WO2011024891A1

WO2011024891A1 - Dichroic dye composition, polarizing film, liquid crystal cells and display devices

Info

Publication number: WO2011024891A1
Application number: PCT/JP2010/064468
Authority: WO
Inventors: 亮司後藤; 伸卓岩橋
Original assignee: 富士フイルム株式会社
Priority date: 2009-08-28
Filing date: 2010-08-26
Publication date: 2011-03-03
Also published as: TW201127943A; JP5437744B2; JP2011046904A

Abstract

Provided is a dichroic dye composition which exhibits a high dichroic ratio and excellent orientation properties. The dichroic dye composition contains at least one liquid-crystalline dichroic dye represented by general formula (I): Ar¹-N=N-Ar²-L¹-Ar³-L²-Ar⁴ [wherein Ar¹ to Ar⁴ are each an aromatic hydrocarbon group, an aromatic heterocyclic group or a cyclohexane ring group, each group being optionally substituted; L¹ and L² are each an azo group, an ester group, an inimo group, or a vinylene group, with the proviso that L¹ and L² are not both azo groups].

Description

Dichroic dye composition, polarizing film, liquid crystal cell, and display device

The present invention relates to a dichroic dye composition useful for forming a film for various uses such as a polarizing film, and a polarizing film formed using the same. The present invention also relates to a liquid crystal cell and a liquid crystal display device having the polarizing film.

Conventionally, a polarizing element formed using an organic dichroic dye has been studied.
As an example, like a polarizing element containing iodine, an organic dye having a dichroism (dichroic dye) is dissolved or adsorbed in a polymer material such as polyvinyl alcohol, and the film is formed into a film in one direction. A polarizer prepared by stretching and orienting a dichroic dye has been proposed. However, when produced by this method, there is a problem that a process such as a stretching process is troublesome.
Therefore, other methods have recently attracted attention. As this method, in Non-Patent Document 1, a dichroic dye is oriented on a substrate such as glass or transparent film by utilizing intermolecular interaction of organic dye molecules, and a polarizing film (anisotropic dye film) is formed. There is a method of forming. However, the method described in this document has a problem of heat resistance.

In addition, it has also been proposed to produce a polarizer by a wet film forming method in which a dichroic dye is oriented on a substrate such as glass or a transparent film using intermolecular interaction of organic dye molecules. Examples of the process in the wet film forming method include a method for depositing and orienting a dye on a substrate and a method for controlling the orientation. Patent Documents 1 to 3 propose materials suitable for the above process. In addition, as a material suitable for the process, Patent Document 4 proposes a dye represented by (chromogen) (SO ₃ M) n.

On the other hand, in order to reduce scattered light caused by depolarization of linearly polarized light incident on a color filter layer disposed in a liquid crystal cell, it has been proposed to dispose a polarizing layer in the liquid crystal cell (for example, Patent Documents 5 and 6).

Japanese Patent Laid-Open No. 2002-180052 JP-T-2002-528758 JP 2002-338838 A JP-T 8-511109 JP-A-10-161105 JP 2008-90317 A

In recent years, various display devices and the like have been required to be thin, and a polarizing film used therefor is also required to achieve a high degree of polarization with a thin film thickness. In particular, this characteristic is strongly required for the polarizing layer disposed in the cell. For this purpose, a dichroic dye composition that exhibits a high dichroic ratio and good orientation is effective.
An object of the present invention is to provide a dichroic dye composition having a high dichroic ratio and good orientation.
Another object of the present invention is to provide a dichroic dye composition useful for producing a polarizing film capable of achieving a high degree of polarization with a thin film thickness.
Moreover, this invention makes it a subject to provide a dichroic dye composition useful for formation of the polarizing film arrange | positioned in a liquid crystal cell.
Another object of the present invention is to provide a polarizing film capable of achieving a high degree of polarization with a thin film thickness, a liquid crystal cell having the polarizing film, and a display device.

Means for solving the above problems are as follows.
[1] Dichroic dye composition containing at least one dichroic dye having liquid crystallinity represented by the following general formula (I):

In the formula, each of Ar ¹ to Ar ⁴ represents an aromatic hydrocarbon group, an aromatic heterocyclic group and a cyclohexane ring group, each of which may have a substituent; L ¹ and L ² are an azo group and an ester group, respectively. Represents an imino group or a vinylene group, provided that L ¹ and L ² are not both azo groups.

[2] The dichroic dye composition according to [1] which does not substantially contain a liquid crystalline non-colored material.
[3] The dichroic dye composition of [1] or [2], wherein at least one of the dichroic dyes represented by the general formula (I) is a compound represented by the following general formula (II): :

Wherein, L ¹¹ and L ¹² are each, azo group, an ester group, an imino group, or a vinylene group, provided that never L ¹¹ and L ¹² is an azo group together; R ¹¹ ~ R ¹⁵ each Represents a hydrogen atom or a substituent, and R ¹¹ and R ¹³ may form a ring with each other; A ¹ represents a substituted or unsubstituted carbon atom or a nitrogen atom.

[4] It contains at least two dichroic dyes having liquid crystallinity represented by the general formula (II), and at least one of the two or more dichroic dyes is represented by the formula (II) The dichroic dye composition of [3], wherein L ¹¹ is a compound having an azo group.
[5] The dichroism of any one of [1] to [4], wherein at least one dichroic dye represented by the general formula (I) is a compound represented by the following general formula (III): Dye composition:

In the formula, L ²¹ represents an ester group, an imino group, or a vinylene group; L ²² represents an azo group, an ester group, an imino group, or a vinylene group; R ²¹ to R ²⁵ each represent a hydrogen atom or a substituent. R ²¹ and R ²³ may form a ring with each other; A ² represents a substituted or unsubstituted carbon atom or a nitrogen atom.

