13.6Hz, 6.0Hz), δ1.29-1.30 (m, 1H), δ1.65-1.87 (m, 3H), δ3.83( t, 2H, J = 5.6Hz), δ 3.89 (t, 2H, J = 5.6Hz), δ 4.37 (t, 2H, J = 5.2Hz), δ 4.62 (t, 2H, J = 6.2Hz), δ4.74 (t, 2H, J = 6.2Hz), δ6.79 (d, 2H, J = 9.2Hz), δ7.02 (d, 2H, J = 9.2Hz) , δ7.92-8.09 (m, 8H), δ8.20 (d, 2H, J=8.5Hz)

The concentration of the cyclopentanone saturated solution for dye (II-4) was also measured in the same manner as for dye (II-1). The results are shown in Table 1.

<Dye (II-5)>
Dye (II-5) was synthesized according to the synthesis method described below.

Synthesis of (II-5-a):
4-[(4-aminophenyl)diazenyl]benzoic acid (500 mg, 2.07 mmol) was dissolved in acetic acid (15 mL) and N-methyl-2-pyrrolidone (NMP) (5 mL) at room temperature under a nitrogen atmosphere. Thereafter, it was cooled to an internal temperature of 0°C. A nitrosyl sulfuric acid/sulfuric acid solution (40% by mass, 850 mg, 1.3 eq.) was added dropwise at an internal temperature of 0 to 3°C, and the mixture was stirred for 1 hour at an internal temperature of 0 to 2°C. In another reactor, (II-4-a) (572 mg, 1.5 eq.) was dissolved in methanol (6 mL) and THF (6 mL) at room temperature under nitrogen atmosphere, and then sodium acetate (440 mg, 2 .6 eq.) was added, and the mixture was cooled to an internal temperature of 0°C.
The above 4-[(4-aminophenyl)diazenyl]benzoic acid solution was added thereto, and stirring was continued for 1 hour and 50 minutes at an internal temperature of 0 to 5°C for 14 hours while returning to room temperature. Purified water (20 mL) was added, and the precipitate was collected by suction filtration to obtain 425 mg of (II-5-a).

Synthesis of dye (II-5):
(II-5-a) (425 mg, 0.960 mmol), n-BuBr (198 mg, 1.5 eq.), DMF (4 mL), and potassium carbonate (200 mg, 1.5 eq.) were prepared and heated at 90°C under nitrogen atmosphere. The mixture was heated and stirred for 4.5 hours. After cooling to room temperature, purified water (30 mL) was added, and the precipitated solid was filtered off to obtain 380 mg of a reddish brown solid. This crude product was purified by silica gel column chromatography (dichloromethane/ethyl acetate/hexane = 5/3/50) to obtain 149 mg of dye (II-5).

The maximum absorption wavelength (λmax2) of dye (II-5) in a 10 ppm chloroform solution was 456 nm.
In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ1.00 (t, 3H, J=7.8Hz), δ1.47-1.56 (m, 4H), δ1.76-1.83 (m, 2H) , δ2.67 (s, 1H, J=13.6Hz, 6.0Hz), δ1.29-1.30 (m, 1H), δ1.65-1.87 (m, 3H), δ3.83( t, 2H, J = 5.6Hz), δ 3.89 (t, 2H, J = 5.6Hz), δ 4.37 (t, 2H, J = 5.2Hz), δ 4.62 (t, 2H, J = 6.2Hz), δ4.74 (t, 2H, J = 6.2Hz), δ6.79 (d, 2H, J = 9.2Hz), δ7.02 (d, 2H, J = 9.2Hz) , δ7.92-8.09 (m, 8H), δ8.20 (d, 2H, J=8.5Hz)

For dye (II-5), the concentration of the cyclopentanone saturated solution was measured in the same manner as for dye (II-1). The results are shown in Table 1.

<Dye (II-6)>
Dye (II-6) was synthesized according to the synthesis method described below.

