JP2022028423A - Anisotropic dye film-forming composition, anisotropic dye film, and optical element - Google Patents

Abstract

To provide an anisotropic dye film-forming composition which contains a pigment and a liquid crystal compound and offers superior coatability and optical performance.SOLUTION: Provided are a liquid crystal compound having a partial structure represented by a formula (1) below, and an anisotropic dye film-forming composition containing a pigment represented by a formula (D1) below: -Cy-X2-C≡C-X1- ...(1), where -Cy- represents a hydrocarbon ring group or heterocyclic group, -X1- represents a linking group such as -C(=O)O- and -OC(=O)-, and -X2- represents a single bond or a linking group such as -C(=O)O- and -OC(=O)-; A1-N=N-A2-(N=N-A3)n-X3 ...(D1), where -A1 represents a monovalent group of the benzothiazole ring, -A2- and -A3- independently represent a divalent group of an aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent, -X3 represents a monovalent organic group, and n represents 1, 2, or 3.SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY The present invention is an anisotropic dye film formed by applying a liquid crystal composition, particularly a polarizing film provided in a display element of a dimming element, a liquid crystal element (LCD), and an organic electroluminescence element (OLED). The present invention relates to a composition for forming an anisotropic dye film showing high dichroism, an anisotropic dye film, and an optical element, which are useful for the above.

In the LCD, a linear polarizing film and a circular polarizing film are used in order to control the optical rotation and birefringence in the display. Also in the OLED, a circularly polarizing film is used to prevent reflection of external light in a bright place.

Conventionally, as such a polarizing film, for example, a polarizing film obtained by dyeing polyvinyl alcohol (PVA) with a low concentration of iodine (iodine-PVA polarizing film) is known (Patent Document 1). However, the low-concentration iodine-PVA polarizing plate has problems such as iodine sublimation or alteration depending on the usage environment, which causes the color to change, and warpage due to relaxation of PVA stretching. There is a problem that it occurs.
As another approach, a polarizing film in which the dye itself having a polymerizable end introduced is oriented is also known (Patent Document 2). However, the dye having the polymerizable end introduced tends to cause color unevenness depending on the coating film conditions.
An anisotropic dye film using a liquid crystal compound and a benzothiazole dye is also known (Patent Document 3). However, the dichroism of this anisotropic dye film is insufficient, and further studies are needed to find an appropriate combination of the liquid crystal compound and the dye.

Japanese Unexamined Patent Publication No. 1-105204 International Publication No. 2019/102922 Japanese Unexamined Patent Publication No. 2013-210624

It is desired that the polarizing film formed by applying the liquid crystal composition containing a dye has high light absorption selectivity even in a thin film and has no light loss in the wavelength region of 350 nm to 800 nm. Therefore, it is necessary to use a plurality of highly dichroic dyes and adjust them so as to comprehensively absorb the wavelength region of 350 nm to 800 nm. There is a problem that the dye is easily deposited and the coating performance is deteriorated.

In order to suppress the precipitation of the dye, it is conceivable to suppress the addition amount of the dye by using a dye having a high absorbance, or to suppress the type of the dye to be added by using a dye having a plurality of maximum absorptions.
However, when a dye having a high absorbance is used, if an attempt is made to cover a wide wavelength region with the dye alone, it becomes necessary to add an excessive amount, which causes a problem that the absorbance at the maximum absorption wavelength becomes saturated.
To solve this problem, the present inventor can efficiently cover a wide wavelength region by adding a small amount of a benzothiazole-based dye having a plurality of maximum absorptions, and suppress the precipitation of the dye. Found that is possible.
Further, it is known that in a polarizing film formed by applying a liquid crystal composition containing a dye, the two-color ratio and the maximum absorption wavelength differ depending on the combination of the liquid crystal compound and the dichroic dye. Therefore, it is important to combine a dichroic dye that is compatible with the liquid crystal compound used.

Under such circumstances, development of a composition for forming an anisotropic dye film containing a dichroic dye so that the anisotropic dye film to be formed exhibits high dichroism and exhibits good coating film performance. Is desired.

The present invention comprises anisotropy containing a benzothiazole-based dye having a plurality of maximum absorptions and capable of achieving both excellent coating film properties and excellent optical performance, and a liquid crystal compound having a structure suitable for the benzothiazole dye. It is an object of the present invention to provide a composition for forming a sex dye film.
Another object of the present invention is to provide an anisotropic dye film using this anisotropic dye film composition.
It is also an object of the present invention to provide an optical element including this anisotropic dye film.

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

[1] A composition for forming an anisotropic dye film containing a dye and a liquid crystal compound, wherein the liquid crystal compound has a partial structure represented by the following formula (1) (hereinafter, "liquid crystal compound (1)". ) ”), And the dye is a composition for forming an anisotropic dye film, which comprises a dye represented by the following formula (D1) (hereinafter referred to as“ dye (D1) ”).
^-Cy -X ² -C≡C-X ¹ -... (1)
(In equation (1),
^-Cy- represents a hydrocarbon ring group or a heterocyclic group;
-X ^1- is -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S-,- SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ Represents S- or -SCH _2- ;
-X ^2- is a single bond, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S -, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ S- or -SCH _2- . )
A ¹ -N = N-A ^2- (N = NA ³ ) _n -X ³ ... (D1)
(In equation (D1),
-A ¹ represents a monovalent group of the benzothiazole ring which may have a substituent (except for structures whose terminal is a vinyl group);
-A ^2- and -A ³ --independently have a divalent group of an aromatic hydrocarbon ring which may have a substituent or a divalent of an aromatic heterocycle which may have a substituent. Represents a group;
-X ³ represents a monovalent organic group;
n represents 1, 2, or 3.
When n is 2 or ³ , the plurality of -A3- may be the same or different from each other. )

[2] The composition for forming an anisotropic dye film according to [1], wherein -A ^3- is a phenylene group which may have a substituent.

[3] The composition for forming an anisotropic dye film according to [1] or [2], wherein -A ^2- is a divalent group of an aromatic hydrocarbon ring which may have a substituent.

[4] The composition for forming an anisotropic dye film according to any one of [1] to [3], wherein -X ³ is -OR ^x or -N (-R ^y ) -R ^x .
However, -R ^x and -R ^y are each independently an alkyl group having 1 to 15 carbon atoms which may have a branch, or a cycloalkyl group or an aryl group having 5 to 14 atoms constituting a ring. Represents;
-R ^x and -R ^y may be integrated to form an alkylene group having 2 to 15 carbon atoms which may have a branch;
The alkyl group having 1 to 15 carbon atoms which may have the branch and the aryl group having 5 to 14 atoms constituting the ring may each have a substituent;
One or more methylene groups contained in the alkyl group having 1 to 15 carbon atoms which may have the branch or the alkylene group having 2 to 15 carbon atoms which may have the branch is ether. The structure may be replaced by an oxygen atom, a thioether sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF _2- , -CHCl- or -CCl _2- . ;
The amine nitrogen atom is -NH- or -N ( ^Rz )-;
R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[5] The ratio (r _n1 / r _n2 ) of the number of ring structures ( _rn1 ) of the liquid crystal compound (1) to the number of ring structures ( _rn2 ) of the dye (D1) is 0.7. The composition for forming an anisotropic dye film according to any one of [1] to [4], which is ~ 1.5.

[6] The composition for forming an anisotropic dye film according to any one of [1] to [5], wherein the dye (D1) contains a maximum absorption wavelength in the wavelength range of 501 nm to 800 nm and 350 nm to 500 nm. ..

[7] Further includes a dye whose wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm is shorter than the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm of the dye (D1). The composition for an anisotropic dye film according to any one of [1] to [6].

[8] An anisotropic dye film formed by using the composition for forming an anisotropic dye film according to any one of [1] to [7].

[9] An optical element including the anisotropic dye film according to [8].

The composition for forming an anisotropic dye film of the present invention can realize excellent coating properties and excellent optical performance by containing a dye having a plurality of maximum absorptions and a liquid crystal compound suitable for the dye.
Since the anisotropic dye film of the present invention is formed by using such an anisotropic dye film forming composition of the present invention, excellent coating properties and excellent optical performance can be realized.
Since the optical element of the present invention contains such an anisotropic dye film of the present invention, excellent optical performance can be realized.

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

The anisotropic dye film as used in the present invention refers to electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system in the thickness direction of the anisotropic dye film and two directions in any orthogonal plane. It is a dye film having anisotropy. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.
Examples of the film having optical anisotropy such as absorption and refraction include a linear polarizing film, a polarizing film such as a circular polarizing film, a retardation film, and a conductive anisotropic dye film. 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.

[mechanism]
The reason why the effect of the present invention is exhibited is that a dye having a benzothiazole ring represented by the formula (D1) having a plurality of maximum absorptions and excellent optical performance (hereinafter, referred to as "dye (D1)") may be used. This is because it is a composition for forming an anisotropic dye film containing both a liquid crystal compound having a structure suitable for the above).

The dye according to the present invention has a structure having a benzothiazole ring represented by the formula (D1), exhibits high absorbance, and has a plurality of dyes in a wavelength region of 350 nm to 800 nm in the composition for forming an anisotropic dye film. Has maximum absorption of.
By containing the above dye having high absorbance and multiple maximum absorptions, the composition for forming an anisotropic dye film of the present invention has a low dye content even when the wavelength region of 350 nm to 800 nm is comprehensively absorbed. Therefore, the dye tends to be less likely to precipitate. Therefore, it is considered that the composition for forming an anisotropic dye film of the present invention has good coating properties capable of forming a coating film in which color unevenness and defects are suppressed in the coating step.
Further, the compound having a partial structure represented by the formula (1) used in the present invention (hereinafter, may be referred to as “liquid crystal compound (1)”) has a characteristic skeleton represented by the formula (1). By having the above, the molecular arrangement can be highly oriented when oriented due to the intermolecular interaction that works not only between the liquid crystal molecules but also with the dye (D1).
Therefore, it is considered that a composition for forming an anisotropic dye film showing a high two-color ratio can be obtained by combining the liquid crystal compound (1) and the dye (D1).

[Composition for forming an anisotropic dye film]
The composition for forming an anisotropic dye film of the present invention contains a dye and a liquid crystal compound.
The composition for forming an anisotropic dye film of the present invention may be a solution, a liquid crystal display, or a dispersed state as long as it does not cause phase separation, but the anisotropic dye film may be in a dispersed state. The forming composition is preferably a solution from the viewpoint of easy application to a substrate. On the other hand, the solid content component obtained by removing the solvent from the composition for forming an anisotropic dye film is preferably in a liquid crystal phase state at an arbitrary temperature from the viewpoint of orientation on the substrate as described later.
In the present invention, the state of the liquid crystal phase is specifically described on pages 1 to 16 of "Fundamentals and Applications of Liquid Crystals" (Shoichi Matsumoto, Ryo Tsunoda; 1991). As described above, it is a liquid crystal state exhibiting both liquid and crystal properties or intermediate properties, and is a nematic phase, a smectic phase, a cholesteric phase, or a discotic phase.

<Dye>
In the present invention, the dye is a substance or compound that absorbs at least a part of the wavelength in the visible light region (350 nm to 800 nm).
Examples of the dye that can be used in the present invention include a dichroic dye. The dichroic dye refers to a dye having a property in which the absorbance in the major axis direction and the absorbance in the minor axis direction of the molecule are different. Further, the dye may be a dye having liquid crystallinity or may not have liquid crystallinity. In addition, having liquid crystal property means that the liquid crystal phase is expressed at an arbitrary temperature.

The dye contained in the composition for forming an anisotropic dye film of the present invention contains at least the dye (D1) represented by the formula (D1).
The composition for an anisotropic dye film of the present invention may contain only one kind of dye (D1) alone, or may contain two or more kinds in any combination and ratio.

A ¹ -N = N-A ^2- (N = NA ³ ) _n -X ³ ... (D1)
(In equation (D1),
-A ¹ represents a monovalent group of the benzothiazole ring which may have a substituent (except for structures whose terminal is a vinyl group);
-A ^2- and -A ³ --independently have a divalent group of an aromatic hydrocarbon ring which may have a substituent or a divalent of an aromatic heterocycle which may have a substituent. Represents a group;
-X ³ represents a monovalent organic group;
n represents 1, 2, or 3.
When n is 2 or ³ , the plurality of -A3- may be the same or different from each other. )

(-A ¹ )
-A ¹ represents a monovalent group of a benzothiazole ring which may have a substituent (excluding a structure having a vinyl group at the end).
The bond to the azo group (-N = N-) in the formula (D1) of the ^monovalent group of the benzothiazole ring of -A1 is preferably the 2-position of the benzothiazole ring.

Substituents other than those having a vinyl group at the end that -A ¹ may have include ^-RA , -OH, -O- ^RA , -OC (= O) ^-RA , and-. NH ₂ , -NH- ^RA , -N ( ^-RB ) ^-RA , -C (= O) ^{-RA, -C (= O) -OR A ,} -C (= O) -NH ₂ , -C (= O) -NH- ^RA , -C (= O) -N ( ^-RB ) ^-RA , -SH, -S- ^RA , trifluoromethyl group, sulfamoyl group, carboxy group , Cyano group, nitro group, halogen and the like. Here, ^-RA and ^-RB each independently represent a linear or branched alkyl group having 1 to 15 carbon atoms. The carbon atoms of ^—RA and ^—RB are preferably 1 to 12 and even more preferably 1 to 9 from the viewpoint of improving the molecular orientation with the liquid crystal compound (1) used in the present invention.

One or more methylene groups contained in the linear or branched alkyl group may be an ether oxygen atom, a thioether sulfur atom, or an amine nitrogen atom (the amine nitrogen atom is -NH-,. -N (R ^z )-, where R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms), a carbonyl group and an ester bond. , Amido bond, -CHF-, -CF _2- , -CHCl- or -CCl _2- may be replaced by a polymerizable group of an acryloyloxy group, a metaacryloyloxy group, a glycidyloxy group. It may be replaced.

Of these, as the substituent excluding those having a vinyl group at the end which ^{—A 1} may have, —RA, ^—ORA , a trifluoromethyl group and a fluoro group are preferable. Examples of ^RA include n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 5,5-dimethyl-3-methylhexyl and the like. Having the above substituent tends to improve the molecular orientation with the liquid crystal compound (1).

The substitution position of these substituents is not particularly limited, but the 6-position of the benzothiazole ring tends to cause the transition moment of absorption of the dye (D1) to coincide with the major axis direction of the dye (D1), resulting in two colors. It is preferable from the viewpoint that the ratio can be increased.

(-A ^2- and -A ^2- )
-A ^2- and -A ^2- are each independently divalent of an aromatic hydrocarbon ring which may have a substituent or divalent of an aromatic heterocycle which may have a substituent. Represents a group.

The aromatic hydrocarbon ring in -A ^2- and -A ^3- is a monocyclic or condensed aromatic hydrocarbon ring. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 or more and 20 or less, and more preferably 10 or less. With these carbon atoms, the transition moment of absorption of the dye (D1) tends to coincide with the long axis direction of the dye (D1), and the two-color ratio can be increased.

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

As the ^divalent group of the aromatic hydrocarbon ring of —A2－, the absorption transition moment of the dye (D1) tends to coincide with the major axis direction of the dye (D1), and the two-color ratio can be increased. A divalent group of the ring (phenylene group) and a divalent group of the naphthalene ring (naphthylene group) are preferable, 1,4-phenylene group, 1,4-naphthylene group and 2,6-naphthylene group are more preferable, and 1,4 -A phenylene group is more preferred.
As the divalent group of the aromatic hydrocarbon ring of ^−A3 −, the absorption transition moment of the dye (D1) tends to coincide with the major axis direction of the dye (D1), and phenylene can be increased because the two-color ratio can be increased. A group and a naphthylene group are preferable, a phenylene group is more preferable, and a 1,4-phenylene group is further preferable.

The aromatic heterocycles in -A ^2- and -A ^3- are monocyclic or condensed aromatic heterocycles. The number of carbon atoms of the aromatic heterocycle is preferably 4 or more and 20 or less, and more preferably 10 or less. With these carbon atoms, the transition moment of absorption of the dye (D1) tends to coincide with the long axis direction of the dye (D1), and the two-color ratio can be increased.

Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiazylazole ring, a triazole ring, and an indole ring. Carbazole ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrazole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Flotiazole ring, Thienofranc ring, Thienothiazole ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzo Examples thereof include an imidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxalin ring, a phenanthridin ring, a quinazoline ring, and an azulene ring.

As the substituents allowed for the divalent group of the aromatic hydrocarbon ring or the divalent group of the aromatic heterocyclic ring in -A ^2- and -A ^3- , the substituent that -A ¹ may have is used. Similar things can be mentioned.