[6] The dichroism of any one of [1] to [5], wherein at least one of the dichroic dyes represented by the general formula (I) is a compound represented by the following general formula (IV) Dye composition:

Represents wherein, L ³¹ is an imino group, or a vinylene group; R ³¹ ~ R ³⁵ each represents a hydrogen atom or a substituent, R ³¹ and R ³³ may form a mutually ring; A ³ is a substituted Alternatively, it represents an unsubstituted carbon atom or a nitrogen atom.

[7] R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ and R ³² are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R ¹³ , R ²³ and R ³³ are each R ¹⁴ , R ²⁴ , R ³⁴ , R ¹⁵ , R ^25, and R ³⁵ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a plurality of carbon atoms having 1 to 6 carbon atoms. An alkoxy group which may contain a hetero atom; A ¹ , A ² and A ³ may contain a nitrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a plurality of hetero atoms The dichroic dye composition according to any one of [4] to [6], which is a carbon atom substituted with an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a substituted amino group.
[8] The two colors according to any one of [1] to [7], containing at least one dichroic dye having liquid crystallinity represented by the general formula (I) as a magenta dye and / or a yellow dye Pigment composition.
[9] The dichroic dye composition according to [8] containing at least one compound represented by formula (III) as a yellow dye.
[10] The dichroic dye composition according to [8] or [9], which contains at least one compound represented by formula (IV) as a magenta dye.
[11] The dichroic dye composition according to any one of [1] to [10], further containing at least one dichroic azo dye having liquid crystallinity as a cyan dye.
[12] A polarizing film comprising the dichroic dye composition according to any one of [1] to [11].
[13] The polarizing film of [12] formed by coating.
[14] The polarizing film according to [13], wherein transmitted light when a C light source is used as the light source satisfies 0.28 <x <0.36 and 0.28 <y <0.36 in the xy chromaticity diagram .
[15] A liquid crystal cell having a pair of substrates, a liquid crystal layer, a color filter layer, and a polarizing film of any one of [12] to [14] disposed therebetween.
[16] The liquid crystal cell according to [15], wherein the polarizing film is provided between the color filter layer and the liquid crystal layer.
[17] A display device having the polarizing film of any one of [12] to [14].
[18] A liquid crystal display device having the liquid crystal cell of [15] or [16].

[19] Dichroic dye having liquid crystallinity represented by the following general formula (III):

In the formula, L ²¹ represents an ester group, an imino group, or a vinylene group; L ²² represents an azo group, an ester group, an imino group, or a vinylene group; R ¹¹ to R ¹⁵ each represent a hydrogen atom or a substituent. R ¹¹ and R ¹³ may form a ring with each other; A ² represents a substituted or unsubstituted carbon atom or a nitrogen atom.

[20] R ²¹ and R ²² are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R ²³ is a hydrogen atom; R ²⁴ and R ²⁵ are a hydrogen atom or a carbon atom, respectively. An alkyl group having 1 to 6 atoms or an alkoxy group having 1 to 6 carbon atoms which may contain a plurality of heteroatoms; A ² is a nitrogen atom or a substituted or unsubstituted group having 1 to 6 carbon atoms; [19] The dichroic dye according to [19], which is a substituted alkyl group, a carbon atom substituted with an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a substituted amino group, which may contain a plurality of heteroatoms.

[21] A dichroic dye having liquid crystallinity represented by the following general formula (IV):

[22] R ³¹ and R ³² are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R ³³ is a hydrogen atom; R ³⁴ and R ³⁵ are a hydrogen atom and a carbon atom, respectively. An alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms which may contain a plurality of heteroatoms; A ³ is a nitrogen atom, or substituted or unsubstituted having 1 to 6 carbon atoms [21] The dichroic dye of [21], which is a carbon atom substituted with an alkyl group, a plurality of heteroatoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a substituted amino group.

The dichroic dye composition of the present invention exhibits a high dichroic ratio and good orientation. Therefore, according to the dichroic dye composition of the present invention, a polarizing film capable of achieving a high degree of polarization with a thin film thickness can be provided. Moreover, according to this invention, the dichroic dye composition useful for formation of the polarizing film arrange | positioned in a liquid crystal cell can be provided. Furthermore, according to the present invention, it is possible to provide a polarizing film capable of achieving a high degree of polarization with a thin film thickness, a liquid crystal cell having the polarizing film, and a liquid crystal display device.

Hereinafter, the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
1. Dichroic dye composition -1 Dichroic dye The present invention relates to a dichroic dye composition containing at least one dichroic dye having liquid crystallinity represented by the following general formula (I).

In the above general formula, Ar ¹ is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent; it may be a phenyl group or a naphthyl group which may have a substituent. Is more preferable; it is more preferably a phenyl group which may have a substituent.
Examples of the substituent of Ar ¹ include a substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, For example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, an anilino group, etc.), a hydroxy group, an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, especially Preferably, it has 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group); a substituted or unsubstituted amino group is more preferable. In particular, Ar ¹ is preferably a phenyl group having a substituted or unsubstituted amino group at the para position relative to the azo group, and is preferably unsubstituted except for the para position.

In the above general formula, Ar ² is preferably an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent; an phenylene group or a naphthylene group which may have a substituent is more preferable; A phenylene group which may have a substituent is more preferable.
Examples of the substituent that Ar ² has include an optionally substituted alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms). Groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl , A cyclohexyl group, etc.), an alkoxy group which may contain a plurality of heteroatoms (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, the alkoxy group containing a methoxy group, an ethoxy group, a butoxy group heteroatoms _{_{such, -. (OCH 2 CH 2}} ) represented by _n OX N represents an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and a hydroxy group are preferable; among them, an alkyl group and an alkoxy group which may contain a plurality of heteroatoms are more preferable. In particular, Ar ² is preferably an unsubstituted phenylene group or a phenylene group having an alkyl group.