Synthesis of (II-6-a):
(II-1-g) (500 mg, 1.13 mmol) and 1-nitroso-4-bromobenzene (273 mg, 1.47 mmol) were dissolved in acetic acid (30 mL) and stirred at room temperature for 6 hours. Purified water was added, and the precipitate was washed with acetonitrile and filtered to obtain 469 mg of a red solid (II-6-a).

Synthesis of dye (II-6):
Amphos (3.90 mg, 3 mol%) and Pd ₂ (dba) ₃ (2.24 mg, 0.5 mol%) were dissolved in toluene (10 mL) at room temperature under a nitrogen atmosphere, and the mixture was stirred at 60° C. for 15 minutes.
In a separate reactor, (II-6-a) (0.40 g, 0.49 mmol) and 3,3-difluoropyrrolidine hydrochloride (0.212 mg, 1.96 mmol) were mixed with toluene ( 20 mL), heated to 100°C, and the above palladium solution was added dropwise thereto. After stirring for 8 hours, purified water (80 mL) was added dropwise and the precipitate was collected by suction filtration. This crude product was purified by silica gel column chromatography (toluene/dichloromethane = 1/1) to obtain 207 mg of dye (II-6).

The maximum absorption wavelength (λmax2) of dye (II-6) in a 10 ppm chloroform solution was 466 nm.
In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ0.92 (s, 9H), δ1.02 (d, 3H, J=6.8Hz), δ1.12-1.33 (m, 5H), δ1.65 -1.89 (m, 3H), δ2.50-2.59 (m, 2H), δ3.69 (t, 2H, J=6.8Hz), δ3.81 (q, 2H, J=12. 9Hz), δ4.09 (t, 2H, J=6.8Hz), δ6.65 (d, 2H, J=9.2Hz), δ7.03 (d, 2H, J=9.0Hz), δ7. 95-8.10 (m, 12H)

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

Synthesis of (III-1-a):
At room temperature under a nitrogen stream, 4-butylaniline (43.3 g, 0.290 mol) and acetic acid (2 L) were added, stirred and dissolved, and 1-nitroso-4-nitrobenzene (43.7 g, 1.0 eq.) was added. The mixture was added in portions and stirring was continued at room temperature overnight. Dichloromethane (5 L) and purified water (1.5 L) were poured in, and after stirring for a while, the organic phase was washed successively with saturated sodium bicarbonate solution (1.3 L) and saturated brine (500 mL), filtered, and the filtrate was concentrated to reddish brown. A solid was obtained. This crude product was purified by silica gel column chromatography (hexane/dichloromethane = 3/1) to obtain 52.08 g of (III-1-a).

Synthesis of (III-1-b):
(III-1-a) (52.0 g, 0.184 mol), ethanol (520 mL), purified water (52 mL) and Na ₂ S 5H ₂ O (62.13 g, 2.0 equiv.) were added and the external temperature was 80. Stirred at ℃ for 6 hours. After cooling to room temperature, the reaction solution was poured into purified water (500 mL), stirred for a while, collected by suction filtration, and rinsed with purified water (250 mL). The obtained solid was purified by silica gel column chromatography (dichloromethane) to obtain 34.40 g of (III-1-b).

Synthesis of (III-1-c):
(III-1-b) (2.00 g, 5.60 mmol) and hydrochloric acid (HCl) (2.63 mL) were dissolved in NMP (50 mL) and cooled to an internal temperature of 0°C. Sodium nitrate (0.538 g, 7.76 mmol) was dissolved in 5 mL of purified water, added dropwise to the above solution at an internal temperature of 0 to 3°C, and stirred for 1 hour at an internal temperature of 0 to 2°C.
In a separate reactor, aniline (2.54 g, 1.5 eq.) was dissolved in methanol (24 mL) at room temperature under a nitrogen atmosphere, then sodium acetate (1.96 g) was added, and the internal temperature was brought to 0°C. Cooled. The above solution (III-1-b) was added thereto over 30 minutes at an internal temperature of 0 to 5°C, and stirring was continued for 2 hours at an internal temperature of 0 to 5°C and for 3 hours while returning to room temperature. Purified water was added, filtered and washed with methanol, and the obtained crude product was purified by silica gel column chromatography (toluene/dichloromethane = 1/1) to obtain (III-1-c) in 2. I got 50g.