As —A ² −, a divalent group of an aromatic hydrocarbon ring which may have a substituent is preferable, a phenylene group which may have a substituent is more preferable, and 1 which does not have a substituent 1. , 4-Phenylene groups are more preferred. As a result of the above, the transition moment of absorption of the dye (D1) tends to coincide with the long axis direction of the dye (D1), and the two-color ratio can be increased.
As ^—A3 −, a divalent group of an aromatic hydrocarbon ring which may have a substituent is preferable, a phenylene group which may have a substituent is more preferable, and 1 which does not have a substituent 1. , 4-Phenylene groups are more preferred. As a result of the above, the transition moment of absorption of the dye (D1) tends to coincide with the long axis direction of the dye (D1), and the two-color ratio can be increased.

(-X ³ )
-X ³ represents a monovalent organic group.

The monovalent organic group in ^-X3 is hydrogen atom, hydroxy group, amino group, cyano group, carbamoyl group, nitro group, halogen atom, -R ^x , -OR ^x , -NH-R ^x ,-. N (-R ^y ) -R ^x , -C (= O) -R ^x , -C (= O) -OR ^x , -C (= O) -NH-R ^x , -C (= O) -N (-R ^y ) -R ^x , -OC (= O) -R ^x , -NH-C (= O) -R ^x , -N (-R ^y ) -C (= O) -R Examples include ^x and the like. It should be noted that each of -R ^x and -R ^y has 1 to 15 carbon atoms which may have a branch, preferably 1 to 6 alkyl groups or 5 to 14 atoms constituting a ring. It preferably represents 5-10 cycloalkyl or aryl groups. Here, the aryl group is a broadly defined aryl group including a heteroaryl group. Further, —R ^x and —R ^y may be integrated to form an alkylene group having 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, which may have a branch.

The alkyl group having 1 to 15 carbon atoms which may have a branch and the cycloalkyl group or aryl group having 5 to 14 atoms constituting the ring may each have a substituent, and may have a substituent. One or more methylene groups contained in the alkyl group having 1 to 15 carbon atoms which may have a branch and the alkylene group having 2 to 15 carbon atoms which may have a branch are etheric oxygen atoms. , Thioethery sulfur atom, amine nitrogen atom (-NH-, or -N (R ^z )-: where R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms. ), A carbonyl group, an ester bond, an amide bond, -CHF-, -CF _{2-, -CHCl-, -CCl 2 --} replaced (displace) structure.

The allowable substituents for the alkyl groups having 1 to 15 carbon atoms which may have a branch at —R ^x and —R ^y are —OH, —OR ^f , —OC (= O). -R ^f , -NH ₂ , -NH-R ^f , -N (-R ^g ) -R ^f , -C (= O) -R ^f , -C (= O) -OR ^f , -C ( = O) -NH ₂ , -C (= O) -NH-R ^f , -C (= O) -N (-R ^g ) -R ^f , -SH, -S-R ^f , sulfamoyl group, carboxy group , Cyano group, nitro group, halogen and the like. Here, -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.
The methylene group contained in the linear or branched alkyl group having 1 to 15 carbon atoms is an ether oxygen atom, a thioether sulfur atom, an amine nitrogen atom (-NH-, or an amine nitrogen atom). -N (R ^h )-: where R ^h represents a linear or branched alkyl group having 1 to 6 carbon atoms), a carbonyl group, an ester bond, an amide bond, -CHF-,-. The structure may be substituted with CF _2- , -CHCl-, -CCl _2- , or a polymerizable group of an acryloyloxy group, a metaacrylloyloxy group, or a glycidyloxy group may be substituted.
Of these, —OR ^f is preferable as the substituent allowed for the alkyl group having 1 to 15 carbon atoms which may have a branch at —R ^x and —R ^y , and for example, methoxy and ethoxy. , N-propoxy, n-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, acryloyloxy, methacryloyloxy, glycidyloxy and the like.

Possible substituents for cycloalkyl or aryl groups with 5 to 14 atoms constituting the ring at —R ^x and —R ^y include —R ⁱ , —OH, —OR ⁱ , —O. -C (= 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, halogen and the like. 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.
Of these, -R ⁱ and -O-R ⁱ are preferable as the substituents allowed for the cycloalkyl group or the aryl group having 5 to 14 atoms constituting the ring in -R ^x and -R ^y . , For example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, methoxy, ethoxy, n-propoxy, n-butoxy, n-pentoxy. , N-hexoxy, n-heptoxy, n-octoxy, 2-ethylhexyloxy, 5,5-dimethyl-3-methylhexyloxy and the like.

Examples of the cycloalkane ring of the cycloalkyl group having 5 to 14 atoms constituting the -R ^x and -R ^y rings include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane. Examples thereof include a ring, a cyclohexene ring, a norbornane ring, a bornan ring, an adamantane ring, a tetrahydronaphthalene ring, and a bicyclo [2.2.2] octane ring.
Examples of the aryl group having 5 to 14 atoms constituting the rings of —R ^x and —R ^y include the aromatic hydrocarbon ring and the aromatic heterocycle in −A ² − and −A ³ − of the formula (D1). Can be mentioned as the monovalent group of the ring exemplified as.

-R ^x and -R ^y are alkyl groups having 1 to 15 carbon atoms which may have a branch, or -R ^x and -R ^y are integrated and have a branch. It is preferable to form an alkylene group having 2 to 15 carbon atoms, which is an alkyl group having 1 to 6 carbon atoms which may have a branch, or -R ^x and -R ^y are integrated. , It is more preferable to form an alkylene group having 2 to 10 carbon atoms which may have a branch, and an alkyl group having 1 to 3 carbon atoms which may have a branch, or -R ^x and It is more preferable that —R ^y is integrated to form an alkylene group having 2 to 6 carbon atoms which may have a branch. By the above, the molecular orientation with the liquid crystal compound (1) tends to be good.

The monovalent organic groups in -X ³ are -R ^x , -OR ^{x, -OC (= O) -R x ,} -C (= O) -OR ^x , -N (-N (-). R ^y ) -R ^x is preferable, -OR ^{x, -OC (= O) -R x ,} -N (-R ^y ) -R ^x is more preferable, and -OR ^x , -N ( —R ^y ) —R ^x is more preferred, and —N (−R ^y ) —R ^x is particularly preferred. Specific examples of -N (-R ^y ) -R ^x include a dimethylamino group, a diethylamino group, a din-propylamino group, an ethylmethylamino group, a methylpropylamino group, an azetidinyl group, a pyrrolidinyl group and a piperidinyl group. , Azepanyl group, morpholinyl group, piperazinyl group and thiomorpholinyl group are preferable, and diethylamino group, pyrrolidinyl group and piperidinyl group are more preferable. As a result of the above, the transition moment of absorption of the dye (D1) coincides with the long axis direction of the dye (D1), so that the dichroism tends to be good.

(N)
n represents 1, 2, or 3.
n is preferably 1 or 2, more preferably 1. By the above, the molecular orientation with the liquid crystal compound (1) tends to be good.
When n is 2 or 3, each −A ³⁻ may be the same or different.

It should be noted that —N = N— in the formula (D1) is preferably a trans type from the viewpoint of enhancing the linearity of the dye (D1).

(Preferable combination of -A ¹ , -A ^2- , -A ^3- , -X ³ and n)
The combination of -A ¹ , -A ^2- , -A ^3- , -X ³ and n is not particularly limited, and the effect of the present invention tends to be obtained more effectively by combining the preferable groups of each of the above-mentioned substituents. It is in.

(Specific example of dye (D1))
Specifically, the dye (D1) includes, but is not limited to, the following compounds.

(Absorption characteristics)
The waveform and maximum absorption wavelength of the dye (D1) contained in the composition for forming an anisotropic dye film of the present invention in the anisotropic dye film prepared by the method described later are not limited, but have a wavelength of 350 to 800 nm. It may have a plurality of maximum absorptions in the range of. The absorption waveform can be measured using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100") equipped with a Gran Thomson spectrometer described later.

When the dye (D1) has a plurality of maximum absorptions, it is preferable that the dye (D1) has a maximum absorption in a wavelength range of 350 to 500 nm and a wavelength range of 501 nm to 800 nm, respectively, and more preferably 350 to 460 nm. It has absorption maximums in the wavelength region and the wavelength region of 560 to 700 nm, respectively, and more preferably has maximum absorption in the wavelength regions of 350 to 450 nm and 570 to 690 nm, respectively. By having the maximum absorption in these wavelength ranges, each maximum absorption becomes independent, and it becomes possible to cover a wide range of wavelengths. This makes it possible to reduce the amount of dye contained in the composition for forming an anisotropic dye film, and by producing an anisotropic dye film having neutral hue and suppressing color unevenness and defects. It tends to be more advantageous.

The dye (D1) contained in the composition for forming an anisotropic dye film of the present invention has a maximum absorption (λmax1) in the anisotropic dye film as compared with a maximum absorption (λmax2) measured by dissolving in a solvent. Is preferably present at long wavelengths. This long wavelength shift is a phenomenon that occurs when the dye (D1) is dispersed in a polymer having a unit based on the liquid crystal compound (1) and / or the liquid crystal compound (1). It is shown that the liquid crystal compound (1) and / or the polymer having a unit based on the liquid crystal compound (1) strongly interacts between molecules. The long wavelength shift means that the difference in maximum absorption (λmax1-λmax2) becomes a positive value, and the difference is preferably 10 nm or more, and more preferably 20 nm or more.

(Other pigments)
The composition for forming an anisotropic dye film of the present invention may contain other dyes other than the dye (D1), and examples of the other dyes other than the dye (D1) include azo dyes and quinone dyes. Includes naphthoquinone dyes, anthraquinone dyes, etc.), stilben dyes, cyanine dyes, phthalocyanine dyes, indigo dyes, condensed polycyclic dyes (perylene dyes, oxazine dyes, acridine dyes, etc.). ) Etc. can be mentioned.
The composition for an anisotropic dye film of the present invention may contain only one kind of dye other than the dye (D1) alone, or may contain two or more kinds in any combination and ratio. good.

Among the dyes exemplified above, azo dyes are preferable because they can have a high molecular arrangement in the anisotropic dye film.

The azo dye refers to a dye having at least one azo group (-N = N-), and the number of azo groups in one molecule thereof is the solubility in a solvent and the phase with the liquid crystal compound (1). From the viewpoint of solubility, color tone and ease of manufacture, 1 or more is preferable, 2 or more is more preferable, 6 or less is preferable, 4 or less is more preferable, and 3 or less is further preferable.

Examples of the azo dye include a compound represented by the following formula (A).
R ¹¹ -E ¹ -N = N- (E ² -N = N) _p -E ³ -R ¹² ... (A)
(In formula (A),
-E ^1- , -E ^2- and -E ^3- each independently have a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a substituent. Represents a divalent heterocyclic group that may be;
p represents an integer from 0 to 4;
If p is an integer greater than or equal to 2, multiple -E ² -s may be the same or different from each other;
R ¹¹ and R ¹² each independently represent a monovalent organic group. )

-E ^1- , -E ^2- and -E ^3- each independently have a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a substituent. Represents a divalent heterocyclic group that may be present.
As the substitution position of the phenylene group, a 1,4-phenylene group is preferable because the linearity of the molecule is high.
As the substitution position of the naphthylene group, a 1,4-naphthylene group or a 2,6-naphthylene group is preferable because of the high linearity of the molecule.

The divalent heterocyclic group is preferably a heterocyclic group having 3 or more and 14 or less carbon atoms forming a ring, and more preferably 10 or less. In particular, monocyclic or bicyclic heterocyclic groups are preferable.
Examples of the atom other than carbon constituting the divalent heterocyclic group include at least one selected from a nitrogen atom, a sulfur atom and an oxygen atom. When the heterocyclic group has a plurality of atoms constituting a ring other than carbon, they may be the same or different.
Specific examples of the divalent heterocyclic group include a pyridinediyl group, a quinolinediyl group, an isoquinolindiyl group, a thiazolediyl group, a benzothiazolediyl group, a thienothiazolediyl group, a thienothiophendiyl group, and a benzimidazolidinonediyl group. , Benzofrangyl group, phthalimidediyl group, oxazolediyl group, benzoxazolediyl group and the like.

The substituents arbitrarily possessed by the phenylene group, the naphthylene group, and the divalent heterocyclic group in -E ^1- , -E ^2- , and -E ^3- are alkyl groups having 1 to 4 carbon atoms; methoxy group, ethoxy group. An alkoxy group having 1 to 4 carbon atoms such as a group and a butoxy group; an alkyl fluoride group having 1 to 4 carbon atoms such as a trifluoromethyl group; a cyano group; a nitro group; a hydroxyl group; a halogen atom; an amino group, a diethylamino group, and Substituent or unsubstituted amino group such as pyrrolidino group (Substituent amino group is an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or two substituted alkyl groups bonded to each other and having 2 to 2 carbon atoms. It means an amino group forming an alkandiyl group of 8. The unsubstituted amino group is −NH ₂ , and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group and a butyl group. Examples of the alcandiyl group having 2 to 8 carbon atoms include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1, Examples thereof include 5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like).
The phenylene group, naphthylene group, and divalent heterocyclic group at -E ^1- , -E ^2- , and -E ^3- are unsubstituted or substituted because of their high molecular linearity. In some cases, it is preferably substituted with a methyl group, a methoxy group, a hydroxyl group, a fluorine atom, a chlorine atom, a dimethylamino group, a pyrrolidinyl group and a piperidinyl group.

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

R ¹¹ and R ¹² represent the same or different monovalent organic groups.
The monovalent organic group in R ¹¹ and R ¹² is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms which may have a branch; an alicyclic alkyl group having 1 to 15 carbon atoms; a methoxy group. An alkoxy group having 1 to 15 carbon atoms which may have a branch such as an ethoxy group and a butoxy group; an alkyl fluoride group having 1 to 15 carbon atoms which may have a branch such as a trifluoromethyl group; cyano Group; Nitro group; Hydroxyl group; Halogen atom; Substituent or unsubstituted amino group such as amino group, diethylamino group, and pyrrolidino group (substituent amino group is an alkyl group having 1 to 15 carbon atoms which may have a branch. It means an amino group having one or two of the above, or an amino group in which two substituted alkyl groups are bonded to each other to form an alcandiyl group having 2 to 15 carbon atoms. The unsubstituted amino group is -NH ₂ Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group and a butyl group. Examples of the arcandyl group having 2 to 15 carbon atoms include an ethylene group and a propane-1,3-. Diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane- Examples include 1,8-diyl group; carboxy group; alkyloxycarbonyl group having 1 to 15 carbon atoms which may have a branch such as butoxycarbonyl group; 2- (4-butylphenyl) ethenyl group. Alkylphenylalkenyl groups such as; carbamoyl group; may have a branch such as a butylcarbamoyl group; an alkylcarbamoyl group having 1 to 15 carbon atoms; a sulfamoyl group; even if it has a branch such as a butylsulfamoyl group. Good alkylsulfamoyl group having 1 to 15 carbon atoms; may have a branch such as a butylcarbonylamino group; may have an acylamino group having 1 to 15 carbon atoms; may have a branch such as a butylcarbonyloxy group. An acyloxy group having 1 to 15 carbon atoms; a sulfanyl group; an alkylsulfanyl group having 1 to 15 carbon atoms such as a butylsulfanyl group; and -R ¹ and -R ² in the liquid crystal compound (1) described later can be mentioned.

Examples of R ¹¹ and R ¹² include hydrogen atom, chain group, aliphatic organic group (“aliphatic organic group” includes chain and cyclic group), and a part of carbon atom is nitrogen atom and / Or aliphatic organic groups replaced with oxygen atoms (“Adioxyorganic groups in which a part of carbon atoms are replaced with nitrogen atoms and / or oxygen atoms” includes chain-like and cyclic ones, and fats. (Including those in which some of the methyl groups of the group organic groups are replaced with hydroxyl groups, oxo groups (= O), amino groups, imino groups, etc.), etc. are mentioned, and in one embodiment, hydrogen atoms, chains, etc. are mentioned. Groups are preferred, in another embodiment a hydrogen atom, an aliphatic organic group is preferred, and in yet another embodiment, a hydrogen atom, an aliphatic organic in which a part of a carbon atom is replaced with a nitrogen atom and / or an oxygen atom. Groups are preferred.

As the chain group, the above-mentioned alkyl group having 1 to 15 carbon atoms which may have a branch; an alkoxy group having 1 to 15 carbon atoms which may have a branch; even if it has a branch. A good alkyl fluoride group having 1 to 15 carbon atoms; a substituted or unsubstituted amino group (a substituted amino group is an amino group having one or two alkyl groups having 1 to 15 carbon atoms which may have a branch. The unsubstituted amino group is -NH ₂ ); carboxy group; an alkyloxycarbonyl group having 1 to 15 carbon atoms which may have a branch; a carbamoyl group; even if it has a branch. Good alkylcarbamoyl group with 1 to 15 carbon atoms; sulfamoyl group; alkylsulfamoyl group with 1 to 15 carbon atoms which may have a branch; acylamino group having 1 to 15 carbon atoms which may have a branch. An acyloxy group having 1 to 15 carbon atoms which may have a branch; a sulfanyl group; an alkylsulfanyl group having 1 to 15 carbon atoms and the like can be mentioned. The chain group and the aliphatic organic group partially overlap.