In the above general formula, Ar ³ is preferably an aromatic hydrocarbon group, aromatic heterocyclic group or cyclohexane ring group which may have a substituent; a phenylene group or naphthylene which may have a substituent; A group is more preferable; a phenylene group which may have a substituent is more preferable. Examples of substituents which Ar ² has are the same as examples of the substituent Ar ² has preferred ranges are also the same.

In the above general formula, Ar ⁴ is preferably an aromatic hydrocarbon group, an aromatic heterocyclic group or a cyclohexane ring group which may have a substituent; a phenyl group or a naphthyl group which may have a substituent Or a pyridyl group is more preferable; a phenyl group or a pyridyl group which may have a substituent is more preferable.
Examples of the substituent that Ar ⁴ has include an alkyl group which may have a substituent (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms). Groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl , A cyclohexyl group, etc.), an alkenyl group (preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as a vinyl group, an allyl group, etc. , 2-butenyl group, 3-pentenyl group, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferred) Or an alkynyl group having 2 to 8 carbon atoms, such as a propargyl group or 3-pentynyl group, or an aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably Is an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, a 2,6-diethylphenyl group, a 3,5-ditrifluoromethylphenyl group, a naphthyl group, and a biphenyl group), substituted or unsubstituted Amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, such as an unsubstituted amino group, a methylamino group, a dimethylamino group, A diethylamino group, an anilino group, etc.), an alkoxy group which may contain a plurality of heteroatoms (preferably having a carbon number of 1 to 20, more preferably The number of carbon atoms is 1 to 10, particularly preferably 1 to 6, and includes, for example, a methoxy group, an ethoxy group, a butoxy group, etc. As an alkoxy group containing a hetero atom, for example, — (OCH ₂ CH ₂ ) an oligoethyleneoxy group represented by _n OX, _n represents an integer of 1 to 10, preferably 1 to 6, more preferably 1 to 3, and X is a hydrogen atom or a carbon number of 1 And an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group). Acyloxy groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms such as acetoxy group, Oxy group and the like), acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 6 carbon atoms, such as acetylamino group and benzoylamino group). An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, such as a methoxycarbonylamino group), aryloxy A carbonylamino group (preferably having a carbon number of 7 to 20, more preferably a carbon number of 7 to 16, particularly preferably a carbon number of 7 to 12, such as a phenyloxycarbonylamino group), a sulfonylamino group (preferably Has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. For example, methanesulfonylamino group, benzenesulfonylamino group, etc.), sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, A sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, a phenylsulfamoyl group, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably carbon atoms). For example, an unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group and the like, an alkylthio group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 10, particularly preferably 1 to 6 carbon atoms, such as methylthio group, ethyl An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as a phenylthio group), sulfonyl A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms such as mesyl group and tosyl group), sulfinyl group (preferably 1 to 20, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include methanesulfinyl groups and benzenesulfinyl groups), ureido groups (preferably having 1 to 20 carbon atoms, More preferably, it has 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, and examples thereof include an unsubstituted ureido group, a methylureido group, and a phenylurea. A phosphoric acid amide group (preferably having a carbon number of 1 to 20, more preferably a carbon number of 1 to 10, particularly preferably a carbon number of 1 to 6, such as a diethylphosphoric acid amide group, phenyl Phosphoric acid amide group etc.), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group Group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, Imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzil A thiazolyl group), a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms. Phenylsilyl group and the like are preferred; an alkyl group, an aryl group, an alkoxy group that may contain a plurality of heteroatoms, an alkoxycarbonyl group, an acyloxy group, a halogen atom, a cyano group, a nitro group, and a substituted amino group. More preferably; an alkyl group, an alkoxy group optionally containing a plurality of heteroatoms, a cyano group, and a substituted amino group are more preferable. These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.
In particular, Ar ⁴ is an unsubstituted pyridyl group or a phenyl having an alkyl group, an alkoxy group that may contain a plurality of heteroatoms, a cyano group, or a substituted amino group at the para position relative to L ² . A group is preferred.

Note that the compound represented by the above general formula may have a polymerizable group as a substituent. It is preferable to have a polymerizable group because the hardening property is improved. As a polymerizable group. Examples of the polymerizable group include an unsaturated polymerizable group, an epoxy group, and an aziridinyl group, preferably an unsaturated polymerizable group, and particularly preferably an ethylenically unsaturated polymerizable group. Examples of the ethylenically unsaturated polymerizable group include acryloyl group and methacryloyl group.
The polymerizable group is preferably located at the end, ie, preferably present as a substituent for Ar ¹ and / or Ar ⁴ .

In the above general formula, L ¹ and L ² are each an azo group (—N═N—), an ester group (—C (═O) O— or —OC (═O) —), an imino group (—CH═ N- or -N = CH-) and a vinylene group (-CH = CH-). L ¹ is preferably —N═N—, —C (═O) O—, —OC (═O) —, or —CH═N—; —N═N—, —C (═O) O— Or —CH═N— is more preferred. L ² is preferably —N═N—, —C (═O) O—, —OC (═O) —, —CH═N—, or —CH═CH—; —N═N—, —C (═O) O— or —CH═N— is more preferred. However, L ¹ and L ² are not both azo groups.
Preferred examples of the combination of L ¹ and L ² include (L ¹ / L ² ) = (— N═N — / — C (═O) O—), (—N═N — / — CH═N—). ), (—N═N — / — CH═CH—), (—C (═O) O — / — N═N—), (—C (═O) O — / — CH═CH—), And (—CH═N — / — N═N—); (L ¹ / L ² ) = (— N═N — / — CH═N—), and (—C (═O) O— / -N = N-) is more preferable.

Examples of the compound represented by the general formula (I) include a compound represented by the following general formula (II).