Synthesis of dye (III-1):
(III-1-c) (2.00 g, 5.44 mmol) and HCl (1.93 mL) were dissolved in NMP (50 mL) and cooled to an internal temperature of 0°C. Sodium nitrate (0.395 g, 5.712 mmol) was dissolved in 5 mL of purified water, added dropwise to the above solution at an internal temperature of 0 to 3°C, and stirred for 1 hour at an internal temperature of 0 to 2°C.
In another reactor, aniline (1.22 g, 1.5 eq.) was dissolved in methanol (40 mL) at room temperature under a nitrogen atmosphere, then sodium acetate (1.44 g) was added, and the internal temperature was brought to 0°C. Cooled. The above solution (III-1-c) was added thereto over 30 minutes at an internal temperature of 0 to 5°C, and the mixture was stirred for 1 hour at an internal temperature of 0 to 5°C, and for 2 hours while returning to room temperature. Purified water was added, filtered and washed with methanol, and the resulting crude product was purified by column chromatography on silica gel (toluene/dichloromethane = 1/3) to obtain 2.39 g of dye (III-1). Obtained.

The maximum absorption wavelength (λmax2) of the dye (III-1) in a 10 ppm chloroform solution was 509 nm.

In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ0.96 (t, 3H), δ1.25 (t, 6H, J=6.8Hz), δ1.37-1.42 (m, 2H), δ1.63 -1.71 (m, 2H), δ2.71 (t, 2H, J=7.8Hz), δ3.48 (q, 4H, J=8.2Hz), δ6.74 (d, 2H, J= 9.2Hz), δ7.34 (d, 2H, J=8.4Hz), δ7.74-8.10 (m, 12H)

The concentration of the cyclopentanone saturated solution for dye (III-1) was also measured in the same manner as for dye (II-1). The results are shown in Table 1.

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

Synthesis of (III-2-a):
4-Amino-4'-hydroxyazobenzene (23.0 g, 108 mmol) and HCl (19 mL, 230 mmol) were dissolved in NMP (460 mL) and purified water (330 mL), and the mixture was cooled to an internal temperature of 0°C. Sodium nitrate (8.21 g, 119 mmol) was dissolved in purified water (33 mL), added dropwise to the above solution, and stirred for 1 hour at an internal temperature of 0 to 2°C. An aqueous solution of sulfamic acid (2.10 g, 21.6 mmol) dissolved in purified water (19 mL) was added dropwise to the above solution, and the mixture was stirred for 10 minutes at an internal temperature of 0 to 2°C.
Aniline (12.1 g, 130 mmol), sodium hydroxymethanesulfonate (17.4 g, 130 mmol), and purified water (340 mL) were placed in another reactor at room temperature under a nitrogen atmosphere, and the mixture was stirred at 70°C for 3 hours. . After cooling, the mixture was dissolved in methanol (340 mL), cooled on ice, and the above 4-amino-4'-hydroxyazobenzene solution was added over 40 minutes at an internal temperature of 0 to 5°C. At this time, the dropwise addition was carried out while adjusting the pH to 4-5 with a 25% NaOH aqueous solution. The mixture was stirred for 1 hour at an internal temperature of 0 to 5°C, and 70% sulfuric acid was added to adjust the pH to 2.5. The reaction solution was poured into a 5% NaCl aqueous solution (1 L), and the precipitated solid was filtered and washed with saturated brine.
This solid was placed in another reaction vessel, 1M NaOH aqueous solution (1.1L) was added, and the mixture was stirred at 90°C for 2.5 hours. After cooling, the pH was adjusted to 6 with concentrated hydrochloric acid and 2M hydrochloric acid, and the precipitated solid was collected by filtration and washed with purified water and hexane. The obtained crude product was suspended and washed with dichloromethane and recrystallized from ethyl acetate to obtain 13.0 g of (III-2-a).