Examples of the aliphatic organic group include the above-mentioned alkyl group having 1 to 15 carbon atoms which may have a branch, an alicyclic alkyl group having 1 to 15 carbon atoms, and the like.
As the aliphatic organic group in which a part of the carbon atom is replaced with a nitrogen atom and / or an oxygen atom, the above-mentioned alkoxy group having 1 to 15 carbon atoms which may have a branch; a substituted or unsubstituted amino group (The substituted amino group is an amino group having one or two alkyl groups having 1 to 15 carbon atoms which may have a branch, or two substituted alkyl groups bonded to each other and having 2 to 15 carbon atoms. It means an amino group forming an alkanediyl group. The unsubstituted amino group is -NH _2. Examples of the alkyl group having 1 to 15 carbon atoms include a methyl group, an ethyl group and a butyl group. The alkanediyl group having 2 to 15 carbon atoms includes an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5-. Examples include a diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, an octane-1,8-diyl group, etc.); Carboxy group; 1 carbon number which may have a branch. Alkyloxycarbonyl group to 15; carbamoyl group; alkylcarbamoyl group having 1 to 15 carbon atoms which may have a branch; acylamino group having 1 to 15 carbon atoms which may have a branch; having a branch Examples thereof include an acyloxy group having 1 to 15 carbon atoms which may be present.

From the point of high molecular linearity, R ¹¹ and R ¹² are independently hydrogen atoms or alkyl groups having 1 to 10 carbon atoms such as butyl group, pentyl group, hexyl group, heptyl group and octyl group; It is preferably substituted with an alkoxy group having 1 to 10 carbon atoms such as a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group and an octyloxy group, a diethylamino group, a pyrrolidino group and a piperidinyl group. Further, —R ¹ and —R ² in the liquid crystal compound (1), which will be described later, are also preferable.

The azo dye other than the dye (D1) contained in the composition for forming an anisotropic dye film of the present invention is not particularly limited, and known azo dyes can also be used.
As known azo dyes, for example, the dyes described in the above-mentioned Patent Document 1, Patent No. 5982762, JP-A-2017-025317, and JP-A-2014-095899 (dichroic dye, dichroic). Dye).

Specific examples thereof include, but are not limited to, the azo dyes described below.

As the dyes other than the dye (D1) contained in the composition for forming an anisotropic dye film of the present invention, the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm is the dye (D1). ) Is shorter than the wavelength showing the maximum value in the absorption curve in the wavelength range of 350 nm to 800 nm.

Further, the dye other than the dye (D1) is more preferably a dye satisfying the following conditions <1> or <2>. By satisfying <1> or <2>, when the anisotropic dye film formed by using the anisotropic dye film forming composition of the present invention is applied to a polarizing element such as a display, a wide visible region is widened. Polarization characteristics can be exhibited in the range.

<1> The wavelength showing the maximum value in the absorption curve of the other dyes in the wavelength range of 350 nm to 800 nm is longer than the wavelength showing the maximum value in the absorption curve of the dye (D1) in the wavelength range of 350 nm to 500 nm, and the dye (D1). It is shorter than the wavelength showing the maximum value in the absorption curve in the wavelength range of 501 nm to 800 nm of D1).
In this case, the wavelength showing the maximum value in the absorption curve of the other dyes in the wavelength range of 350 nm to 800 nm is 2 nm or more longer than the wavelength showing the maximum value in the absorption curve of the dye (D1) in the wavelength range of 350 nm to 500 nm. , It is preferable that the dye (D1) is 5 nm or more shorter than the wavelength showing the maximum value in the absorption curve in the wavelength range of 501 nm to 800 nm. In particular, the wavelength showing the maximum value in the absorption curve of the other dyes in the wavelength range of 350 nm to 800 nm is 5 nm or more longer than the wavelength showing the maximum value in the absorption curve of the dye (D1) in the wavelength range of 350 nm to 500 nm, and the dye. It is more preferable that the wavelength is 10 nm or more shorter than the wavelength showing the maximum value in the absorption curve in the wavelength range of 501 nm to 800 nm of (D1).

<2> The wavelength showing the maximum value in the absorption curve of the other dyes in the wavelength range of 350 nm to 800 nm is shorter than the wavelength showing the maximum value in the absorption curve of the dye (D1) in the wavelength range of 350 nm to 500 nm.
In this case, the wavelength showing the maximum value in the absorption curve of the other dyes in the wavelength range of 350 nm to 800 nm is shorter than the wavelength showing the maximum value in the absorption curve of the dye (D1) in the wavelength range of 350 nm to 500 nm by 2 nm or more. Is preferable. In particular, the wavelength showing the maximum value in the absorption curve of the other dyes in the wavelength range of 350 nm to 800 nm is 5 nm or more shorter than the wavelength showing the maximum value in the absorption curve of the dye (D1) in the wavelength range of 350 nm to 500 nm. More preferred.

(Molecular weight of dye)
The molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention (when two or more kinds of dyes are used in combination, each molecular weight) is preferably 300 or more, more preferably 350 or more, and 380 or more. Is more preferable, 1500 or less is preferable, 1200 or less is more preferable, and 1000 or less is further preferable. Specifically, the molecular weight of the dye contained in the composition for forming an anisotropic dye film of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and even more preferably 380 to 1000. When the molecular weight of the dye is in the above range, the molecular length and bulk are appropriate, so that the molecular orientation with the liquid crystal compound (1) tends to be good.

(Dye content)
The content occupied by a dye such as a dichroic dye in the composition for forming an anisotropic dye film of the present invention (when two or more kinds of dyes are used in combination, the total content of each is different) is, for example, different. 0.01 parts by mass or more is preferable, 0.05 parts by mass or more is more preferable, 30 parts by mass or less is preferable, and 10 parts by mass or less is preferable with respect to the solid content (100 parts by mass) of the composition for forming a sex dye film. More preferred. Specifically, the content occupied by the dye such as the dichroic dye in the anisotropic dye film forming composition is, for example, with respect to the solid content (100 parts by mass) of the anisotropic dye film forming composition. It is 0.01 to 30 parts by mass, preferably 0.05 to 10 parts by mass.
When 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 obtained without disturbing the orientation of the liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention. There is a tendency that the contained polymerizable liquid crystal compound can be polymerized. Further, when the content occupied by the dye) is at least the above lower limit value, sufficient light absorption can be obtained and sufficient polarization performance tends to be obtained. Further, when the content occupied by the dye is not more than the upper limit value, the inhibition of the orientation of the liquid crystal molecules tends to be suppressed easily.
Here, the solid content of the anisotropic dye film composition corresponds to the total of all the components other than the solvent in the anisotropic dye film composition.

The composition for an anisotropic dye film of the present invention may contain the dye (D1) as an essential component as the dye, and may contain the other dyes described above together with the dye (D1). When the composition for an anisotropic dye film of the present invention contains other dyes, the composition for an anisotropic dye film of the present invention is used from the viewpoint of more effectively obtaining the effect of the present invention by using the dye (D1). The proportion of the dye (D1) in 100% by mass of the total amount of the dye in the composition is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly 15 to 100% by mass. Is preferable.

(Dye manufacturing method)
The dye (D1) and other dyes contained in the composition for forming an anisotropic dye film of the present invention include an alkylation reaction, an esterification reaction, an amidation reaction, an etherification reaction, an ypso substitution reaction, and a diazo coupling reaction. It can be produced by combining known chemical reactions such as a coupling reaction using a metal catalyst.
For example, the dye (D1) can be described in the method described in the examples below, "New Dye Chemistry" (written by Yutaka Hosoda, December 21, 1973, Gihodo), "Review Synthetic Dye" (written by Hiroshi Horiguchi,). It can be synthesized according to the method described in "Theoretical Manufacturing Dye Chemistry" (written by Yutaka Hosoda, 1957, Gihodo), Sankyo Publishing Co., Ltd., 1968.

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

The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention includes a liquid crystal compound (1) having a partial structure represented by the following formula (1).

^-Cy -X ² -C≡C-X ¹ -... (1)
(In equation (1),
^-Cy- represents a hydrocarbon ring group or a heterocyclic group;
-X ^1- is -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S-,- SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ Represents S- or -SCH _2- ;
-X ^2- is a single bond, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S -, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ S- or -SCH _2- . )

( ^-Cy- )
The hydrocarbon ring group in ^—Cy − includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.
Aromatic hydrocarbon ring groups include unlinked aromatic hydrocarbon ring groups and linked aromatic hydrocarbon ring groups.

The unconnected aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the carbon number thereof is preferably 6 to 20 for the reason that the orientation is good. The number of carbon atoms of the unconnected aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. ..

The linked aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms of the monocyclic or condensed ring is preferably 6 to 20, because the orientation is improved by an appropriate core size. The number of carbon atoms of 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 condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. It has a first bond on an atom that is bonded to the ring by a single bond and constitutes a first single ring having 6 to 20 carbon atoms or a fused aromatic hydrocarbon ring, and has a second carbon number. Examples thereof include divalent groups having a second bond on the atoms constituting the ring of 6 to 20 monocyclic or condensed aromatic hydrocarbon rings. Specific examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable because the orientation is good.
Of 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 preferable. When —C ^y − is these groups, the linearity of the liquid crystal molecule is enhanced, and the effect of improving the 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 unconnected non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and its carbon number is 3 to 20, depending on the appropriate core size. Is preferable because it is good. The number of carbon atoms of the unconnected non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of the non-aromatic hydrocarbon ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, and bicyclo [2]. .2.2] Octane ring and the like can be mentioned.

The unconnected non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the ring of the non-aromatic hydrocarbon ring, and a ring of the non-aromatic hydrocarbon ring. It contains an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the above. As the unconnected 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 have a bond on the atom constituting the ring; or a monocyclic ring. A single or single ring with one or more rings selected from the group consisting of aromatic hydrocarbon rings, fused aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings, and fused non-aromatic hydrocarbon rings. It is a divalent group that is bonded to a condensed non-aromatic hydrocarbon ring by a single bond and has a bond on the atom constituting the ring.
The carbon number of the monocyclic or condensed ring is preferably 3 to 20 because the orientation is good depending on the appropriate core size.
Examples of the linked non-aromatic hydrocarbon ring group include a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. It has a first bond on an atom that is bonded to a hydrocarbon ring by a single bond and constitutes a first single ring having 3 to 20 carbon atoms or a condensed non-aromatic hydrocarbon ring, and a second bond. Examples thereof include a divalent group having a second bond on an atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Further, for example, a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond to have 3 to 20 carbon atoms. It has a first bond on the atom constituting the ring of 20 monocyclic or fused aromatic hydrocarbon rings, and constitutes a ring of a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Examples thereof include a divalent group having a second bond on the atom.
Specific examples of the linked non-aromatic hydrocarbon ring group include a bis (cyclohexane) -4,4'-diyl group and a 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 orientation is good.

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

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

Aromatic heterocyclic groups include unlinked aromatic heterocyclic groups and linked aromatic heterocyclic groups.

The unconnected aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocycle, and its carbon number is 4 to 20, so that the orientation is good depending on the appropriate core size. Preferred for a reason. The unconnected aromatic heterocyclic group preferably has 4 to 15 carbon atoms.
Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiazylazole ring, a triazole ring, and an indole ring. Carbazole ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrazole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Flotiazole ring, Thienofranc ring, Thienothiazole ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzo Examples thereof include an imidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxalin ring, a phenanthridin ring, a quinazoline ring, and an azulene ring.

A linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms of the monocyclic or condensed ring is preferably 4 to 20, because the orientation is improved by an appropriate core size. The number of carbon atoms of the linked aromatic heterocyclic group is more preferably 4 to 15.
Examples of the linked aromatic heterocyclic group include a first monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms. It has a first bond on an atom that is bonded by a single bond and constitutes a ring of a first monocyclic ring having 4 to 20 carbon atoms or a fused aromatic heterocyclic ring, and has a second carbon number of 4 to 20 carbon atoms. Examples thereof include a divalent group having a second bond on the atom constituting the ring of the monocyclic or condensed aromatic heterocycle.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

The unconnected non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocycle, and its carbon number is 4 to 20, which is good for orientation depending on the appropriate core size. It is preferable because it becomes. The unlinked non-aromatic heterocyclic group preferably has 4 to 15 carbon atoms.
Examples of the divalent non-aromatic heterocycle 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 tetrahydropyran ring, and a pyrrolidine ring. , Piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzoimidazole ring, quinuclidine ring and the like. Be done.

A linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms of the monocyclic or condensed ring is preferably 4 to 20, because the orientation is improved by an appropriate core size. The number of carbon atoms of 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 heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. Has a first bond on an atom constituting a first single ring having 4 to 20 carbon atoms or a fused non-aromatic heterocyclic ring, and having a second carbon number of 4 carbon atoms. Examples thereof include a divalent group having a second bond on the atoms constituting the ring of up to 20 monocyclic or condensed non-aromatic heterocycles.

The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in ^-Cy- are -R ^k , -OH, -OR ^k , and-, respectively. OC (= O) -R ^k , -NH ₂ , -NH-R ^k , -N (R ^m ) -R ^k , -C (= O) -R ^k , -C (= O) -O- R ^k , -C (= O) -NH ₂ , -C (= O) -NH-R ^k , -C (= O) -N (R ^m ) -R ^k , -SH, -S-R ^k , It 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. Here, -R ^k and -R ^m each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in ^−Cy— have high linearity in molecular structure, and the liquid crystal compounds (1) are associated with each other. 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 and a bromine atom, and is preferably unsubstituted, from the viewpoint that it is easy to easily develop a liquid crystal state. More preferred.

The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in ^−Cy— may be the same or different, and may be aromatic. All of the hydrocarbon ring groups, non-aromatic hydrocarbon ring groups, aromatic heterocyclic groups, and non-aromatic heterocyclic groups may be substituted, all may be unsubstituted, and some may be substituted. It may be partially unsubstituted.

As ^—Cy— , a hydrocarbon ring group is preferable, and a phenylene group and a cyclohexanediyl group are more preferable, because the molecular orientation of the liquid crystal compound (1) is good. Further, since the linearity of the molecular structure of the liquid crystal compound (1) can be increased, 1,4-phenylene group and cyclohexane-1,4-diyl group are more preferable as ^-Cy- , and 1,4 -Phenylene groups are particularly preferred.

(-X ^1- )
-X ^1- is -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S-,- SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ S- or -SCH _2- , of which the linearity of the liquid crystal compound (1) and the tendency to rotate around the short axis of the molecule tend to be easy, so that -X ^1- has π-bonding property. Small, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S-, -SC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -CH ₂ S-, -SCH _2- and the like are preferable. Of these, more preferred are -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, and -OCH _2- , and even more preferably -X. ¹ -is -C (= O) O- or -OC (= O)-, and in another embodiment, -X ¹ -is -CH ₂ CH _2- , -CH ₂ O-, or -OCH. It is preferably ₂ −.

(-X ^2- )
-X ^2- is a single bond, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S -, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ S-, or -SCH _2- . ^-X2- is preferably single-bonded or π-bonded -C (= O) O-, -OC (= O)-,-for reasons of good orientation of the liquid crystal compound (1). C (= S) O-, -OC (= S)-, -C (= O) S-, -SC (= O)-, -CH = CH-, -C (= O) NH-, -NHC (= O)-is more preferably a single bond because of its higher linearity.
-X ^2- is a single bond means that -C ^y- and -C ≡ C- are linked, and by being a single bond, the core of the liquid crystal compound (1) is enlarged, and the present invention is made. There is a tendency that the dichroism of the anisotropic dye film formed from the composition for forming an anisotropic dye film can be increased.

(Preferable combination of ^-Cy- , ^-X2- and ^-X1- )
The combination of ^—Cy −, ^—X2 − and ^—X1 − is not particularly limited, and the effects of the present invention tend to be further obtained by combining the preferred groups of each of the above-mentioned substituents.

The liquid crystal compound (1) contained in the composition for forming an anisotropic dye film of the present invention may be referred to as a liquid crystal compound represented by the following formula (2) (hereinafter, referred to as “liquid crystal compound (2)”). There is.).