In the general formula (II), R ¹¹ and R ¹² are each a hydrogen atom or an optionally substituted alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably An alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group , A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and the like.
R ¹³ is the same as the preferable substituent of Ar ^{2 in} the general formula (I), and may form a ring with R ^11, and a 5-membered ring and a 6-membered ring containing a nitrogen atom are preferable.
R ¹⁴ and R ¹⁵ are respectively the same as the preferred substituents for Ar ² and Ar ^{3 in} the general formula (I).

In the general formula (II), preferred examples of L ¹¹ and L ¹² and preferred examples of the combination thereof are preferred examples of L ¹ and L ^{2 in} the general formula (I) and preferred examples of the combination thereof. It is the same.

Further, examples of the compound represented by the general formula (I) include compounds represented by the following general formulas (III) and (IV). A compound represented by the following general formula (III) will be used as a yellow dye, and a compound represented by the following general formula (IV) will be used as a magenta dye.

In the general formula (III), A ² represents a substituted or unsubstituted carbon atom or a nitrogen atom, and as a substituent when A ² represents a carbon atom, preferred substitution of Ar ^{4 in} the general formula (I) Same as the group.
In the general formula (III), preferred examples of L ²¹ and L ²² and preferred examples of the combination thereof are preferred examples of L ¹ and L ^{2 in} the general formula (I) and preferred examples of the combination thereof. It is the same.
In the compound of formula (III), L ²¹ cannot be an azo group. By making L ²¹ other than an azo group, the absorption maximum wavelength of the dye can be shortened. Even if L ²² is an azo group, the effect is the same.

In general formula (IV), the preferred ranges of R ³¹ to R ³⁵ are the same as R ¹¹ to R ^{15 in} general formula (II), respectively. R ³⁴ is located at a position below and is an alkyl group of C ₁ ~ _5, the solubility is improved, which is preferable.

In the general formula (IV), L ³¹ represents an imino group (—CH═N— or —N═CH—) or a vinylene group (—CH═CH—), and a vinylene group (—CH═N—) Is preferred. When L ³¹ is an imino group or vinylene group, the dichroic ratio becomes higher. Specifically, for example, the dichroic ratio is higher than that of a compound in which L ³¹ is an ester group.
In the general formula (IV), A ³ represents a substituted or unsubstituted carbon atom or a nitrogen atom. As the substituent when A ³ represents a carbon atom, preferred substitution of Ar ^{4 in} the general formula (I) Same as the group.

In the general formulas (II) to (IV), R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ and R ³² are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; ¹³ , R ²³ and R ³³ are each a hydrogen atom; R ¹⁴ , R ²⁴ , R ³⁴ , R ¹⁵ , R ²⁵ and R ³⁵ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or carbon An alkoxy group having 1 to 6 atoms which may contain a plurality of heteroatoms; A ¹ , A ² and A ³ are nitrogen atoms, or substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms; A carbon atom substituted with an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a substituted amino group, which may contain a plurality of heteroatoms is preferable.
When R ¹¹ , R ¹² , R ²¹ , R ²² , R ³¹ and R ³² are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, examples of the substituent of the alkyl group include polymerizable Groups, for example, acryloyl groups and methacryloyl groups.
When A ¹ , A ² and A ³ are carbon atoms substituted with a substituted amino group, examples of the amino group substituent include substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms. Examples of the substituent of the alkyl group include a polymerizable group, for example, an acryloyl group and a methacryloyl group.

Examples of the dichroic dye represented by the general formula (I) that can be used in the present invention are shown below, but are not limited thereto.

There is no particular limitation on the method for producing the compounds represented by the general formulas (I) to (IV). For example, it can be easily synthesized according to the method described in Journal of Materials Chemistry (1999), 9 (11), 2755-2863.
An example of a method for producing a compound of the formula (IV) wherein L ³¹ is an imino group is as follows.

An example of the method for producing the compound of the formula (IV), wherein L ^{31 in} the formula is an ester group, is as follows.

In the above two reaction formulas, R represents a substituent.
By using compounds in which R ³¹ to R ³⁵ are hydrogen atoms or various substituents as raw materials, various compounds represented by the formula (IV) can be produced.
Furthermore, by referring to the following production example of the compound of formula (III), a compound in which A ³ is a nitrogen atom can be produced in the same manner.

An example of the method for producing the compound of the formula (III), wherein A ² is a nitrogen atom, is as follows.

By using compounds in which R ²¹ to R ²⁵ are hydrogen atoms or various substituents as raw materials, various compounds represented by the formula (III) can be produced.
In the above production method, a compound in which L ²¹ is an ester group is produced. By replacing 4-aminobenzoic acid and cresol used as raw materials with 4-aminobenzaldehyde and toluidine, respectively, A compound in which ²¹ is an imino group can be similarly produced.
Furthermore, by referring to the production examples of the compound of the formula (IV), a compound in which A ² is a substituted or unsubstituted carbon atom can be produced in the same manner.

The dichroic dye represented by the general formula (I) used in the present invention exhibits liquid crystallinity. The compound preferably exhibits a nematic liquid crystal phase, preferably a compound exhibiting a nematic liquid crystal phase at a temperature of 10 to 300 ° C., more preferably at a temperature of 100 to 250 ° C.

In the composition of the present invention, the content of the one or more dichroic dyes represented by the general formula (I) is not particularly limited. Depending on the application, the preferred range will be determined. In an embodiment used for forming a film that requires high absorption anisotropy such as a polarizing film, one or more dichroic dyes represented by the general formula (I) are included in the composition. It is preferably 10 to 90% by mass, particularly preferably 30 to 80% by mass, based on the total mass of all the dyes. The content of the one or more dichroic dyes represented by the general formula (I) in the total solid content excluding the solvent is preferably 20% by mass or more, and preferably 30% by mass or more. Particularly preferred.
In the embodiment in which the composition is prepared as a solution, the concentration of the total solid content is preferably 0.1 to 10% by mass, and particularly preferably 0.5 to 5% by mass.