Synthesis of dye (III-2):
(III-2-a) (1.00 g, 3.15 mmol) and HCl (0.55 mL, 6.6 mmol) were dissolved in NMP (20 mL) and cooled to an internal temperature of 0°C. Sodium nitrate (0.239 g, 3.46 mmol) was dissolved in 1 mL of purified water, added dropwise to the (III-2-a) solution, and stirred for 1 hour at an internal temperature of 0 to 2°C. An aqueous solution of sulfamic acid (61 mg, 0.63 mmol) dissolved in purified water (0.55 mL) was added dropwise to the above solution, and the mixture was stirred for 10 minutes at an internal temperature of 0 to 2°C.
In another reactor, N-phenylpyrrolidine (0.464 mg, 3.15 mmol) was dissolved in methanol (10 mL) at room temperature under a nitrogen atmosphere, and then 2M hydrochloric acid was added to adjust the pH to 5. Cooled to ℃. The above solution (III-2-a) was added thereto over 40 minutes at an internal temperature of 0 to 5°C. At this time, the dropwise addition was carried out while adjusting the pH to 4-5 with a 25% NaOH aqueous solution. The mixture was stirred for 30 minutes at an internal temperature of 0 to 5°C, and 70% sulfuric acid was added to adjust the pH to 2.5. Purified water was added, and the mixture was filtered and washed with methanol and hexane to obtain a crude product. The crude product was suspended and washed with acetonitrile and dichloromethane/methanol=1/1 to obtain 0.86 g of dye (III-2).

The maximum absorption wavelength (λmax2) of dye (III-2) in a 10 ppm chloroform solution was 510 nm.
In addition, the structure was confirmed by NMR spectrum measurement. The results are shown below.
¹ H-NMR (CDCl ₃ , 400MHz) δ0.92 (s, 9H), δ1.02 (d, 3H, J=6.8Hz), δ1.12-1.33 (m, 4H), δ1.65 -1.89 (m, 3H), δ2.50-2.59 (m, 4H), δ3.78-3.80 (m, 4H), δ4.09 (t, 2H, J=6.8Hz) , δ6.65 (d, 2H, J=9.2Hz), δ7.03 (d, 2H, J=9.0Hz), δ7.95-8.10 (m, 12H)

The chemical structures of the polymerizable liquid crystal compound (I-1) and dyes (II-1) to (II-6), (III-1), and (III-2) synthesized above are shown below.

[Example 1]
Add 40.00 parts of polymerizable liquid crystal compound (I-1) and 0.80 parts of dye (II-1) to 8032.1 parts of chloroform, stir to dissolve, and then remove the solvent. As a result, Composition 1 for forming an anisotropic dye film was obtained. The rn ₁ /rn ₂ of the composition 1 for forming an anisotropic dye film is 0.75.
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 1.

[Example 2]
Anisotropic pigment film forming composition 2 and An anisotropic dye film 2 was obtained. The rn ₁ /rn ₂ of the composition 2 for forming an anisotropic dye film is 0.75.
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.
Furthermore, the dichroic ratio of the anisotropic dye film 2 was determined.
The results are shown in Table 1.

[Example 3]
Anisotropic pigment film forming composition 3 and An anisotropic dye film 3 was obtained. The rn ₁ /rn ₂ of the composition 3 for forming an anisotropic dye film is 0.75.
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.
Furthermore, the dichroic ratio of the anisotropic dye film 3 was determined.
The results are shown in Table 1.

[Example 4]
Anisotropic pigment film forming composition 4 and An anisotropic dye film 4 was obtained. The rn ₁ /rn ₂ of the composition 4 for forming an anisotropic dye film is 0.75.
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.
Furthermore, the dichroic ratio of the anisotropic dye film 4 was determined.
The results are shown in Table 1.

[Example 5]
Anisotropic pigment film forming composition 5 and An anisotropic dye film 5 was obtained. The rn ₁ /rn ₂ of the composition 5 for forming an anisotropic dye film is 1.
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.
Furthermore, the dichroic ratio of the anisotropic dye film 5 was determined.
The results are shown in Table 1.