R ¹ -F ¹ -Y ¹ -F ² -Y ² -F ³ -R ² ... (2)

(In equation (2),
-R ¹ and -R ² each independently represent a chain organic group;
-F ^1- and -F ^3- each independently represent a partial structure represented by the above formula (1), a divalent organic group, or a single bond;
-F2- represents a partial structure or a ^divalent organic group represented by the above formula (1);
-Y ^1- and -Y ^2- are independently single-bonded, -C (= O) O-, -OC (= O)-, -C (= S) O-, and -OC (= S). -, -C (= O) S-, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-,- Represents CH ₂ O-, -OCH _2- , -CH ₂ S-, or -SCH _2- ;
One of -F ^1- and -F ^3- is a partial structure represented by the above formula (1) or a divalent organic group;
At least one of -F ^1- , -F ^2- , and -F ^3- is a partial structure represented by the above formula (1). )

When −F ¹ − is a partial structure represented by the formula (1), the formula (2) may be the following formula (2A) or the following formula (2B).
R ¹ -Cy-X ² -C≡C-X ¹ - ^{Y 1} -F ² -Y ² -F ³ -R ² ... (2A)
R ¹ -X ¹ -C≡C-X ² -Cy-Y ¹ -F ² -Y ² -F ³ -R ² ... (2B)

Further, when —F ² − is a partial structure represented by the formula (1), the formula (2) may be the following formula (2C) or the following formula (2D).
R ¹ -F ¹ -Y ¹ -C ^y -X ² -C≡C-X ¹ -Y ² -F ³ -R ² ... (2C)
R ¹ -F ¹ -Y ¹ -X ¹ -C≡C-X ² -Cy- ^{Y 2} -F ³ -R ² ... (2D)

Further, when ^−F3− is a partial structure represented by the formula (1), the formula (2) may be the following formula (2E) or the following formula (2F).
R ¹ -F ¹ -Y ¹ -F ² -Y ² -C ^y -X ² -C≡C-X ¹ -R ² ... (2E)
R ¹ -F ¹ -Y ¹ -F ² -Y ² -X ¹ -C≡C-X ² -Cy-R ² ... (2F)

Similarly, when two or more of -F ^1- , -F ^2- and -F ^3- are partial structures represented by the formula (1), they are independently represented by the formula (1). The orientation of the partial structure may be reversed.

Further, as described above, -F ^1- , -F ^2- and -F ^3- are each independently a partial structure or a divalent organic group represented by the formula (1), and in addition, -F. ¹ -and -F ^3- may be single-bonded, but -F ^1- and -F ^3- are not both single-bonded. Further, at least one of -F ^1- , -F ^2- and -F ^3- represents a partial structure represented by the above formula (1).

The chain organic group in -R ¹ and -R ² does not contain a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic hetero ring, non-aromatic hetero ring (however,-). When the chain organic group in R ¹ and −R ² has a cyclic polymerizable group described later, such as an oxylan ring, an oxetane ring, and a vinylbenzene ring, the portion excluding the polymerizable group has the above cyclic structure. It is a monovalent organic group.

Examples of such a chain organic group include- (alkyl group), -O- (alkyl group), -S- (alkyl group), -NH- (alkyl group), and -N (alkyl group)-(alkyl group). ), -OC (= O)-(alkyl group), -C (= O) O- (alkyl group). As such a chain organic group, − (alkyl group) and —O— (alkyl group) are preferable. In one embodiment, such a chain organic group is − (alkyl group), and in another embodiment, such a chain organic group is —O— (alkyl group).

Examples of the alkyl group in these chain organic groups include a linear or branched alkyl group having 1 to 25 carbon atoms, and the carbon-carbon bond of the alkyl group is partially unsaturated. Also, one or more methylene groups contained in the alkyl group may be an ether oxygen atom, a thioether sulfur atom, an amine nitrogen atom (-NH- or -N ( ^RA )-: here. , ^RA represents a linear or branched alkyl group having 1 to 6 carbon atoms), a carbonyl group, an ester bond, an amide bond, -CHF-, -CF _2- , -CHCl-, -CCl. The structure may be replaced by _2- .

Since the alkyl group in these chain organic groups has high molecular linearity, a part of the carbon of the alkyl group may have an unsaturated bond, and one or more contained in the alkyl group. Is preferably a linear alkyl group having 1 to 25 carbon atoms, which may have a structure in which the methylene group of the above is substituted with the above-mentioned group.

Main chain in a chain organic group (meaning the longest chain portion in a chain organic group, and when the chain organic group is substituted with a polymerizable group described later, the most in the portion excluding the polymerizable group The number of atoms in (meaning a long chain portion) is preferably 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

Further, these alkyl groups may be substituted with 1 to 3 polymerizable groups. The polymerizable group is a group having a partial structure capable of being polymerized by light, heat, and / or radiation, and is a functional group or an atomic group necessary for ensuring the function of polymerization. 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, metaacryloyl group, acryloyloxy group, metaacryloyloxy group, acryloylamino group, metaacryloylamino group, vinyl group, vinyloxy group, ethynyl group, ethynyloxy group, 1,3-. Examples include butadienyl group, 1,3-butadienyloxy group, oxylanyl group, oxetanyl group, glycidyl group, glycidyloxy group, styryl group, styryloxy group, etc., acryloyl group, metaacryloyl group, acryloyloxy group, metaacryloyl. Oxy group, acryloyl amino group, metaacryloylamino group, oxylanyl group, glycidyl group, glycidyloxy group are preferable, and acryloyl group, metaacryloyl group, acryloyloxy group, metaacryloyloxy group, acryloylamino group, metaacryloylamino group, glycidyl. Groups and glycidyloxy groups are more preferable, and acryloyloxy groups, metaacryloyloxy groups, and glycidyloxy groups are even more preferable.

When these alkyl groups are substituted with a polymerizable group, it is preferable that one polymerizable group is substituted for the reason of good orientation, and one polymerizable group is substituted with the terminal of the alkyl group. Is more preferable.

Examples of the chain organic group include-(CH ₂ ) _r -CH ₃ ,-(CH ₂ ) _r -CH ₂ -polymerizable group, -O- (CH ₂ ) _r -CH ₃ , -O- (CH ₂ ). _r -CH ₂ -polymerizable group,-(O) _r1- (CH ₂ CH ₂ O) _r2- (CH ₂ ) _r3 -CH ₃ ,-(O) _r1- (CH ₂ CH ₂ O) _r2- (CH ₂ ) _r3 -polymerizable group,-(O) _r1- (CH ₂ ) _r2- (CH ₂ CH ₂ O) _r3 -CH ₃ ,-(O) _r1- (CH ₂ ) _r2- (CH ₂ CH ₂ O) ) _R3 -polymerizable groups are preferred. Note that r in these equations is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and even more preferably an integer of 5 to 19. When r is in these ranges, the effect of improving the orientation tends to be obtained.
Further, r1, r2 and r3 in these formulas independently represent integers, respectively, and represent the main chain in the chain organic group (meaning the longest chain portion in the chain organic group, and the chain organic group is polymerized. When substituted with a sex group, it means the longest chain portion in the portion excluding the polymerizable group.) The number of atoms is preferably 3 to 25, more preferably 5 to 20, and even more preferably. Is appropriately adjusted to be 6 to 20.

-R ¹ and -R ² may be independently substituted with a polymerizable group- (alkyl group), and the alkyl group may be substituted with a polymerizable group-O- (alkyl group). It is preferably present, and more preferably − (alkyl group) substituted with a polymerizable group and —O— (alkyl group) substituted with a polymerizable group.

When X ¹ and -R ¹ or X ¹ and -R ² are bonded as in the formulas (2B) and (2E), and when -F ^3- is a single bond in the formula (2B), the formula is a single bond. In (2E), when -R ¹ or -R ² is bonded to -Y ^1- or -Y ^2- , such as when -F ^1- is a single bond, -X ^1- , -R ¹ or -R ² , which binds to -Y ^1- or -Y ^2- , may be substituted with a polymerizable group- (alkyl group), and is preferably substituted with a polymerizable group. -(Alkyl group) is more preferable.
Further, as described above, -R ¹ or -R ² bonded to -X ^1- , -Y ^1- or -Y ^2- may be substituted with a polymerizable group -O- (alkyl). Group) is preferable, and —O— (alkyl group) substituted with a polymerizable group is more preferable.

The divalent organic group in -F ^1- , -F ^2- and -F ^3- is a group represented by the following formula (3), which is the reason why the orientation is good depending on the appropriate core size. More preferred.

-Q ¹ -... (3)
(In the formula (3), ^−Q1 − represents a hydrocarbon ring group or a heterocyclic group.)

The hydrocarbon ring group in ^−Q1 − includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

Aromatic hydrocarbon ring groups include unlinked aromatic hydrocarbon ring groups and linked aromatic hydrocarbon ring groups.

The unconnected aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and the number of carbon atoms thereof is preferably 6 to 20. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. ..

The linked aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 6 to 20 because the orientation is improved by an appropriate core size. The number of carbon atoms of the linked aromatic hydrocarbon ring group is more preferably 6 to 15. The linked aromatic hydrocarbon ring group includes a first monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second monocyclic or condensed aromatic hydrocarbon ring having 6 to 20 carbon atoms. Have a first bond on the atom constituting the ring of the first monocyclic ring having 6 to 20 carbon atoms or the fused aromatic hydrocarbon ring, and the second carbon atoms have 6 to 20 carbon atoms. Examples thereof include a divalent group having a second bond on the atom constituting the ring of 20 monocyclic or condensed aromatic hydrocarbon rings. Specific examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferable.
Of 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 preferable. Since -Q ^1- is these groups, the orientation tends to be good.

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

The unconnected non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and its carbon number is 3 to 3 because the orientation is good depending on the appropriate core size. It is preferably 20. The number of carbon atoms of the unconnected non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of the non-aromatic hydrocarbon ring include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norbornane ring, bornane ring, adamantane ring, tetrahydronaphthalene ring, and bicyclo [2]. .2.2] Octane ring and the like can be mentioned.

The unconnected non-aromatic hydrocarbon ring group is an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the ring of the non-aromatic hydrocarbon ring, and a ring of the non-aromatic hydrocarbon ring. It contains an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the above. As the unconnected 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 have a bond on the atom constituting the ring; monocyclic aromatic. Single or fused non-cyclic with one or more rings selected from the group consisting of hydrocarbon rings, fused aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings and fused non-aromatic hydrocarbon rings. It is a divalent group that is bonded to an aromatic hydrocarbon ring by a single bond and has a bond on the atom constituting the ring.
The carbon number of the single ring or the fused ring is preferably 3 to 20 because the orientation is good depending on the appropriate core size.

The linked non-aromatic hydrocarbon ring group includes a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. A second bond having a first bond on an atom that is bonded to the hydrogen ring by a single bond and constitutes the first ring of a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. A divalent group having a second bond on an atom constituting a monocycle having 3 to 20 carbon atoms or a fused ring of a non-aromatic hydrocarbon ring, for example, a monocyclic ring having 3 to 20 carbon atoms or a condensed product. A single ring of an aromatic hydrocarbon ring having 3 to 20 carbon atoms or a fused non-aromatic hydrocarbon ring is bonded by a single bond, and a monocyclic ring having 3 to 20 carbon atoms or a fused aromatic hydrocarbon ring ring. A divalent group having a first bond on the atom constituting the above and a second bond on the atom constituting the ring of a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Can be mentioned.
Specific examples of the linked non-aromatic hydrocarbon ring group include a bis (cyclohexane) -4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.

As the non-aromatic hydrocarbon ring group, a non-linked non-aromatic hydrocarbon ring group is preferable because of good orientation.
The unlinked non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl group) for the reason of enhancing the linearity of the molecular structure of the liquid crystal compound (1), and the cyclohexanediyl group is cyclohexane-1, A 4-diyl group is preferred.

The heterocyclic group in ^−Q1 − includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

Aromatic heterocyclic groups include unlinked aromatic heterocyclic groups and linked aromatic heterocyclic groups.

The unconnected aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocycle, and its carbon number is 4 to 20 because the orientation is good depending on the appropriate core size. Is preferable. The unlinked non-aromatic heterocyclic group preferably has 4 to 15 carbon atoms.
Examples of the aromatic heterocycle include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiazylazole ring, a triazole ring, and an indole ring. Carbazole ring, Pyrolobymidazole ring, Pyrrolopyrazole ring, Pyrrolopyrazole ring, Thienopyrrole ring, Thienothiophene ring, Flopyrole ring, Flofran ring, Flotiazole ring, Thienofranc ring, Thienothiazole ring, Benzoisoxazole ring, Benzoisothiazole ring, Benzo Examples thereof include an imidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxalin ring, a phenanthridin ring, a quinazoline ring, and an azulene ring.

A linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20 because the orientation is improved by an appropriate core size. The number of carbon atoms of the linked non-aromatic heterocyclic group is more preferably 4 to 15.
As the linked non-aromatic heterocyclic group, a first monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocycle having 4 to 20 carbon atoms are simple. It has a first bond on an atom that is bonded by a bond and constitutes a first single ring having 4 to 20 carbon atoms or a fused ring of an aromatic heterocycle, and a second single ring having 4 to 20 carbon atoms. Examples thereof include a divalent group having a second bond on the atom constituting the ring or the condensed ring of the aromatic heterocycle.

The non-aromatic heterocyclic group includes a non-linked non-aromatic heterocyclic group and a linked non-aromatic heterocyclic group.

The unconnected non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocycle, and its carbon number is 4 to 20 because the orientation is good depending on the appropriate core size. It is preferable to have. The unlinked non-aromatic heterocyclic group preferably has 4 to 15 carbon atoms.
Examples of the divalent non-aromatic heterocycle 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 tetrahydropyran ring, and a pyrrolidine ring. , Piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazole ring, tetrahydrobenzoimidazole ring, quinuclidine ring and the like. Be done.

A linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocycles are bonded by a single bond and have a bond on an atom constituting the ring. The carbon number of the single ring or the fused ring is preferably 4 to 20 because the orientation is good depending on the appropriate core size. The number of carbon atoms of the linked non-aromatic heterocyclic group is more preferably 4 to 15. The linked non-aromatic heterocyclic group includes a first monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms and a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms. Have a first bond on an atom constituting a first single ring having 4 to 20 carbon atoms or a fused non-aromatic heterocyclic ring, and having a second 4 to 20 carbon atoms. Examples thereof include a divalent group having a second bond on the atom constituting the ring of 20 monocyclic or condensed non-aromatic heterocycles.

The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in -Q ^1- are -R ⁿ , -OH, -OR ⁿ , and-, respectively. OC (= O) -R ⁿ , -NH ₂ , -NH-R ⁿ , -N (R ^p ) -R ⁿ , -C (= O) -R ⁿ , -C (= O) -O- R ⁿ , -C (= O) -NH ₂ , -C (= O) -NH-R ⁿ , -C (= O) -N (R ^p ) -R ⁿ , -SH, -S-R ⁿ , It 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. Here, -R ⁿ and -R ^p each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms.

The aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in ^−Q1 − have high linearity in molecular structure, and the liquid crystal compounds (1) are associated with each other. 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 and a bromine atom, and is preferably unsubstituted, from the viewpoint that it is easy to easily develop a liquid crystal state. More preferred.

The substituents of the aromatic hydrocarbon ring group, the non-aromatic hydrocarbon ring group, the aromatic heterocyclic group, and the non-aromatic heterocyclic group in ^−Q1 − may be the same or different, and may be aromatic. All of the hydrocarbon ring groups, non-aromatic hydrocarbon ring groups, aromatic heterocyclic groups, and non-aromatic heterocyclic groups may be substituted, all may be unsubstituted, and some may be substituted. It may be partially unsubstituted.

Further, the substituents of the divalent organic groups in -Q ^1- , -F ^1- , -F ^2- , and -F ^3- may be the same or different, and are -Q ^1- . All of the ^divalent organic groups in ^1- , ^-F2- , and -F3- may be substituted, all may be unsubstituted, and some are substituted and some are unsubstituted. May be.

As —Q ¹ −, a hydrocarbon ring group is preferable, and a phenylene group and a cyclohexanediyl group are more preferable. Further, since the linearity of the molecular structure of the liquid crystal compound (1) can be increased, a 1,4-phenylene group and a cyclohexane-1,4-diyl group are more preferable as ^—Q1 −.

As the divalent organic group of -F ^1- , -F ^2- and -F ^3- , -Q ^1- is a hydrocarbon ring group, that is, the divalent organic group is a hydrocarbon ring group. preferable. Further, as the divalent organic group, a phenylene group and a cyclohexanediyl group are more preferable, and since the linearity of the molecular structure of the liquid crystal compound (1) can be increased, the 1,4-phenylene group and the cyclohexane-1,4 are used. -The diyl group is more preferred.

As the liquid crystal compound (2), one of -F ^1- , -F ^2- and -F ^3- in the above formula (2) has a partial structure represented by the formula (1), and the other two have a partial structure. Those that are independently divalent organic groups are preferable. Further, among -F ^1- , -F ^2- and -F ^3- , it is preferable that ^-Cy- of the partial structure represented by the formula (1) is a hydrocarbon ring group, and the divalent organic group is preferable. It is particularly preferable that it is a hydrocarbon ring group. By being these groups, the orientation tends to be good.
Further, for the reason of enhancing the linearity of the core, it is preferable that the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group. Further, it is more preferable that one of -F ^1- and -F ^3- is a cyclohexane-1,4-diyl group.
Further, one of -F ^1- and -F ^3- is a partial structure represented by the formula (1), and the other one and -F ^2- are divalent organic groups. preferable. In this case, it is preferable that at least one of -F ^1- and -F ^3- is a cyclohexane-1,4-diyl group, and it is particularly preferable that -F ^2- is a 1,4-phenylene group. By being these groups, the orientation tends to be good.