1. -2 Additive The dichroic dye composition of the present invention may contain one or more additives together with one or more dichroic dyes represented by the general formula (I). However, it is preferable that substantially no liquid crystalline compounds (low molecular liquid crystalline compounds and high molecular liquid crystalline compounds) are contained as materials other than coloring materials such as pigments. The dichroic dye composition of the present invention includes a liquid crystal material as a host and a dichroic dye as a guest, and is used as an aspect in which the dichroic dye is aligned with the alignment of the liquid crystal material. However, it is preferable to use the dichroic dye as an embodiment in which the dichroic dye is aligned by its liquid crystallinity. Compared with the GH type, it is preferable in that a higher dichroic ratio can be achieved. In the case of a GH type polarizer, the composition used for formation usually contains 80% by mass or more of a liquid crystal compound as a host in the total solid content, and the content of the guest dye is about 5 to 15% by mass. A preferred embodiment of the present invention is a non-GH embodiment that does not substantially contain a liquid crystalline non-colored material. Specifically, the proportion of the liquid crystalline non-colored material in the composition is 30% by mass or less. The aspect which is is preferable, More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less. It is particularly preferable that no liquid crystalline non-colored material is contained.

Hereinafter, various additives that can be used in the dichroic dye composition of the present invention will be described.
A non-liquid crystalline polyfunctional monomer having a radical polymerizable group;
The composition of the present invention preferably contains a non-liquid crystalline polyfunctional monomer having a radical polymerizable group.
In the present invention, the non-liquid crystalline polyfunctional monomer having a radical polymerizable group refers to a polyfunctional monomer in which a growth active species undergoes a radical polymerization reaction. This polyfunctional monomer is preferably a polyfunctional monomer having two or more double bonds in the molecule, particularly preferably an ethylenic (aliphatic) unsaturated double bond, specifically, Polyfunctional monomers having functional groups such as alkenes, dienes, acrylates, methacrylates, diesters of unsaturated polycarboxylic acids, amides of α, β-unsaturated carboxylic acids, unsaturated nitriles, styrene and derivatives thereof, vinyl esters, vinyl ethers, etc. Can be mentioned. The number of double bonds in the molecule is preferably 2 to 20, more preferably 2 to 15, and most preferably 2 to 6. The polyfunctional monomer is preferably an ester of a polyol having two or more hydroxyl groups in the molecule and an unsaturated fatty acid. Examples of unsaturated fatty acids include acrylic acid, methacrylic acid, maleic acid and itaconic acid, with acrylic acid and methacrylic acid being preferred. The polyol having 4 or more hydroxyl groups in the molecule is preferably a tetrahydric or higher alcohol or a trihydric or higher alcohol oligomer. The oligomer has a molecular structure in which polyhydric alcohols are linked by an ether bond, an ester bond or a urethane bond. Oligomers having a molecular structure in which polyhydric alcohols are linked by ether bonds are preferred.
The polyfunctional monomer is particularly preferably soluble in an organic solvent.
An example of such a monomer is a compound having a boiling point of 100 ° C. or higher at normal pressure.

Among the polyfunctional monomers described above, examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate and the like are listed, and commercially available products thereof include, for example, Aronix M-210, M-240, M-6200 (Toa Synthetic Chemical Industry Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.), Biscote 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.), etc. Is mentioned.

Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, pentaerythritol tetra (meth) acrylate, Examples thereof include dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, and examples of commercially available products thereof include Aronix M-309, M-400, M-405, M-450, and the like. M-7100, M-8030, M-8060 (all trade names, manufactured by Toa Gosei Chemical Industry Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (both Product name, manufactured by Nippon Kayaku Co., Ltd.), BISCOAT 295, the 300, the 360, the same GPT, the same 3PA, the 400 (trade name, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like.

As examples of further monomers and oligomers, bifunctional or trifunctional or higher (meth) acrylates include, for example, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane diacrylate. , Neopentyl glycol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyl) Oxyethyl) cyanurate, glycerin tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, dipen Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; polyfunctional acrylates and polyfunctionals such as those obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as trimethylolpropane and glycerin and then (meth) acrylated Methacrylate; Poly (meth) acrylate of polyether-based polyol, poly (meth) acrylate of polyester-based polyol, and poly (meth) acrylate of polyurethane-based polyol.

Monomers composed of an ester of polyol and acrylic acid are commercially available from Mitsubishi Rayon Co., Ltd. (trade name: Diabeam UK-4154) and Nippon Kayaku Co., Ltd. (trade name: KYARAD / DPHA, SR355).

These bifunctional or trifunctional or higher functional (meth) acrylates may be used alone or in combination, and may be used in combination with monofunctional (meth) acrylate.

Examples of monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 2- (meth) acryloyloxyethyl. -2-Hydroxypropyl phthalate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, ethylene glycol (meth) acrylate, and the like. -101, M-111, M-114 (manufactured by Toa Gosei Chemical Co., Ltd.), KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku Co., Ltd.), Biscote 158, 2311 (large) Made Organic Chemical Industry Co., Ltd.) and the like.

As will be described later, when preparing a polarizer, it is preferable to fix the alignment state of the nematic liquid crystalline dye, and as a means for fixing, the alignment of the dye is fixed using a polymerization reaction. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator.

In the composition of the present invention, the total content of the pigment and the non-liquid crystalline polymerizable polyfunctional monomer in the total solid content excluding the solvent is preferably 50% by mass or more, particularly preferably 70% by mass or more.