[Comparative example 1]
Anisotropic dye film forming composition 6 and An anisotropic dye film 6 was obtained. The rn ₁ /rn ₂ of the composition 6 for forming an anisotropic dye film is 0.75.
It was confirmed that the anisotropic dye film-forming composition 6 exhibited liquid crystallinity by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
Furthermore, the dichroic ratio of the anisotropic dye film 6 was determined.
The results are shown in Table 1.

From Table 1, the dye (II-1) used in Example 1, the dye (II-2) used in Example 2, the dye (II-3) used in Example 3, and the dye used in Example 4. (II-4) The dye (II-5) used in Example 5 has high solubility in cyclopentanone, and the maximum absorption wavelength of the obtained anisotropic dye film is shorter than that of Comparative Example 1. The dichroic ratio showed a good value in the short wavelength range of 450 nm. On the other hand, Comparative Example 1 showed that the dichroic ratio and solubility in cyclopentanone were lower than those of the examples.

[Example 6]
Anisotropic pigment film forming composition 7 and An anisotropic dye film 7 was obtained. The rn ₁ /rn ₂ of the composition 7 for forming an anisotropic dye film is 0.75.
The fact that Composition 7 for Forming an Anisotropic Dye Film exhibits liquid crystallinity was confirmed by observing birefringence at 40° C. using a polarizing microscope equipped with a hot stage.
Furthermore, the dichroic ratio of the anisotropic dye film 7 was determined.
The results are shown in Table 2.

[Comparative example 2]
Anisotropic dye film-forming composition 8 and An anisotropic dye film 8 was obtained. The rn ₁ /rn ₂ of the composition 8 for forming an anisotropic dye film is 0.75.
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.
Furthermore, the dichroic ratio of the anisotropic dye film 8 was determined.
The results are shown in Table 2.

From Table 2, the maximum absorption wavelength of the obtained anisotropic dye film of the dye (II-6) used in Example 6 is shorter than that of Comparative Example 2, and the dichroic ratio is in the short wavelength range. Good values were shown at a certain wavelength of 450 nm. On the other hand, Comparative Example 2 showed that the obtained anisotropic dye film had a low dichroic ratio.

Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various changes can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2022-044888 filed on March 22, 2022, which is incorporated by reference in its entirety.

Claims

A compound represented by the following formula (1).

(In formula (1),
-X 1 represents a monovalent organic group.
-R 11 represents an alkyl group substituted with one or more fluorine atoms.
-R 12 represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
The alkyl group substituted with one or more fluorine atoms in -R 11 , the alkyl group substituted with one or more fluorine atoms in -R 12 , and the alkyl group substituted with one or more fluorine atoms may further have a substituent.
In addition, one or more methylene groups contained in the alkyl group substituted with one or more fluorine atoms in -R 11 , the alkyl group in -R 12 , and the alkyl group substituted with one or more fluorine atoms are , -O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHCl-, or -CCl 2 - The structure may be replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
-R 11 and -R 12 may be combined to form a ring, and the ring may have a substituent.
-A 11 -, -A 12 -, -A 13 - and -A 14 - each independently represent a 1,4-phenylene group which may have a substituent. )
The compound according to claim 1, wherein -R 11 in the formula (1) is an alkyl group substituted with one or more and five or less fluorine atoms.
The compound according to claim 1, wherein -R 11 in the formula (1) is an alkyl group having 1 or more and 10 or less carbon atoms and substituted with one or more fluorine atoms.
-X 1 in the formula (1) is a hydrogen atom, -R a , -O-R a , -NH-R a , -C(=O)-R a , -C(=O)-O-R a , -C(=O)-NH-R a , -C(=O)-N(-R b )-R a , -OC(=O)-R a , -NH-C(=O ) -R a , -N(-R b )-C(=O)-R a , or -S-R a (-R a and -R b may each independently have a branch Represents an alkyl group having 1 to 15 carbon atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms. and the aryl group may each have a substituent.Also, -R a and -R b may be combined to form a ring having 2 to 15 carbon atoms, and the ring may be unsubstituted. In addition, one or more methylene groups contained in the ring formed by combining the alkyl group, cycloalkyl group, aryl group, and R a and R b may have a - O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl - or -CCl 2 -, or a structure replaced with a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.) , a compound according to any one of claims 1 to 3.
An anisotropic dye film-forming composition comprising a compound represented by the following formula (2) and a polymerizable liquid crystal compound.