Since the liquid crystal compound (1) tends to have linearity and rotational movement around the short axis of the molecule, -Y ^1- and -Y ^2- in the formula (2) have independent π-bonding properties. Small, 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- , but preferably single bond, -C (= O) O-, -OC (= O)-, -CH ₂ CH _2- , -CH ₂ O-, or -OCH _2- .

When -X ^1- and -Y ^1- or -X ^1- and -Y ^2- are combined as in the above formula (2A), formula (2C), formula (2D), and formula (2F). It is preferable that -Y ^1- that binds to -X ^1- or -Y ^2- that binds to -X ^1- is a single bond. Further, the other of -X ^1- and -Y ^1- and -Y ^2- is preferably -C (= O) O- or -OC (= O)-.
Further, when -X ^1- is not bound to any of -Y ^1- and -Y ^2- as in the above formulas (2B) and (2E), -X ^1- is -CH ₂ It is preferably CH _2- , -CH ₂ O-, or -OCH _2- ; both -Y ^1- and -Y ^2- are -C (= O) O- or -OC (= O)-. Is preferable.

As the liquid crystal compound (2), the compound represented by the formula (2A), (2B), (2E) or (2F) is preferable.

Specific examples thereof include, but are not limited to, the following compounds as the liquid crystal compound (1).

(Content of liquid crystal compound)
The liquid crystal compound contained in the composition for forming an anisotropic dye film of the present invention is preferably composed of the liquid crystal compound (1). The composition for forming an anisotropic dye film of the present invention may contain only one kind of the liquid crystal compound (1) alone, or may contain two or more kinds in any combination and ratio. ..

The content of the liquid crystal compound in the composition for anisotropic dye film of the present invention (when two or more kinds of liquid crystal compounds are used in combination, the total content of each) is the solid content of the composition for anisotropic dye film. With respect to (100 parts by mass), 50 parts by mass or more is preferable, 55 parts by mass or more is more preferable, 99 parts by mass or less is preferable, and 98 parts by mass or less is more preferable. When the content of the liquid crystal compound in the composition for an anisotropic dye film is not more than the above lower limit, the orientation of the liquid crystal molecules tends to be high.

The composition for an anisotropic dye film of the present invention may contain one or more of a polymerizable or non-polymerizable liquid crystal compound other than the liquid crystal compound (1), but the liquid crystal compound. From the viewpoint of further effectively obtaining the effect of the present invention by using (1), the ratio of the liquid crystal compound (1) in 100% by mass of the total amount of the liquid crystal compounds contained in the composition for an anisotropic dye film of the present invention. Is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15 to 100% by mass.

(Isotropic phase appearance temperature)
From the viewpoint of the process, the 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 generally 200 ° C. or lower and 160 ° C. or lower. , 140 ° C. or lower is more preferable, 115 ° C. or lower is further preferable, 110 ° C. or lower is further preferable, and 105 ° C. or lower is particularly preferable.
Here, the isotropic phase appearance temperature means the phase transition temperature from the liquid crystal to the liquid and the phase transition temperature from the liquid to the liquid crystal. In the present invention, at least one of these phase transition temperatures is preferably not more than or equal to the above upper limit, and more preferably both of these phase transition temperatures are not more than or equal to the above upper limit.

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

<Preferable combination of dye (D1) and liquid crystal compound (1)>
From the viewpoint that it is easy to improve the orientation of the anisotropic dye film formed by using the composition for forming an anisotropic dye film, the composition for forming an anisotropic dye film includes the molecular length of the liquid crystal compound and the dye. It is preferable that the difference from the molecular length of the liquid crystal molecule is small because the interaction between the liquid crystal molecule and the dye molecule is strong and the dye molecule does not easily inhibit the association between the liquid crystal molecules.

Therefore, in the anisotropic dye film forming composition of the present invention, the number of ring structures ( _rn1 ) contained in the liquid crystal compound (1) contained in the anisotropic dye film forming composition and the anisotropic dye. The ratio (r _n1 / r _n2 ) to the number of ring structures (r _n2 ) of the dye (D1) contained in the film-forming composition is preferably 0.7 to 1.5.
A condensed ring in which two or more rings are condensed is counted as one as a ring structure.

Here, the number of ring structures ( _rn2 ) possessed by the dye (D1) is the sum of A ¹ −, − A ² −, and − A ³ − in the formula (D1), and 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 ³ is a cyclic functional group such as a pyrrolidinyl group or a piperidinyl group, the ring structure contained in -X ³ is not included in the number of ring structures (r _n2 ) possessed by the dye (D1). ..

More specifically, when n is 1, r _n2 is 3, so r _n1 is 3 or 4; when n is 2, r _n2 is 4, so r _n1 is 3, 4, 5 or 6; when n is 3, _rn2 is 5, so if _rn1 is 4, 5, 6, or 7, the liquid crystal compound contained in the anisotropic dye film forming composition ( The ratio (r n1 / r n2) of the number of ring structures (r _n1 ) possessed by 1) to the number of ring structures (r _n2 ) possessed by the dye (D1) contained in the anisotropic dye film forming composition (r _n1 / r _n2 ). Is preferable because it is 0.7 to 1.5.

When the liquid crystal compound (1) has a polymerizable group, the number of ring structures ( _rn1 ) contained in the liquid crystal compound (1) contained in the composition for forming an anisotropic dye film includes the polymerizable group. The included ring structure (eg, oxylan ring, oxetane ring, etc.) is not included.

<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 liquid crystal compound, and is, for example, methanol. , Ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether and other alcohol solvents; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether. Ester solvents such as acetate and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methylisobutylketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; aromatics such as toluene and xylene Group hydrocarbon solvent; nitrile solvent such as acetonitrile; ether solvent such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether; perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, hexafluoro-2-propanol and the like. Fluorine-containing solvents; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene; can be mentioned.
Only one kind of these solvents may be used, or two or more kinds of these solvents may be used in combination.

The solvent is preferably a solvent capable of dissolving the liquid crystal compound and the dye, and more preferably a solvent in which the liquid crystal compound and the dye are completely dissolved. When the liquid crystal compound is a polymerizable compound, it is preferably a solvent that is inert to the polymerization reaction. Further, from the viewpoint of applying the composition for forming an anisotropic dye film of the present invention described later, a solvent having a boiling point in the range of 50 to 200 ° C. is preferable.

When the composition for forming an anisotropic dye film of the present invention contains a solvent, the content ratio of the solvent in the composition for forming an anisotropic dye film is the total amount (100% by mass) of the composition of the present invention. Therefore, 50 to 98% by mass is preferable. In other words, the solid content in the anisotropic dye film forming composition of the present invention is preferably 2 to 50% by mass.
When the solid content in the anisotropic dye film forming composition is not more than the upper limit, the viscosity of the anisotropic dye film forming composition does not become too high, and the thickness of the obtained polarizing film becomes uniform. , The polarizing film tends to be less likely to be uneven.
The solid content can be determined in consideration of the thickness of the polarizing film to be manufactured.

The viscosity of the composition for an anisotropic dye film of the present invention is not particularly limited as long as a uniform film having no uneven thickness is produced by the coating method described later, but the thickness uniformity over a large area, the coating speed, and the like are not particularly limited. From the viewpoint of obtaining in-plane uniformity of productivity and optical characteristics, 0.1 mPa · s or more is preferable, 500 mPa · s or less is preferable, 100 mPa · s or less is more preferable, and 50 mPa · s or less is further preferable.

<Other additives>
The composition for forming an anisotropic dye film of the present invention further contains a polymerization initiator, a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, and a surfactant as components other than the dye and the liquid crystal compound, if necessary. , Leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic / inorganic fillers, organic / inorganic nanosheets, organic / inorganic nanofibers, metal oxides and other additives may be contained. .. By containing these additives, the coatability and stability of the anisotropic dye film forming composition of the present invention can be improved, or the anisotropic dye film forming composition of the present invention can be formed. It may be possible to improve the stability of the anisotropic dye film.

In particular, the composition for an anisotropic dye film of the present invention preferably contains a polymerization initiator as other additives, and examples of the polymerization initiator include titanosen derivatives; biimidazole derivatives; halomethylated oxadi. Azole derivatives; halomethyl-s-triazine derivatives; alkylphenone derivatives; oxime ester derivatives; benzoins; benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; acetophenone derivatives; Examples thereof include thioxanthone derivatives; benzoic acid ester derivatives; aclysine derivatives; phenazine derivatives; anthlon derivatives and the like.
Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.

Specifically, examples of the titanium derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, and dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluorophenyl). 1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluoropheni-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheni-1-yl) Il), Dicyclopentadienyl Titanium Di (2,6-difluoropheni-1-yl), Dicyclopentadienyl Titanium Di (2,4-difluoropheni-1-yl), Di (Methylcyclopentadienyl) ) Titanium bis (2,3,4,5,6-pentafluoropheni-1-yl), di (methylcyclopentadienyl) titanium bis (2,6-difluoropheni-1-yl), dicyclopentadi Examples thereof include enyl titanium [2,6-di-fluoro-3- (pyro-1-yl) -pheni-1-yl].

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

Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole and 2-trichloromethyl-5-[β- (2'-). Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5-[β- (2'-(6''-benzofuryl) vinyl)]-1,3,4-oxadiazole, Examples thereof 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 and 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-Triazine and the like can be mentioned.

Examples of alkylphenone derivatives include diethoxyacetophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, and 2-benzyl-2-dimethylamino-1-(. 4-Morphorinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamyl Benzoyl, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3-3 Examples thereof include (4-diethylaminobenzoyl) coumarin and 4- (diethylamino) chalcone.

Examples of oxime ester derivatives include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone and O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazole-3-yl] Etanone oxime, oxime ester derivatives described in JP-A-2000-80068, JP-A-2006-36750, International Publication No. WO2009 / 131189, etc. Be done.

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

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

Examples of the acylphosphine oxide derivatives include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4). 6-trimethylbenzoyl) phenylphosphine oxide and the like can be mentioned.

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

Examples of sulfonium salts include triphenylsulfonium / hexafluorophosphate, triphenylsulfonium / hexafluoroantimonate, triphenylsulfonium / tetrakis (pentafluorophenyl) borate, and diphenyl [4- (phenylthio) phenyl] sulfonium / hexafluorophosphate. , 4,4'-bis [diphenylsulfonio] diphenylsulfide bishexafluorophosphate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonate] diphenylsulfide bishexafluoroantimonate, 4,4 '-Bis [di (β-hydroxyethoxy) phenylsulfonate] diphenylsulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfonate] -2-isopropylthioxanthone hexafluoroantimonate, 7- [di (di (p-toluyl) sulfonate) p-Truyl) Sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonate-diphenylsulfide hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-di (p-toluyl) sulfonate-diphenylsulfide tetrakis (pentafluorophenyl) borate, etc. Can be mentioned.

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

Examples of acetophenone derivatives include 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanol, and 1-hydroxy. -1-Methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanol, 1, Examples thereof include 1,1-trichloromethyl- (p-butylphenyl) ketone.

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

Examples thereof include benzoic acid ester derivatives; ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like.

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

Examples of phenazine derivatives include 9,10-dimethylbenzphenazine.

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

Only one kind of these polymerization initiators may be used, or two or more kinds thereof may be used in combination.

A commercially available product can also be used as the polymerization initiator.
Examples of commercially available products include IRGACURE (registered trademark; the same applies hereinafter) 250, IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379, IRGACURE 379. , OXE-01, OXE-02 (all manufactured by BASF); Sakeol (registered trademark) BZ, Z, and BEE (manufactured by Seiko Kagaku Co., Ltd.); kayacure (registered trademark) BP100, and UVI-6992. (Manufactured by Dow Chemical Co., Ltd.); ADEKA PTOMER SP-152 and SP-170 (manufactured by ADEKA Corporation); TAZ-A and TAZ-PP (manufactured by Nippon Sibel Hegner Co., Ltd.); and TAZ-104 (stocks). (Manufactured by Sanwa Chemical Co., Ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO. Made).

When the anisotropic dye film forming composition of the present invention contains a polymerization initiator, the content of the polymerization initiator in the anisotropic dye film forming composition of the present invention does not easily disturb the orientation of the liquid crystal compound. From this point of view, it is usually 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the liquid crystal compound.

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

In addition, a sensitizing dye may be used in combination for the purpose of increasing the sensitivity, if necessary. An appropriate sensitizing dye is used depending on the wavelength of the exposure light source. For example, the xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc .; JP-A-3-239703. Cmarin-based dyes having a heterocycle described in JP-A, JP-A-5-289335; JP-A-3-239703; 3-Ketokumarin-based dyes described in JP-A-5-289335, etc .; JP-A-6. Pyrromethene dyes described in JP-A-19240 and the like; JP-A-47-2528, JP-A-54-155292, JP-A-45-373777, JP-A-48-84183, JP-A-A. 52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57-16888, JP. Examples thereof include dyes having a dialkylaminobenzene skeleton described in JP-A-5-107761, JP-A-5-210240, JP-A-4-288818 and the like.
The sensitizing dye may also be used alone or in combination of two or more.

<Method for producing a composition for forming an anisotropic dye film>
The method for producing the composition for an anisotropic dye film of the present invention is not particularly limited. For example, a dye, a liquid crystal compound, a solvent, other additives and the like are mixed, and the dye is dissolved by stirring and shaking at 0 to 80 ° C. In the case of poor solubility, a homogenizer, a bead mill disperser, or the like may be used.

As a method for producing the composition for an anisotropic dye film of the present invention, a filtration step may be provided for the purpose of removing foreign substances and the like in the composition.

In the composition for forming an anisotropic dye film of the present invention, the composition obtained by removing the solvent from the composition for forming an anisotropic dye film may or may not be a liquid crystal display at an arbitrary temperature, but at any temperature. It is preferable to show liquid crystallinity. The composition obtained by removing the solvent from the composition for forming an anisotropic dye film of the present invention has an isotropic phase appearance temperature of generally less than 200 ° C. and 160 ° C. from the viewpoint of the coating process described below. It is preferably less than, more preferably less than 140 ° C, even more preferably less than 115 ° C, even more preferably less than 110 ° C, and particularly preferably less than 105 ° C.

[Anisotropy dye film]
The anisotropic dye film of the present invention formed by using the composition for an anisotropic dye film of the present invention contains a dye (D1) and a liquid crystal compound (1) (however, the liquid crystal compound (1) is polymerized. When it is a sex compound, it contains a dye (D1) and one or both of a liquid crystal compound (1) and a polymer having a unit based on the liquid crystal compound (1)).

The anisotropic dye film of the present invention contains dyes other than the dye (D1), polymerizable or non-polymerizable liquid crystal compounds other than the liquid crystal compound (1), and polymerization as components other than the dye (D1) and the liquid crystal compound (1). Initiators, polymerization inhibitors, polymerization aids, polymerizable non-liquid crystal compounds, non-polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic / inorganic fillers , Organic / inorganic nanosheets, organic / inorganic nanofibers, metal oxides and the like may be contained.

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, and also has a film forming process and a substrate or an organic compound (dye). By selecting a composition containing (or transparent material), it can be functionalized as various anisotropic dye films such as refractive anisotropy and conduction anisotropy.

When the anisotropic dye film of the present invention is used as a polarizing element of an antireflection film for a liquid crystal display or an OLED, the orientation characteristic of the anisotropic dye film can be expressed by using a two-color ratio. When the two-color ratio is 8 or more, it functions as a polarizing element, but 11 or more is preferable, 15 or more is more preferable, 20 or more is further preferable, 25 or more is more preferable, 30 or more is particularly preferable, and 40 or more is particularly preferable. .. Further, the higher the two-color ratio, the more preferable. When the two-color ratio is at least the above lower limit value, it is useful as an optical element described later, particularly a polarizing element.

When used as a polarizing element of an antireflection film for an OLED, even if the performance of a peripheral material such as a retardation film is low, if the performance of the polarizing element is high, the characteristics as an antireflection film are improved. Therefore, if the performance of the polarizing element is high, the layer structure can be easily simplified, and even a thin film structure can easily exhibit a sufficient function, and can be suitably used for applications including folding and bending. In addition, the cost can be kept low.

The two-color ratio (D) referred to in the present invention is expressed by the following formula when the dyes are uniformly oriented.
D = Az / Ay
Here, Az is the absorbance observed when the polarization direction of the light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye, and Ay is the polarization of the light incident on the anisotropic dye film. Absorbance observed when the direction is perpendicular.
The absorbance of each of them is not particularly limited as long as it has the same wavelength, and any wavelength may be selected depending on the purpose. However, when expressing the degree of orientation of the anisotropic dye film, 350 nm of the anisotropic dye film is used. It is preferable to use a value corrected by luminosity factor in a specific wavelength range of about 800 nm or a value in the maximum absorption wavelength in the visible range.