Polymerization initiator:
In order to cure the composition containing the radical polymerizable polyfunctional monomer, the composition of the present invention preferably contains a polymerization initiator.
As the polymerization initiator, known ones can be suitably used according to photopolymerization and thermal polymerization. For example, α-carbonyl compounds (US Pat. Nos. 2,367,661 and 2,367,670) can be used as examples of the photopolymerization initiator. ), Acyloin ether (described in U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compound (described in U.S. Pat. No. 2,722,512), polynuclear quinone compound (U.S. Pat. Nos. 3,046,127 and 2,951,758). No. 3), a combination of a triarylimidazole dimer and p-aminophenyl ketone (described in US Pat. No. 3,549,367), an acridine compound and a phenazine compound (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850) Oxadiazole compounds (US Pat. No. 42129) No. 70).

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by mass, and more preferably 1 to 10% by mass, based on the total solid content excluding the solvent.
Examples of the photopolymerization initiator, the amount of the photopolymerization initiator used, and the value of the light irradiation energy for the polymerization are described in paragraphs [0050] to [0051] of JP 2001-91741 A. Applicable.

In the composition of the present invention, an organic solvent or an arbitrary additive can be blended and used in addition to the above-mentioned pigment, non-liquid crystalline polyfunctional monomer, and polymerization initiator. Examples of the additive include an anti-wind unevenness agent, an anti-repellency agent, an additive for controlling the tilt angle of the alignment film (the tilt angle of the liquid crystalline dye at the light absorption anisotropic film / alignment film interface), air Additives for controlling the tilt angle of the interface (the tilt angle of the dye at the polarizer film / air interface), saccharides, agents having at least one of antifungal, antibacterial and antibacterial functions, non-liquid crystalline binder polymers Etc. Hereinafter, each additive will be described.

Wind unevenness prevention agent:
When the composition of the present invention is prepared as a coating solution to form a film coated on the surface, a material for preventing wind unevenness during coating, an anti-wind uneven agent, is added to the composition. May be. Generally, a fluorine-based polymer is used as the wind unevenness preventing agent. There is no restriction | limiting in particular as a fluorine-type polymer to be used unless the tilt angle change and orientation of a pigment | dye are inhibited significantly. Examples of fluoropolymers that can be used as wind unevenness inhibitors are described in JP-A No. 2004-198511, JP-A No. 4190275, JP-A No. 2004-333852, and JP-A No. 2005-206638. By using the pigment and the fluorine-based polymer in combination, an image with high display quality can be displayed without causing unevenness. Furthermore, applicability such as repelling is improved. In order not to disturb the alignment of the liquid crystalline dye, the amount of the fluorine-based polymer used for the purpose of preventing wind unevenness is preferably in the range of 0.1 to 10% by mass with respect to the liquid crystalline dye. More preferably, it is in the range of 5 to 10% by mass, and still more preferably in the range of 0.5 to 5% by mass.

Anti-repellent agent:
When the composition of the present invention is prepared as a coating solution to form a film coated on the surface, a material for preventing repelling during coating, a repelling agent, may be added to the composition. . Generally, a polymer is used as the repellency inhibitor. The polymer to be used is not particularly limited as long as it is compatible with the liquid crystalline dye and does not significantly inhibit the change in the tilt angle or orientation of the dye. Examples of polymers that can be used as repellency inhibitors are described in JP-A-8-95030, and specific examples of particularly preferred polymers include cellulose esters. Examples of cellulose esters include cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. In order not to inhibit the orientation of the dye, the amount of the polymer used for the purpose of preventing repellency is generally preferably in the range of 0.1 to 10% by weight, preferably 0.1 to 8% by weight with respect to the liquid crystalline dye. % Is more preferable, and a range of 0.1 to 5% by mass is even more preferable.

Alignment film tilt angle control agent:
It is preferable to add an additive for controlling the tilt angle of the alignment film and an alignment film tilt angle control agent to the composition of the present invention. Examples of the alignment film tilt angle control agent include compounds having both a polar group and a nonpolar group in the molecule. Examples of compounds having both polar and nonpolar groups in the molecule include R ⁰ —OH, R ⁰ —COOH, R ⁰ —O—R ⁰ , R ⁰ —NH ₂ , R ⁰ —NH—R ^0. , R ⁰ —SH, R ⁰ —S—R ⁰ , R ⁰ —CO—R ⁰ , R ⁰ —COO—R ⁰ , R ⁰ —CONH—R ⁰ , R ⁰ —CONHCO—R ⁰ , R ⁰ —SO ₃ H, R ⁰ —SO ₃ —R ⁰ , R ⁰ —SO ₂ NH—R ⁰ , R ⁰ —SO ₂ NHSO ₂ —R ⁰ , R ⁰ —C═N—R ⁰ , HO—P (—OR ⁰ ) ₂ , (HO—) ₂ PO—OR ⁰ , P (—OR ⁰ ) ₃ , HO—PO (—OR ⁰ ) ₂ , (HO—) ₂ PO—OR ⁰ , PO (—OR ⁰ ) ₃ , R ^0- NO ₂ and R ⁰ -CN and their organic salts are included. In the formulas, R ⁰ is a non-polar group, if R ⁰ is plural, each R ⁰ is may be the same or different. The Here, as the organic salt, in addition to the organic salt of the above compound (for example, ammonium salt, carboxylate, sulfonate, etc.), pyridinium salt and the like can be preferably employed. Among the compounds having both polar groups and nonpolar groups in the molecule, R ⁰ —OH, R ⁰ —COOH, R ⁰ —O—R ⁰ , R ⁰ —NH ₂ , R ⁰ —SO ₃ H, HO —PO (—OR ⁰ ) ₂ , (HO—) ₂ PO—OR ⁰ , PO (—OR ⁰ ) ₃ or an organic salt thereof is preferred.