(In formula (2),
-X represents a monovalent organic group.
-R 1 represents an alkyl group substituted with one or more fluorine atoms.
-R 2 represents a hydrogen atom, an alkyl group, or an alkyl group substituted with one or more fluorine atoms.
The alkyl group substituted with one or more fluorine atoms in -R 1 , the alkyl group substituted with one or more fluorine atoms in -R 2 , and the alkyl group substituted with one or more fluorine atoms may further have a substituent.
In addition, one or more methylene groups contained in the alkyl group substituted with one or more fluorine atoms in -R 1 , the alkyl group in -R 2 , and the alkyl group substituted with one or more fluorine atoms are - Replaced by O-, -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHCl-, or -CCl 2 - The structure may be replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group.
-R 1 and -R 2 may be combined to form a ring, and the ring may have a substituent.
-A 1 -, -A 2 - and -A 3 - each independently represent a divalent group of an aromatic hydrocarbon ring which may have a substituent.
n represents 1, 2 or 3.
When n is 2 or 3, the plurality of -A 2 -s may be the same or different. )
The composition for forming an anisotropic dye film according to claim 5, wherein -A 3 - in the formula (2) is a 1,4-phenylene group which may have a substituent.
The composition for forming an anisotropic dye film according to claim 5 or 6, wherein -A 2 - in the formula (2) is a 1,4-phenylene group which may have a substituent.
For forming an anisotropic dye film according to any one of claims 5 to 7, wherein -A 1 - in the formula (2) is a 1,4-phenylene group which may have a substituent. Composition.
The composition for forming an anisotropic dye film according to any one of claims 5 to 8, wherein n in the formula (2) is 2.
The composition for forming an anisotropic dye film according to any one of claims 5 to 9, wherein -R 1 in the formula (2) is an alkyl group substituted with one or more and five or less fluorine atoms. thing.
Anisotropic according to any one of claims 5 to 9, wherein -R 1 in the formula (2) is an alkyl group having 1 to 10 carbon atoms and substituted with one or more fluorine atoms. A composition for forming a pigmented film.
In the formula (2), X is a hydrogen atom, -R a , -O-R a , -NH-R a , -C(=O)-R a , -C(=O)-O-R a , -C(=O)-NH-R a , -C(=O)-N(-R b )-R a , -O-C(=O)-R a , -NH-C(=O)- R a , -N(-R b )-C(=O)-R a , or -S-R a (-R a and -R b each independently represent the number of carbon atoms that may have a branch) Represents an alkyl group having 1 to 15 atoms, a cycloalkyl group having 5 to 14 ring atoms, or an aryl group having 5 to 14 ring atoms.The above alkyl groups, cycloalkyl groups, and aryl Each of the groups may have a substituent. Also, -R a and -R b may be combined to form a ring having 2 to 15 carbon atoms, and the ring may have a substituent. In addition, one or more methylene groups contained in the ring formed by combining the alkyl group, cycloalkyl group, aryl group, and R a and R b may have -O- , -S-, -NH-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF 2 -, -CHCl-, or a structure replaced by -CCl 2 -, or a structure replaced by a polymerizable group such as an acryloyloxy group, a methacryloyloxy group, or a glycidyloxy group). The composition for forming an anisotropic dye film according to any one of Items 5 to 11.
The composition for forming an anisotropic dye film according to any one of claims 5 to 12, wherein the polymerizable liquid crystal compound is a low molecular weight polymerizable liquid crystal compound that does not have a repeating unit structure.
An anisotropic dye film formed using the composition for forming an anisotropic dye film according to any one of claims 5 to 13.
An optical element comprising the anisotropic dye film according to claim 14.