The transmittance of the anisotropic dye film of the present invention in the visible light wavelength range is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. Further, the transmittance may be an upper limit according to the application. For example, when the degree of polarization is increased, the transmittance is preferably 50% or less. Having a transmittance in the above range, it is useful as an optical element to be described later, and as an optical element for a liquid crystal display used for color display or an antireflection film in which an anisotropic dye film and a retardation film are combined. It is useful.

The thickness of the anisotropic dye film is preferably 10 nm or more, more preferably 100 nm or more, and further preferably 500 nm or more as a dry film thickness. On the other hand, it is preferably 30 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, and particularly preferably 3 μm or less. When the thickness of the anisotropic dye film is within the above range, it tends to be possible to obtain a uniform orientation and a uniform film thickness of the dye in the film.

[Manufacturing method of 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 composition on a substrate by some method. Therefore, the composition for an anisotropic dye film may or may not contain a solvent as long as it has fluidity. From the viewpoint of viscosity and film uniformity at the time of coating, it is more preferable to contain a solvent.

The orientation of the liquid crystal display or the dye in the anisotropic dye film may be oriented by shearing or the like in the coating process, or may be oriented in the process of drying the solvent. Further, the liquid crystal, the dye and the like may be oriented and laminated on the substrate through a process of reorienting the liquid crystal and the dye by heating after coating and drying. In the wet film forming method, when the composition for an anisotropic dye film is applied onto a substrate, it is already in the composition for an anisotropic dye film, in the process of drying the solvent, or after the solvent is completely removed. Then, the dye or the liquid crystal compound undergoes self-association (molecular association state such as liquid crystal state), so that orientation occurs in a minute area. By giving an external field to this state, it is possible to obtain an anisotropic dye film having desired performance by orienting in a certain direction in a macroscopic region. In this respect, it is different from the method in which a polyvinyl alcohol (PVA) film or the like is dyed with a solution containing a dye, stretched, and the dye is oriented only in the stretching step. Here, the external field includes the influence of the alignment treatment layer previously applied on the substrate, shearing force, magnetic field, electric field, heat, etc., and these may be used alone or in combination of two or more. good. If necessary, a heating step may be performed.

The process of applying the composition for an anisotropic dye film onto the substrate to form a film, the process of applying an external field to align the composition, and the process of drying the solvent may be performed sequentially or simultaneously.

Examples of the method of applying the anisotropic dye film forming composition on 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 by 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 the anisotropic dye film is, for example, the transmission axis (polarization axis) or absorption axis of polarization in the case of a polarizing film, and the phase advance axis in the case of a retardation film. Or it is the slow axis.

The method for applying the composition for an anisotropic dye film to obtain an anisotropic dye film is not particularly limited, but for example, "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., published on March 20, 1971). ), Pages 253 to 277, "Creation and application of molecularly coordinated materials" supervised by Kunihiro Ichimura (CMC Publishing Co., Ltd., published on March 3, 1998), methods described on pages 118 to 149, steps. 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, etc. The method of applying with is mentioned. Of these, the slot die coat method and the bar coat method are preferable because a highly uniform anisotropic dye film can be obtained.

The die coater used in the slot die coating method generally includes a coating machine that discharges a coating liquid, a so-called slit die. The slit die is, for example, JP-A-2-164480, JP-A-6-154678, JP-A-9-131559, "Basics and Applications of Dispersion / Coating / Drying" (2014, Technosystem Co., Ltd.). ISBN978492472287C 305), "Wet coating technology in displays and optical components" (2007, Information Organization, ISBN9784901677752), "Precision coating and drying technology in the electronics field" (2007, Technical Information Association, ISBN9784861041389), etc. There is. These known slit dies can be applied even to a flexible member such as a film or tape or a hard member such as a glass substrate.

As the substrate used for forming the anisotropic dye film of the present invention, glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl Examples thereof include cellulose or urethane films. Further, on the surface of this substrate, in order to control the orientation direction of the dye, a known method (rubbing) described on pages 226 to 239 of "LCD Handbook" (Maruzen Co., Ltd., published on October 30, 2000). Method, method of forming a groove (fine groove structure) on the surface of the alignment film, method of using polarized ultraviolet light / polarized laser (photoalignment method), alignment method by LB film formation, alignment method by diagonal deposition of inorganic substances, etc.) Therefore, the alignment treatment (alignment film) may be applied. In particular, alignment treatment by a rubbing method or a photo-alignment method can be preferably mentioned. Examples of the material used in the rubbing method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin and the like. Examples of the material used in the photo-alignment method include polycinnamate-based materials, polyamic acid / polyimide-based materials, and azobenzene-based materials. When the alignment treatment layer is provided, it is considered that the liquid crystal compound or the dye is oriented due to the influence of the alignment treatment of the alignment treatment layer and the shearing force applied to the composition for the anisotropic dye film at the time of coating.

When the composition for the anisotropic dye film is applied, the supply method and the supply interval of the composition for the anisotropic dye film are not particularly limited. Since the coating liquid supply operation may become complicated or the coating film thickness may fluctuate at the start and stop of the coating liquid, the anisotropic dye film is continuously anisotropic when the film thickness is thin. It is desirable to apply the composition for a sex dye film while supplying it.

The speed at which the composition for an anisotropic dye film is applied is usually 0.001 m / min or more, preferably 0.01 m / min or more, more preferably 0.1 m / min or more, still more preferable. Is 1.0 m / min or more, and particularly preferably 5.0 m / min or more. Further, it is usually 400 m / min or less, preferably 200 m / min or less, more preferably 100 m / min or less, and further preferably 50 m / min or less. When the coating speed is in the above range, the anisotropy of the anisotropic dye film can be obtained, and the coating tends to be uniform.
The coating temperature of the composition for an anisotropic dye film is usually 0 ° C. or higher and 100 ° C. or lower, preferably 80 ° C. or lower, and more preferably 60 ° C. or lower.
The humidity at the time of coating the composition for an anisotropic dye film is preferably 10% RH or more, and preferably 80 RH or less.

The anisotropic dye film may be insolubilized. The insolubilization means a treatment of controlling the elution of the compound from the anisotropic dye film by reducing the solubility of the compound in the anisotropic dye film and enhancing the stability of the film.
Specifically, film polymerization, overcoating, and the like are preferable from the viewpoints of ease of post-process, durability of the anisotropic dye film, and the like.

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

When the polymerization is carried out using light or radiation, it is preferable to irradiate with active energy rays having a wavelength in the range of 190 to 450 nm.
The light source of the active energy ray having a wavelength of 190 to 450 nm is not particularly limited, and is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, and carbon. Lamp light sources such as arcs and fluorescent lamps; laser light sources such as argon ion lasers, YAG lasers, excima lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers can be mentioned. An optical filter can also be used when irradiating light of a specific wavelength for use. The exposure amount of the active energy ray is preferably 1 to 100,000 J / m ² , more preferably 10 to 10,000 J / m ² .

When the polymerization is carried out using heat, it is preferably carried out in the range of 50 to 200 ° C., and more preferably carried out in the range of 60 to 150 ° C.
Polymerization may be carried out using light, heat, and / or radiation, but the use of photopolymerization or the combined use of photopolymerization and thermal polymerization has a shorter film formation process time and is simpler. Is preferable.

[Optical element]
The optical device 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 for obtaining linear polarization, circular polarization, elliptically polarized light, retardation element, refraction anisotropy, conduction anisotropy, etc. by utilizing the anisotropy of light absorption. Represents an element. These functions can be appropriately adjusted by the anisotropic dye film forming process and the selection of a composition containing a substrate or an organic compound (dye or transparent material).

The optical element of the present invention is most preferably used as a polarizing element.
The optical element of the present invention can be suitably used for applications such as flexible displays because 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 another layer in order to maintain and improve the function of the anisotropic dye film. For example, a layer having a function of blocking a specific wavelength or a layer having a function of blocking a specific substance (oxygen blocking film, steam blocking film) used to improve durability such as light resistance, heat resistance, and water resistance. Barrier film, etc.); Examples include a wavelength cut filter and a layer containing a material that absorbs a specific wavelength, which is used for changing the color gamut and improving the optical characteristics.

[Polarizing element]
A polarizing element (hereinafter, may be 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 produced 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.

Further, the polarizing element is not limited to the anisotropic dye film, but is an overcoat layer having functions such as improving polarization performance and mechanical strength; an adhesive layer or an antireflection layer; an alignment film; as a retardation film. It may be used in combination with a layer having optical functions such as a function as a brightness improving film, a function as a reflection or antireflection film, a function as a transflective reflective film, and a function as a diffusion film; .. Specifically, the above-mentioned layers having various functions may be laminated and formed by coating, bonding, or the like, and used as a laminated body.
These layers can be appropriately provided according to the manufacturing process, characteristics, and functions, and the position, order, and the like of the layers are not particularly limited. For example, the position where each layer is formed may be formed on the anisotropic dye film or may be formed on the opposite surface of the substrate provided with the anisotropic dye film. Further, the order of forming each layer may be before or after forming the anisotropic dye film.

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

The layer having a function as a retardation film can be formed by applying or bonding the retardation film to other layers constituting the polarizing element. For example, the retardation film may be subjected to the stretching treatment described in JP-A-2-59703, JP-A-4-230704, etc., or may be subjected to the treatment described in JP-A-7-230007. Can be formed by

The layer having a function as a luminance improving film can be formed by applying or bonding the luminance improving film to other layers constituting the polarizing element. The luminance-improving film is formed by, for example, forming micropores by a method as described in JP-A-2002-1690.25 and JP-A-2003-29030, or two or more layers having different center wavelengths of selective reflection. It can be formed by superimposing the cholesteric liquid crystal layer of.

The layer having a function as a reflective film or a transflective reflective film is formed by, for example, applying or bonding a metal thin film obtained by vapor deposition or sputtering to another layer constituting the polarizing element. Can be done.
The 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 having a function as a retardation film or an optical compensation film is composed of 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, and another layer constituting the polarizing element. It can be formed by applying it to 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 or the like for various display elements such as LCDs and OLEDs, the present invention is directly applied to the surface of the electrode substrate or the like constituting these display elements. An anisotropic dye film may be formed, or the substrate on which the anisotropic dye film of the present invention is formed may be used as a constituent member of these display elements.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
In the following description, "part" means "part by mass".

[Method of identifying liquid crystal phase]
The liquid crystal properties of the obtained anisotropic dye film forming composition are differential scanning calorimetry (Seiko Instruments Co., Ltd. "DSC220CU"), X-ray structure analysis (Rigaku Co., Ltd. "NANO-Viewer"), and hot stage (Co., Ltd.). Observe with a polarizing microscope (Nikon Instech Co., Ltd. "ECLIPSE LV100N POL") attached to Toyo Technica "HCS302-LN190"), and "LCD Handbook" (Maruzen Co., Ltd., published on October 30, 2000) 9 It was identified as a liquid crystal according to the method described on page 50, pages 117 to 176, and the like.

[Measurement of transmittance and two-color ratio for polarization in the absorption axis / polarization axis direction of the anisotropic dye film]
The transmittance of the obtained anisotropic dye film for polarization in the absorption axis / polarization axis direction was determined by using a spectrophotometer equipped with a Glan Thomson modulator (manufactured by Otsuka Electronics Co., Ltd., product name "RETS-100"). It was measured.
The measurement light of linear polarization is incident on the anisotropic dye film, and the transmittance of the anisotropic dye film with respect to the polarization in the absorption axis direction and the transmittance of the anisotropic dye film with respect to the polarization in the polarization axis direction are measured. The two-color ratio (D) was calculated by
D = Az / Ay
(During the ceremony,
Ay = -log (Ty);
Az = -log (Tz);
Tz is the transmittance of the anisotropic dye film for polarization in the absorption axis direction;
Ty is the transmittance of the anisotropic dye film with respect to the polarization in the polarization axis direction. )

Specifically, a sandwich cell (cell gap: 8.0 μm, 10.0 μm, 12.0 μm, film formation) in which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems) is formed on glass as a base material. The anisotropic dye film is formed by injecting the composition for an anisotropic dye film into an isotropic phase and cooling the mixture to 80 ° C at 5 ° C / min. The two-color ratio was measured at each temperature while further cooling to 0 ° C. at 5 ° C./min. Among them, the two-color ratio at the temperature and wavelength showing the maximum two-color ratio was determined as the two-color ratio of the anisotropic dye film.

[Synthesis of liquid crystal compounds]
<Liquid crystal compound (I-1)>
The liquid crystal compound (I-1) was synthesized according to the synthesis method described below.

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

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

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

Synthesis of (I-1-d):
(I-1-c) (2.33 g, 7.0 mmol), tetrahydrofuran (20 mL) was mixed, followed by N, N-dimethylaniline (1.02 g, 8.4 mmol), 2,5-di-t. -Butylphenol (54 mg) was added. After cooling in an ice bath, acryloyl chloride (0.76 g, 8.4 mmol) was slowly added. After stirring under an ice bath for 6 hours, methylene chloride was added, and the mixture was washed in the order of 1 mol / L hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, and saturated brine. Purification by silica gel column chromatography (chloroform / methanol) gave 2.0 g of a white solid (I-1-d).

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

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

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

Synthesis of (I-1-h):
Compound (I-1-h) was synthesized according to the synthetic method described below.

Lub et al. , Recl. Trav. ChIm. (I-1-i) was synthesized by a method according to the compound described in Pays-Bas, 115, 321-328 (1996).
Next, (I-1-i) (trans form only) (42.9 g, 107.6 mmol), p-toluenesulfonic acid pyridinium salt (2.6 g, 10.8 mmol) and ethanol (430 mL) were mixed. The mixture was stirred at 78 ° C. for 2 hours. The solvent was distilled off, it was dissolved in ethyl acetate (150 mL), hexane (750 mL) was added, and the mixture was cooled. The precipitated precipitate was separated by filtration, washed with hexane, and dried to obtain 29.2 g of a white solid (I-1-j).
(I-1-j) (37.2 g, 118.3 mmol), N, N-dimethylaniline (21.5 g, 177.5 mmol), 2,5-di-t-butylphenol (0.24 g), tetrahydrofuran ( 380 mL) was mixed. After cooling in an ice bath, acryloyl chloride (16.1 g, 177.5 mmol) was slowly added. After the dropping, the mixture was stirred at 50 ° C. for 2 hours, the solvent was distilled off until the liquid volume reached 190 mL, and the residue was discharged into 1 mol / L hydrochloric acid under ice-cooling. The precipitated precipitate was separated by filtration and washed with water and hexane. Purification by silica gel column chromatography (hexane / ethyl acetate) gave 39.4 g of a white solid (I-1-h).

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

The results of liquid chromatograph-mass spectrometry of this liquid crystal compound (I-1) are shown below.
LC-MS (APCI) m / z 851.5 (M + Na ⁺ )
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H NMR (CDCl ₃ , 400 MHz) δ1.20-1.70 (m, 38H), 1.74-1.85 (m, 2H), 2.05-2.25 (m, 4H), 2. 49-2.57 (m, 1H), 3.21-3.29 (m, 1H), 3.46 (t, 2H, J = 6.8Hz), 3.99 (t, 2H, J = 6) .8Hz), 4.15 (t, 4H, J = 6.8Hz), 5.80 (d, 2H, J = 10.4Hz), 6.12 (dd, 2H, J = 17.2, 10. 4Hz), 6.39 (d, 2H, J = 17.2Hz), 6.89 (d, 2H, J = 6.8Hz), 7.10 (d, 2H, J = 6.8Hz), 7. 19 (d, 2H, J = 6.8Hz), 7.55 (d, 2H, J = 6.8Hz)

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

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

Synthesis of (II-1-a):
4-Butylaniline (25.0 g, 167 mmol) and acetic acid (210 mL) were mixed under a nitrogen stream, ammonium thiocyanate (54.3 g, 670 mmol) was added, and the mixture was ice-cooled to 3 ° C. Bromine (30.7 g, 384 mmol) dissolved in acetic acid (43 mL) was added dropwise over 1.5 hours, and the mixture was stirred at 20 ° C. for 2 hours. An aqueous solution of sodium hydrogen sulfite was added and quenched, and the insoluble components were filtered and washed with ethyl acetate. A 48% aqueous sodium hydroxide solution was added to the filtrate side to adjust the pH to 8. The reaction solution was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 25.1 g of (II-1-a).

Synthesis of (II-1-b):
(II-1-a) (25.1 g, 121 mmol) and 85% phosphoric acid (350 mL) were mixed, heated at 80 ° C. for 30 minutes, and then cooled to 3 ° C. 40% Nitrosylsulfuric acid (46.0 g, 145 mmol) was added, and the mixture was stirred at 3 ° C. for 30 minutes.
Aniline (37.3 g, 400 mmol), sodium formaldehyde bisulfite (53.6 g, 400 mmol) and water (2.5 L) were mixed and stirred at 70 ° C. for 2 hours. After cooling to 3 ° C., amidosulfate (11.7 g, 121 mmol) was added, and the above solution containing the diazonium salt was added dropwise over 30 minutes, and then the mixture was stirred at 3 ° C. for 30 minutes. A 48% aqueous sodium hydroxide solution (4.2 L) was added while keeping the temperature below 10 ° C., and the mixture was stirred at 90 ° C. for 2 hours. After allowing to cool, the precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 23.0 g of (II-1-b).