Examples of the nonpolar group R 2 ^O include an alkyl group (preferably a linear, branched, or cyclic substituted or unsubstituted alkyl group having 1 to 30 carbon atoms) and an alkenyl group (preferably a linear chain having 1 to 30 carbon atoms). Branched, cyclic substituted or unsubstituted alkenyl groups), alkynyl groups (preferably linear, branched, cyclic substituted or unsubstituted alkenyl groups having 1 to 30 carbon atoms), aryl groups (preferably having 6 carbon atoms). Examples thereof include ˜30 substituted or unsubstituted aryl groups) and silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms). These nonpolar groups may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (a cycloalkenyl group and a bicycloalkenyl group). Alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonyl Mino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group Preferred examples include carbamoyl group, arylazo group, heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group and the like.

By adding the alignment film tilt control agent to the composition of the present invention and orienting the molecules of the dichroic dye in the presence of the alignment film tilt control agent, the tilt angle of the dye molecules at the alignment film side interface can be reduced. Can be adjusted. In general, the addition amount of the alignment film tilt angle control agent is preferably 0.0001% by mass to 30% by mass, and preferably 0.001% by mass to 20% by mass with respect to the mass of the dichroic dye. More preferably, it is 0.005 to 10% by mass. In the present invention, the alignment film tilt control agent described in JP-A-2006-58801 can be used.

Air interface tilt angle control agent:
It is preferable to add an additive for controlling the tilt angle at the air interface and an air interface tilt angle control agent to the composition of the present invention. An example of the air interface tilt angle control agent is a horizontal alignment agent. As the horizontal alignment agent,
(1) a fluoroaliphatic group-containing compound represented by the following general formula (10); or
(2) selected from the group consisting of polymerized units of fluoroaliphatic group-containing monomers represented by general formula (11) or general formula (12) and polymerized units of amide group-containing monomers represented by general formula (13) A polymer comprising at least one polymerized unit;
It is.
First, (1) the fluoroaliphatic group-containing compound represented by the following general formula (10) will be described.

In the formula, R ⁵¹ , R ⁵² and R ⁵³ each independently represents an alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal, and X ¹¹ , X ²² and X ³³ each independently represent —NH—, Represents —O— or —S—, and m11, m22 and m33 each independently represents an integer of 1 to 3.

Each of the substituents represented by R ⁵¹ , R ⁵² and R ⁵³ is an alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal, and may be linear or branched. The number of carbon atoms is preferably 4 to 20, more preferably 4 to 16, and particularly preferably 6 to 16. The alkoxy group having a CF ₃ group or a CF ₂ H group at the terminal is an alkoxy group in which part or all of the hydrogen atoms contained in the alkoxy group are substituted with fluorine atoms. 50% or more of the hydrogen atoms in the alkoxy group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and particularly preferably 70% or more are substituted. Examples of alkoxy groups having a CF ₃ group or a CF ₂ H group at the ends represented by R ⁵¹ , R ⁵² and R ⁵³ are shown below.

R1: n-C ₈ F ₁₇ —O—
R2: n—C ₆ F ₁₃ —O—
R3: nC ₄ F ₉ —O—
R4: nC ₈ F ₁₇ — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —O—
R5: nC ₆ F ₁₃ — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —O—
R6: nC ₄ F ₉ — (CH ₂ ) ₂ —O— (CH ₂ ) ₂ —O—
R7: nC ₈ F ₁₇ — (CH ₂ ) ₃ —O—
R8: nC ₆ F ₁₃ — (CH ₂ ) ₃ —O—
R9: nC ₄ F ₉ — (CH ₂ ) ₃ —O—
R10: H— (CF ₂ ) ₈ —O—
R11: H— (CF ₂ ) ₆ —O—
R12: H— (CF ₂ ) ₄ —O—
R13: H— (CF ₂ ) ₈ — (CH ₂ ) —O—
R14: H— (CF ₂ ) ₆ — (CH ₂ ) —O—
R15: H— (CF ₂ ) ₄ — (CH ₂ ) —O—
R16: H— (CF ₂ ) ₈ — (CH ₂ ) —O— (CH ₂ ) ₂ —O—
R17: H— (CF ₂ ) ₆ — (CH ₂ ) —O— (CH ₂ ) ₂ —O—
R18: H— (CF ₂ ) ₄ — (CH ₂ ) —O— (CH ₂ ) ₂ —O—

In the general formula (10), X ¹¹ , X ²² and X ³³ each preferably represent —NH— or —O—, and most preferably represents —NH—. m ¹¹ , m ²² and m ³³ are each preferably 2.

Specific examples of the compound represented by the general formula (10) are shown below, but the compound used in the present invention is not limited thereto.

Next, (2) a group consisting of a polymerization unit of a fluoroaliphatic group-containing monomer represented by general formula (11) or general formula (12) and a polymerization unit of an amide group-containing monomer represented by general formula (13) A polymer containing at least one polymer unit selected from the following will be described.

In the formula, R ⁶¹ represents a hydrogen atom, a halogen atom or a methyl group, L ⁶¹ represents a divalent linking group, and m1 represents an integer of 1 or more and 18 or less.

Wherein, R ⁶² represents a hydrogen atom, a halogen atom or a methyl group, L ⁶² represents a divalent linking group, n1 represents an integer of 1 to 18.

In the formula, R ⁷³ represents a hydrogen atom, a halogen atom or a methyl group, and R ⁷¹ and R ⁷² are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a carbon number. 1 to 20 heterocyclic groups are represented. R ⁷¹ and R ⁷² may be connected to each other to form a heterocyclic ring.

In the general formula (11), R ⁶¹ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. L ⁶¹ represents a divalent linking group, m1 represents an integer of 1 to 18, more preferably 2 to 12, still more preferably 4 to 8, and most preferably 4 or 6.

In the general formula (12), R ⁶² represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. L ⁶² represents a divalent linking group, n1 represents an integer of 1 to 18, more preferably 2 to 12, still more preferably 4 to 8, and most preferably 4 or 6.