Synthesis of (II-1):
The reactor was mixed with (II-1-b) (4.0 g, 13 mmol) and N-methylpyrrolidone (80 mL) and cooled to 3 ° C. After adding 35% hydrochloric acid (4 mL) and water (60 mL), sodium nitrite (1.0 g, 14 mmol) dissolved in water (5 mL) was added, and the mixture was stirred at 15 ° C. for 2 hours. Amidosulfate (0.3 g, 3 mmol) dissolved in water (3 mL) was added to prepare a diazonium solution.
Diethylaniline (1.9 g, 13 mmol), methanol (60 mL) and water (6 mL) were mixed and cooled to 3 ° C., and then a 1 M aqueous hydrochloric acid solution was added to adjust the pH to 6. While adjusting the pH to 6-7 with a 25% aqueous sodium hydroxide solution, the above solution containing the diazonium salt was added dropwise over 30 minutes, the mixture was stirred at 3 ° C. for 30 minutes, and water (300 mL) was added. The precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (hexane / dichloromethane) and then reprecipitated with dichloromethane / methanol to obtain 1.5 g of dye (II-1).

The maximum absorption wavelength (λmax) of this dye (II-1) in a 10 ppm chloroform solution was 547 nm, and the gram absorption coefficient was 101.2 Lg ^-1 cm ^-1 .
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H-NMR (CDCl ₃ , 400 MHz) δ0.96 (t, 3H, J = 7.3 Hz), δ1.26 (t, 6H, J = 7.1 Hz), δ1.38-1.44 (m, 2H), δ1.65-1.73 (m, 2H), δ2.78 (t, 2H, J = 7.7Hz), δ3.46-3.52 (m, 4H), δ6.75 (d, 2H, J = 9.2Hz), δ7.36 (d, 1H, J = 8.4Hz), δ7.70 (s, 1H), δ7.91 (d, 2H, J = 8.7Hz), δ8. 00 (d, 2H, J = 8.7Hz), δ8.07 (d, 1H, J = 8.4Hz), δ8.18 (d, 2H, J = 8.8Hz)

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

Synthesis of (II-2-a):
2-Amino-6-ethoxybenzothiazole (3.5 g, 18 mmol) and 85% phosphoric acid (45 mL) were mixed and cooled to 0 ° C. 40% Nitrosylsulfuric acid (6.8 g, 22 mmol) was added, and the mixture was stirred at 0 ° C. for 30 minutes.
Aniline (5.5 g, 59 mmol), sodium formaldehyde bisulfite (7.9 g, 59 mmol) and water (300 mL) were mixed and stirred at 70 ° C. for 2 hours. After cooling to 0 ° C., amidosulfate (1.7 g, 18 mmol) was added, and the above solution containing the diazonium salt was added dropwise over 15 minutes, and then the mixture was stirred at 0 ° C. for 30 minutes. A 48% aqueous sodium hydroxide solution was added while keeping the temperature below 10 ° C., the pH was adjusted to 11, and the mixture was stirred at 90 ° C. for 2 hours. After allowing to cool, the precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (dichloromethane) to obtain 0.9 g of (II-2-a).

Synthesis of (II-2):
The reactor was mixed with (II-2-a) (0.6 g, 2 mmol) and N-methylpyrrolidone (15 mL) and cooled to 0 ° C. After adding 35% hydrochloric acid (1 mL) and water (10 mL), sodium nitrite (0.2 g, 3 mmol) dissolved in water (1 mL) was added, and the mixture was stirred at 15 ° C. for 2 hours. Amidosulfate (0.1 g, 1 mmol) dissolved in water (3 mL) was added to prepare a diazonium solution.
Diethylaniline (0.3 g, 2 mmol), methanol (10 mL), and water (1 mL) were mixed, cooled to 0 ° C., and then a 1 M aqueous hydrochloric acid solution was added to adjust the pH to 6. The solution containing the above diazonium salt was added dropwise over 30 minutes while adjusting the pH to 6-7 with a 25% aqueous sodium hydroxide solution, the mixture was stirred at 0 ° C. for 30 minutes, and water (60 mL) was added. The precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (dichloromethane) to obtain 0.1 g of dye (II-2).

The maximum absorption wavelength (λmax) of this dye (II-2) in a 10 ppm chloroform solution was 548 nm, and the gram absorption coefficient was 112.9 Lg ^-1 cm ^-1 .
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H-NMR (CDCl ₃ , 400 MHz) δ1.28 (t, 6H, J = 7.1 Hz), δ1.51 (t, 3H, J = 7.0 Hz), δ3.51 (q, 4H, J = 7.1Hz), δ4.17 (q, 2H, J = 7.0Hz), δ6.78 (d, 2H, J = 7.8Hz), δ7.14 (dd, 1H, J = 2.5, 9) .0Hz), δ7.33 (d, 1H, J = 2.5Hz), δ7.94 (d, 2H, J = 8.8Hz), δ8.01 (d, 2H, J = 8.7Hz), δ8 .07 (d, 1H, J = 9.0Hz), δ8.17 (d, 2H, J = 8.8Hz)

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

Synthesis of (II-3):
(II-1-b) (3.0 g, 10 mmol) and N-methylpyrrolidone (60 mL) were mixed and cooled to 0 ° C. After adding 35% hydrochloric acid (3 mL) and water (50 mL), sodium nitrite (0.8 g, 12 mmol) dissolved in water (3 mL) was added, and the mixture was stirred at 10 ° C. for 1 hour. Amidosulfate (0.2 g, 2 mmol) dissolved in water (2 mL) was added to prepare a diazonium solution.
1-Phenylpyrrolidine (1.4 g, 10 mmol), methanol (43 mL) and water (3 mL) were mixed and cooled to 5 ° C., and then a 1 M aqueous hydrochloric acid solution was added to adjust the pH to 6. While adjusting the pH to 6-7 with a 25% aqueous sodium hydroxide solution, the above solution containing the diazonium salt was added dropwise over 30 minutes, the mixture was stirred at 15 ° C. for 1 hour, and water (200 mL) was added. The precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (chloroform / hexane) to obtain 1.5 g of dye (II-3).

The maximum absorption wavelength (λmax) of this dye (II-3) in a 10 ppm chloroform solution was 548 nm, and the gram absorption coefficient was 98.7 Lg ^-1 cm ^-1 .
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H-NMR (CDCl ₃ , 400 MHz) δ0.96 (t, 3H, J = 7.4 Hz), δ1.36-1.45 (m, 2H), δ1.65-1.72 (m, 2H) , Δ2.05-2.09 (m, 4H), δ2.77 (t, 2H, J = 7.8Hz), δ3.44 (t, 4H, J = 6.6Hz), δ6.63 (d, 2H, J = 9.2Hz), δ7.35 (dd, 1H, J = 1.7, 8.4Hz), δ7.69 (s, 1H), δ7.92 (d, 2H, J = 9.0Hz) ), δ8.00 (d, 2H, J = 8.9Hz), δ8.07 (d, 1H, J = 8.4Hz), δ8.17 (d, 2H, J = 9.2Hz),

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

Synthesis of (II-4-a):
4-Aminobenzotrifluoride (50.0 g, 310 mmol) and acetic acid (250 mL) were mixed under a nitrogen stream, sodium thiocyanate (100.0 g, 1240 mmol) was added, and the mixture was ice-cooled to 10 ° C. Bromine (57.0 g, 713 mmol) dissolved in acetic acid (250 mL) was added dropwise over 30 minutes, and the mixture was stirred at 20 ° C. for 1 hour. Saturated sodium hydrogen carbonate water (500 mL) was added, a 48% aqueous sodium hydroxide solution was added to adjust the pH to 7 to 8, filtration was performed, and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain 45.0 g of (II-4-a).

Synthesis of (II-4-b):
(II-4-a) (30.1 g, 138 mmol) and 85% phosphoric acid (450 mL) were mixed, heated at 80 ° C. for 30 minutes, and then cooled to 5 ° C. 40% Nitrosylsulfuric acid (52.6 g, 166 mmol) was added, and the mixture was stirred at 3 ° C. for 1 hour.
Aniline (52.8 g, 566 mmol), sodium formaldehyde bisulfite (76.1 g, 566 mmol) and water (2.8 L) were mixed and stirred at 70 ° C. for 2 hours. After cooling to 5 ° C., amidosulfate (6.7 g, 69 mmol) was added, and the above solution containing the diazonium salt was added dropwise over 1 hour, and then the mixture was stirred at 5 ° C. for 30 minutes. A 48% aqueous sodium hydroxide solution (1.9 L) was added while keeping the temperature below 10 ° C., and the mixture was stirred at 90 ° C. for 2 hours. After allowing to cool, the precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain 9.3 g of (II-4-b).

Synthesis of (II-4):
The reactor was mixed with (II-4-b) (2.4 g, 7 mmol) and N-methylpyrrolidone (47 mL) and cooled to 3 ° C. After adding 35% hydrochloric acid (2 mL) and water (33 mL), sodium nitrite (0.6 g, 8 mmol) dissolved in water (2 mL) was added, and the mixture was stirred at 3 ° C. for 1 hour. Amidosulfate (0.1 g, 1 mmol) dissolved in water (1 mL) was added to prepare a diazonium solution.
1-Phenylpiperidine (1.2 g, 7 mmol), methanol (24 mL) and water (2 mL) were mixed and cooled to 3 ° C., and then a 1 M aqueous hydrochloric acid solution was added to adjust the pH to 6. While adjusting the pH to 6-7 with a 25% aqueous sodium hydroxide solution, the above solution containing the diazonium salt was added dropwise over 40 minutes, the mixture was stirred at 3 ° C. for 1 hour, and water (100 mL) was added. The precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (hexane / dichloromethane), reprecipitated with dimethylformamide / water and tetrahydrofuran / water, and suspended and washed with hexane. 0.4 g of the dye (II-4) was obtained.

The maximum absorption wavelength (λmax) of this dye (II-4) in a 10 ppm chloroform solution was 545 nm, and the gram absorption coefficient was 73.8 Lg ^-1 cm ^-1 .
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H-NMR (CDCl ₃ , 400 MHz) δ1.70-1.75 (m, 6H), δ3.43-0.46 (m, 4H), δ6.96 (d, 2H, J = 9.2Hz) , Δ7.76 (d, 1H, J = 1.4Hz), δ7.78 (d, 2H, J = 1.4Hz), δ7.91 (d, 2H, J = 5.3Hz), δ8.01- 8.23 (m, 3H), δ8.28 (d, 1H, J = 8.5Hz)

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

Synthesis of (II-5a):
A mixture of bromobenzene (1.5 g, 10 mmol), potassium t-butoxide (2.1 g, 19 mmol), diisopropylamine (3.9 g, 38 mmol), and dimethyl sulfoxide (15 mL) was sealed and sealed with a microwave reactor. It was heated at 190 ° C. for 20 minutes. After allowing to cool, the mixture was quenched with water (100 mL), extracted with ethyl acetate, washed with water and brine, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (hexane / ethyl acetate) to obtain 0.9 g of (II-5a).

Synthesis of (II-5-b):
2-Amino-6-methylbenzothiazole (2.5 g, 15 mmol) and 85% phosphoric acid (38 mL) were mixed, heated at 80 ° C. for 30 minutes, and then cooled to 0 ° C. 40% Nitrosylsulfuric acid (5.6 g, 18 mmol) was added, and the mixture was stirred at 0 ° C. for 1 hour.
Aniline (4.7 g, 50 mmol), sodium formaldehyde bisulfite (6.7 g, 50 mmol) and water (465 mL) were mixed and stirred at 70 ° C. for 2 hours. After cooling to 0 ° C., amidosulfate (0.3 g, 3 mmol) was added, and the above solution containing the diazonium salt was added dropwise over 15 minutes, and then the mixture was stirred at 0 ° C. for 30 minutes. A 48% aqueous sodium hydroxide solution was added while keeping the temperature below 10 ° C., the pH was adjusted to 11, and the mixture was stirred at 90 ° C. for 2 hours. After allowing to cool, the precipitated solid was collected by filtration, and the obtained crude product was purified by silica gel column chromatography (hexane / chloroform) to obtain 01.8 g of (II-5-b).

Synthesis of (II-5):
The reactor was mixed with (II-5-b) (1.5 g, 6 mmol) and N-methylpyrrolidone (30 mL) and cooled to 0 ° C. After adding 35% hydrochloric acid (2 mL) and water (20 mL), sodium nitrite (0.7 g, 7 mmol) dissolved in water (1 mL) was added, and the mixture was stirred at 15 ° C. for 1 hour. Amidosulfate (0.3 g, 3 mmol) dissolved in water (1 mL) was added to prepare a diazonium solution.
(II-5a) (1.0 g, 6 mmol), methanol (50 mL) and water (5 mL) were mixed, cooled to 0 ° C., and then a 1 M aqueous hydrochloric acid solution was added to adjust the pH to 6. The solution containing the above diazonium salt was added dropwise over 30 minutes while adjusting the pH to 6-7 with a 25% aqueous sodium hydroxide solution, the mixture was stirred at 0 ° C. for 30 minutes, and water (300 mL) was added. The precipitated solid is collected by filtration, the obtained crude product is purified by silica gel column chromatography (chloroform / hexane), and the dye (II-5) is 0 by reprecipitation with dichloromethane / methanol and dimethylformamide / water. Obtained 5.5 g.

The maximum absorption wavelength (λmax) of this dye (II-5) in a 10 ppm chloroform solution was 551 nm, and the gram absorption coefficient was 90.7 Lg ^-1 cm ^-1 .
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H-NMR (CDCl ₃ , 400 MHz) δ1.37 (d, 12H, J = 6.9 Hz), δ2.53 (s, 3H), δ4.02 (q, 2H, J = 6.9 Hz), δ6 .90 (d, 2H, J = 9.4Hz), δ7.35 (dd, 1H, J = 1.1, 7.9Hz), δ7.70 (s, 1H), δ7.87 (d, 2H, J = 9.3Hz), δ8.00 (d, 2H, J = 8.8Hz), δ8.06 (d, 1H, J = 8.4Hz), δ8.17 (d, 2H, J = 8.9Hz) )

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

Synthesis of (II-6-a):
2-Bromothiophene (20.0 g, 123 mmol), pyrrolidine (13.2 g, 185 mmol), the same (0.4 g, 6 mmol), and dimethylaminoethanol (100 mL) were mixed, and the mixture was stirred at 80 ° C. for 48 hours. It was poured into water (250 mL), quenched, extracted with hexane, washed with water and brine, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (hexane / ethyl acetate) to obtain 10.5 g of (II-6-a).

Synthesis of (II-6-b):
4-Nitroaniline (15.0 g, 109 mmol) and water (450 mL) were mixed and mixed.
It was cooled to 0 ° C. After adding 35% hydrochloric acid (43 mL), sodium nitrite (8.3 g, 120 mmol) dissolved in water (32 mL) was added, and the mixture was stirred at 15 ° C. for 30 minutes. An aqueous solution of amidosulfate (2.1 g, 22 mmol) dissolved in water (18 mL) was added to prepare a diazonium solution.
Phenol (10.2 g, 109 mmol), methanol (200 mL), and water (200 mL) were mixed, cooled to 15 ° C., and then a 1 M aqueous hydrochloric acid solution was added to adjust the pH to 6. While adjusting the pH to 6-7 with a 25% aqueous sodium hydroxide solution, the above solution containing the diazonium salt was added dropwise over 30 minutes, and then the mixture was stirred at 15 ° C. for 1 hour, and the precipitated solid was collected by filtration. By drying at 50 ° C. under reduced pressure, 21.4 g of (II-6-b) was obtained.

Synthesis of (II-6-c):
Under a nitrogen stream, (II-6-b) (21.4 g, 88 mmol), dimethylformamide (100 mL), 1-bromopropane (19.1 g, 88 mmol) and potassium carbonate (24.3 g, 176 mmol) were mixed. The mixture was stirred at 100 ° C. for 2.5 hours. The reaction solution was poured into ice water (200 mL), and the precipitated individual was collected by filtration. The obtained crude product was purified by silica gel column chromatography (dichloromethane) to obtain 21.1 g of (II-6-c).

Synthesis of (II-6-d):
Under a nitrogen stream, (II-6-c) (21.1 g, 74 mmol), ethanol (210 mL), water (63 mL) and sodium sulfide nine hydrate (35.5 g, 148 mmol) were mixed and 1 at 70 ° C. Stir for hours. The mixture was allowed to cool to 20 ° C., the reaction solution was poured into water (500 mL), and the precipitated individual was collected by filtration. The filtrate was dissolved in acetonitrile (1 L) at 40 ° C., dried over magnesium sulfate and suction filtered, and then the filtrate was concentrated (II-6-d) to obtain 15.3 g.

Synthesis of (II-6):
(II-6-d) (1.0 g, 4 mmol) and N-methylpyrrolidone (20 mL) were mixed and cooled to 5 ° C. After adding 35% hydrochloric acid (1 mL) and water (15 mL), sodium nitrite (0.3 g, 4 mmol) dissolved in water (1 mL) was added, and the mixture was stirred at 5 ° C. for 1 hour. Amidosulfate (0.1 g, 1 mmol) dissolved in water (1 mL) was added to prepare a diazonium solution.
(II-6-a) (0.6 g, 4 mmol), methanol (10 mL), and water (10 mL) are mixed, cooled to 5 ° C., and then the pH is adjusted to 3.5-4 with a 25% aqueous sodium hydroxide solution. The solution containing the above diazonium salt was added dropwise over 30 minutes while adjusting to 5.5, and then the mixture was stirred at 5 ° C. for 1 hour and then at room temperature for 30 minutes. After adding water (100 mL), the precipitated solid was collected by filtration, the obtained crude product was purified by silica gel column chromatography (chloroform / tetrahydrofuran), and reprecipitated with dichloromethane / methanol to obtain a dye (II-). 6) was obtained in an amount of 0.7 g.

The maximum absorption wavelength (λmax) of this dye (II-6) in a 10 ppm chloroform solution was 550 nm, and the gram absorption coefficient was 130.8 Lg ^-1 cm ^-1 .
In addition, the structure was confirmed by NMR. The results are shown below.
^{1 1} H-NMR (CDCl ₃ , 400 MHz) δ1.07 (t, 3H, J = 7.4 Hz), δ1.82-1.88 (m, 2H), δ2.10-2.13 (m, 4H) , Δ3.45-3.49 (m, 4H), δ4.01 (t, 2H, J = 6.6Hz), δ6.01 (d, 1H, J = 4.5Hz), δ7.00 (d, 2H, J = 8.9Hz), δ7.57 (d, 1H, J = 4.5Hz), δ7.79 (d, 2H, J = 8.7Hz), δ7.89-8.93 (m, 4H) )

<Dye (II-7)>
The dye (II-7) was synthesized according to the synthesis method described below.

Synthesis of (II-7-a):
Tetrahydrofuran (100 mL) and sodium hydride (purity 60%, 6.7 g, 168.0 mmol) were added to the ice-cooled reactor, and diethyl (4-nitrobenzyl) phosphonate (18.0 g, 65.9 mmol) was added. , 4-Butylbenzaldehyde (9.1 g, 56.1 mmol) and tetrahydrofuran (50 mL) were added dropwise over 10 minutes, washed with tetrahydrofuran (30 mL) and then stirred at 50 ° C. for 0.5 hour. The reaction solution was poured into water, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was distilled off. The obtained crude product was dissolved by heating in ethyl acetate (20 mL), cooled by adding hexane (50 mL), the precipitated precipitate was filtered off, washed with hexane, and dried under reduced pressure (II-7-). 15.0 g of a) was obtained.

Synthesis of (II-7-b):
Ammonium chloride (13.3 g) in which (II-7-a) (15.0 g, 53.3 mmol), tetrahydrofuran (150 mL) and iron powder (13.9 g, 248.9 mmol) were mixed and dissolved in water (30 mL). , 248.6 mmol) was added dropwise, and the mixture was stirred at 50 ° C. for 3 hours. The mixture was filtered through Celite, extracted with ethyl acetate, washed with water and saturated brine, and the solvent was evaporated. The obtained crude product was suspended in hexane, the precipitate was filtered off, washed with hexane, and dried to obtain 10.9 g of (II-7-b).

Synthesis of (II-7):
(II-7-b) (2.51 g, 10.0 mmol), N-methylpyrrolidone (40 mL), concentrated hydrochloric acid (2.2 mL), water (20 mL) are mixed, cooled to 3 ° C, and then sodium nitrite. (789 mg, 11.4 mmol) was added, and the mixture was stirred at 15 ° C. for 3.5 hours.
1-Phenylpyrrolidine (1.47 g, 10.0 mmol), methanol (60 mL) and water (30 mL) were mixed and the pH was adjusted to 3.5 with concentrated hydrochloric acid. The solution containing the above diazonium salt was added dropwise while maintaining the pH at 3 to 5 by adding an aqueous sodium hydroxide solution, and then the mixture was stirred at 15 ° C. for 3 hours.
The resulting precipitate was filtered, washed with water and dried under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane / methylene chloride) to obtain 3.06 g of a red solid dye (II-7).

The maximum absorption wavelength (λmax) of this dye (II-7) in a 10 ppm chloroform solution was 459 nm, and the gram absorption coefficient was 107.6 Lg ^-1 cm ^-1 .
In addition, the structure was confirmed by NMR. The results are shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ0.94 (t, 3H, J = 7.2 Hz), 1.32-1.43 (m, 2H), 1.55-1.68 (m, 2H) , 2.00-2.12 (m, 4H), 2.62 (t, 2H, J = 7.6Hz), 3.41 (t, 4H, J = 6.4Hz), 6.63 (d, 2H, J = 8.8Hz), 7.14 (d, 2H, J = 8.8Hz), 7.19 (d, 2H, J = 8.0Hz), 7.45 (d, 2H, J = 8) .0Hz), 7.60 (d, 2H, J = 8.4Hz), 7.84 (d, 2H, J = 8.4Hz), 7.88 (d, 2H, J = 9.2Hz)

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

[Other liquid crystal compounds and dyes]
The chemical structures of liquid crystal compounds and dyes other than the above used in Examples and Comparative Examples are shown below.

[Example 1]
To 399.6 parts of chloroform, 20.00 parts of the liquid crystal compound (I-1) and 0.40 parts of the dye (II-1) were added, and the mixture was stirred and dissolved, and then the solvent was removed. A composition 1 for forming an anisotropic dye film was obtained.
It was confirmed that the composition 1 for forming an anisotropic dye film showed liquid crystallinity by observing birefringence at 40 ° C. with a polarizing microscope attached to a hot stage.
Using the obtained anisotropic dye film forming composition 1, in order to determine the two-color ratio by the above-mentioned method, an anisotropic dye film 1 was prepared using a sandwich cell having a cell gap of 8.0 μm. , The two-color ratio of the anisotropic dye film 1 was determined.
The results are shown in Table 1.

[Example 2]
In the same manner as in Example 1 except that 0.27 part of the dye (II-2) was used instead of 0.40 part of the dye (II-1), the anisotropic dye film forming composition 2 and the anisotropic dye film were formed. A sex dye film 2 was obtained.
It was confirmed that the composition 2 for forming an anisotropic dye film exhibits liquid crystallinity by observing birefringence at 40 ° C. with a polarizing microscope attached to a hot stage.
In addition, the two-color ratio of the anisotropic dye film 2 was determined.
The results are shown in Table 1.

[Example 3]
The composition 3 for forming an anisotropic dye film and anisotropic dye film formation 3 and the same as in Example 1 except that 0.30 part of the dye (II-3) was used instead of 0.40 part of the dye (II-1). A sex dye film 3 was obtained.
It was confirmed that the composition 3 for forming an anisotropic dye film exhibits liquid crystallinity by observing birefringence at 40 ° C. with a polarizing microscope attached to a hot stage.
Moreover, the two-color ratio of the anisotropic dye film 3 was determined.
The results are shown in Table 1.

[Example 4]
In the same manner as in Example 1 except that 0.41 part of the dye (II-4) was used instead of 0.40 part of the dye (II-1), the anisotropic dye film forming composition 4 and the anisotropic dye film were formed. A sex dye film 4 was obtained.
It was confirmed that the composition 4 for forming an anisotropic dye film exhibits liquid crystallinity by observing birefringence at 40 ° C. with a polarizing microscope attached to a hot stage.
Moreover, the two-color ratio of the anisotropic dye film 4 was determined.
The results are shown in Table 1.

[Example 5]
The composition 5 for forming an anisotropic dye film and anisotropic dye film formation 5 and the same as in Example 1 except that 0.33 part of the dye (II-5) was used instead of 0.40 part of the dye (II-1). A sex dye film 5 was obtained.
It was confirmed that the composition 5 for forming an anisotropic dye film exhibits liquid crystallinity by observing birefringence at 40 ° C. with a polarizing microscope attached to a hot stage.
In addition, the two-color ratio of the anisotropic dye film 5 was determined.
The results are shown in Table 1.

[Comparative Example 1]
Anisotropic dye film formation in the same manner as in Example 1 except that 20.00 parts of the liquid crystal compound (III-1) (manufactured by BASF) was used instead of 20.00 parts of the liquid crystal compound (I-1). The composition 6 and the anisotropic dye film 6 were obtained.
It was confirmed that the composition 6 for forming an anisotropic dye film showed liquid crystallinity by observing birefringence at 60 ° C. with a polarizing microscope attached to a hot stage.
Moreover, the two-color ratio of the anisotropic dye film 6 was determined.
The results are shown in Table 1.

[Comparative Example 2]
Instead of 20.00 parts of the liquid crystal compound (I-1), 20.00 parts of the liquid crystal compound (III-1) (manufactured by BASF) was used, and 0.40 parts of the dye (II-1) was replaced with the dye (dye). II-2) The composition 7 for forming an anisotropic dye film and the anisotropic dye film 7 were obtained in the same manner as in Example 1 except that 0.27 part was used.
It was confirmed that the composition 7 for forming an anisotropic dye film showed liquid crystallinity by observing birefringence at 60 ° C. with a polarizing microscope attached to a hot stage.
Moreover, the two-color ratio of the anisotropic dye film 7 was determined.
The results are shown in Table 1.

[Comparative Example 3]
The composition 8 for forming an anisotropic dye film and anisotropic dye film formation 8 and the same as in Example 1 except that 0.23 part of the dye (II-6) was used instead of 0.40 part of the dye (II-1). A sex dye film 8 was obtained.
It was confirmed that the composition 8 for forming an anisotropic dye film exhibits liquid crystallinity by observing birefringence at 40 ° C. with a polarizing microscope attached to a hot stage.
Moreover, the two-color ratio of the anisotropic dye film 8 was determined.
The results are shown in Table 1.

From Table 1, according to the composition for forming an anisotropic dye film of the present invention, a dye having maximum absorption at 350 to 500 nm and 501 to 800 nm, respectively, and a liquid crystal compound suitable for the dye are contained. It can be seen that excellent coating film properties and excellent optical performance can be realized.

[Example 6]
In 19.65 parts of the liquid crystal compound (I-1), 0.09 part of the dye (II-7) dissolved in 885.3 parts of chloroform, and the dye (II-8) dissolved in 1039.9 parts of chloroform (Co., Ltd.) Add 0.23 part of the dissolved dye (II-1) to 0.10 part of (Made by Hayashihara) and 2298.7 part of chloroform, and stir to make them compatible, and then remove the solvent to make it anisotropic. A dye film forming composition 9 was obtained. Further, an anisotropic dye film 6 was obtained in the same manner as in Example 1.
It was confirmed that the composition 9 for forming an anisotropic dye film showed liquid crystallinity by observing birefringence at 40 ° C. with a polarizing microscope attached to a hot stage.
In order to determine the two-color ratio by the above-mentioned method using the obtained anisotropic dye film forming composition 9, an anisotropic dye film 9 is prepared and the two-color ratio of the anisotropic dye film 9 is determined. Were determined.
The maximum two-color ratio of the anisotropic dye film 9 was 40.5 at a wavelength of 630 nm at 40 ° C. The maximum absorption and absorption wavelengths of the dye (II-7) and the dye (II-8) in the liquid crystal compound (I-1) were 495 nm and 530 nm, respectively.

[Example 7]
718.2 parts of cyclopentanone, 243.6 parts of liquid crystal compound (I-1), 4.06 parts of dye (II-1), 5.58 parts of IRGACURE (registered trademark) 369 (BASF product). Add 3.62 parts of BYK-361N (manufactured by BYK-Chemie), heat and stir at 80 ° C., and then filter using a syringe equipped with a syringe filter (Membrane Solutions, PTFE13045, caliber 0.45 μm). The composition 10 for an anisotropic dye film was obtained.
The composition 10 for an anisotropic dye film is formed on a substrate having a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, formed by a rubbing method) formed on a glass plate by a spin coating method. Then, after heating and drying at 120 ° C. for 2 minutes, the film was cooled to the liquid crystal phase and polymerized at an exposure amount of 500 mj / cm ² (365 nm standard) to obtain an anisotropic dye film 10.
When the obtained anisotropic dye film 10 was held over a commercially available polarizing plate and rotated, it became bright and dark, and it was confirmed that it showed good performance that could be used as a polarizing film.

According to the composition for forming an anisotropic dye film of the present invention, excellent coating properties and excellent optical performance can be realized by using a dye and a liquid crystal compound in a suitable combination.
Since the anisotropic dye film of the present invention is formed by using the composition for forming the anisotropic dye film of the present invention, excellent optical performance can be realized.
Since the optical element of the present invention contains the anisotropic dye film of the present invention, excellent optical performance can be realized.

Claims (9)

An anisotropic dye film forming composition containing a dye and a liquid crystal compound.
The liquid crystal compound contains a compound having a partial structure represented by the following formula (1) (hereinafter, referred to as "liquid crystal compound (1)").
The dye is a composition for forming an anisotropic dye film, which comprises a dye represented by the following formula (D1) (hereinafter, referred to as “dye (D1)”).
^-Cy -X ² -C≡C-X ¹ -... (1)
(In equation (1),
^-Cy- represents a hydrocarbon ring group or a heterocyclic group;
-X ^1- is -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S-,- SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ Represents S- or -SCH _2- ;
-X ^2- is a single bond, -C (= O) O-, -OC (= O)-, -C (= S) O-, -OC (= S)-, -C (= O) S -, -SC (= O)-, -CH ₂ CH _2- , -CH = CH-, -C (= O) NH-, -NHC (= O)-, -CH ₂ O-, -OCH _2- , -CH ₂ S- or -SCH _2- . )
A ¹ -N = N-A ^2- (N = NA ³ ) _n -X ³ ... (D1)
(In equation (D1),
-A ¹ represents a monovalent group of the benzothiazole ring which may have a substituent (except for structures whose terminal is a vinyl group);
-A ^2- and -A ³ --independently have a divalent group of an aromatic hydrocarbon ring which may have a substituent or a divalent of an aromatic heterocycle which may have a substituent. Represents a group;
-X ³ represents a monovalent organic group;
n represents 1, 2, or 3.
When n is 2 or ³ , the plurality of -A3- may be the same or different from each other. ) The composition for forming an anisotropic dye film according to claim 1, wherein —A ³ − is a phenylene group which may have a substituent. The composition for forming an anisotropic dye film according to claim 1 or 2, wherein -A ^2- is a divalent group of an aromatic hydrocarbon ring which may have a substituent. The composition for forming an anisotropic dye film according to any one of claims 1 to 3, wherein —X ³ is —OR ^x or —N (−R ^y ) —R ^x .
However, -R ^x and -R ^y are each independently an alkyl group having 1 to 15 carbon atoms which may have a branch, or a cycloalkyl group or an aryl group having 5 to 14 atoms constituting a ring. Represents;
-R ^x and -R ^y may be integrated to form an alkylene group having 2 to 15 carbon atoms which may have a branch;
The alkyl group having 1 to 15 carbon atoms which may have the branch and the aryl group having 5 to 14 atoms constituting the ring may each have a substituent;
One or more methylene groups contained in the alkyl group having 1 to 15 carbon atoms which may have the branch or the alkylene group having 2 to 15 carbon atoms which may have the branch is ether. The structure may be replaced by an oxygen atom, a thioether sulfur atom, an amine nitrogen atom, a carbonyl group, an ester bond, an amide bond, -CHF-, -CF _2- , -CHCl- or -CCl _2- . ;
The amine nitrogen atom is -NH- or -N ( ^Rz )-;
R ^z represents a linear or branched alkyl group having 1 to 6 carbon atoms. The ratio (r _n1 / r _n2 ) of the number of ring structures (r _n1 ) of the liquid crystal compound (1) to the number of ring structures (r _n2 ) of the dye (D1) is 0.7 to 1. 5. The composition for forming an anisotropic dye film according to any one of claims 1 to 4. The composition for forming an anisotropic dye film according to any one of claims 1 to 5, wherein the dye (D1) contains a maximum absorption wavelength in the wavelength range of 501 nm to 800 nm and 350 nm to 500 nm. 1 The composition for an anisotropic dye film according to any one of 6 to 6. An anisotropic dye film formed by using the composition for forming an anisotropic dye film according to any one of claims 1 to 7. An optical element including the anisotropic dye film according to claim 8.