L ⁶¹ and L ⁶² are not limited as long as they are each independently a divalent substituent, but a structure represented by the following general formula (14) is more preferable. Here, (a) shows the position bonded to the double bond side, and (b) shows the position bonded to the fluoroaliphatic group side.
Formula (14): (a) -X 10 -R 20 - (b)
In the general formula (14), X ¹⁰ is a single bond or * -COO-**, * -COS-**, * -O.
Represents a divalent linking group represented by CO-**, * -CON (R ²¹ )-**, * -O-**. Here, * represents a position bonded to the double bond side, and ** represents a position bonded to R ²⁰ .
R ²⁰ represents an optionally substituted polymethylene group (eg, methylene group, ethylene group, trimethylene group), an optionally substituted phenylene group (eg, o-phenylene group, m-phenylene group). , P-phenylene group, and the like, and a group that can be formed by any combination thereof. Among them, a polymethylene group is more preferable, and among the polymethylene groups, a methylene group, an ethylene group, a trimethylene group, and a tetramethylene group are preferable, and a methylene group and an ethylene group are still more preferable.

R ²¹ represents a hydrogen atom or an alkyl group which may have a substituent having 1 to 8 carbon atoms, or an aryl group which may have a substituent having 6 to 20 carbon atoms. A 1-6 alkyl group is more preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is still more preferable.

The fluoroaliphatic group-containing monomer represented by the general formula (11) is more preferably a monomer represented by the following general formula (11 ').

In formula (11 ′), X ¹ represents a divalent group represented by —O—, —S— or —N (R ²²² ) —, and p represents an integer of 1 to 8. X ¹ is more preferably —O— or —N (R ²²² ) —, and most preferably —O—. p is more preferably from 1 to 6, and still more preferably from 1 to 3. R ⁶¹ and m1 have the same meanings as described in the general formula (11), and the preferred ranges are also the same. R ²²² represents a hydrogen atom, an alkyl group which may have a substituent having 1 to 8 carbon atoms, or an aryl group which may have a substituent having 6 to 20 carbon atoms.

Among the fluoroaliphatic group-containing monomers represented by the general formula (12), monomers represented by the following general formula (12 ′) are preferable.

In the general formula (12 ′), X ² represents a substituent represented by —O—, —S— or —N (R ²²² ) —, and q represents an integer of 1 to 8. X ² is more preferably —O— or —N (R ²²² ) —, and most preferably —O—. p is more preferably from 1 to 6, and still more preferably from 1 to 3. R ⁶² and n1 have the same meanings as described in the general formula (12), and the preferred ranges are also the same. R ²²² has the same meaning as that described in formula (11 ′).

Next, the polymerization unit of the amide group-containing monomer represented by the general formula (13) will be described.
In the general formula (13), R ⁷³ represents a hydrogen atom, a halogen atom or a methyl group, and more preferably a hydrogen atom or a methyl group. R ⁷¹ and R ⁷² each independently represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms or a heterocyclic group having 1 to 20 carbon atoms, and these substituents are further substituted It may have a group. Further, an alkyl group having 1 to 12 carbon atoms and an aromatic group having 6 to 15 carbon atoms are more preferable, and an alkyl group having 1 to 6 carbon atoms and an aromatic group having 6 to 12 carbon atoms are further included. preferable. R ⁷¹ and R ⁷² may be linked to each other to form a heterocyclic ring. Examples of the formed heterocyclic ring include a pyrrolidine ring, a piperidine ring, and a morpholine ring.

Further, the polymer used as the horizontal alignment agent may contain either a fluoroaliphatic group-containing monomer or an amide group-containing monomer as a polymerized unit, but preferably a fluoroaliphatic group-containing monomer and an amide group-containing monomer. Both are included as polymerized units. The polymer may contain two or more kinds of each monomer as polymerized units, or may be a copolymer containing one or more other copolymerizable monomers as polymerized units. Other types of such copolymerizable monomers include Polymer Handbook 2nd ed. , J .; Brandrup, Wiley Interscience (1975) Chapter 2, Pages 1-483 can be used. Examples thereof include compounds having one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like.

The preferred mass average molecular weight of the polymer used as the horizontal alignment agent is 2000 to 100,000, more preferably 3000 to 80,000, and still more preferably 4,000 to 60,000. Here, the mass average molecular weight and the molecular weight are converted to polystyrene by GTH analyzer using a column of TSKgel GMHxL, TSKgel G4000HxL, TSKgel G2000HxL (both are trade names manufactured by Tosoh Corporation) and detected by a solvent THF and a differential refractometer. Is the molecular weight.

Hereinafter, examples of specific structures of polymers that can be used as the horizontal alignment agent in the present invention will be shown, but the present invention is not limited to the following specific examples. In addition, the number in a formula shows the mass ratio of each monomer component. Mw represents a mass average molecular weight.

In addition, horizontal alignment agents described in JP-A-2005-99248, JP-A-2005-134484, JP-A-2006-126768, and JP-A-2006-267183 may be selected.

In the present invention, only one horizontal alignment agent may be used, or two or more horizontal alignment agents may be used. The addition amount of the horizontal alignment agent is preferably from 0.1% by mass to 10% by mass, more preferably from 0.5% by mass to 10% by mass, with respect to the addition amount of the dichroic dye. A mass% to 5 mass% is particularly preferred.

In the present specification, “tilt angle” means an angle formed between the major axis direction of the dye molecule and the interface (alignment film interface or air interface). When the composition of the present invention is used for the production of a polarizing film, a preferable optical performance as a polarizing element can be obtained by reducing the tilt angle on the alignment film side and performing horizontal alignment. Therefore, from the viewpoint of polarization performance, the preferred tilt angle on the alignment film side is 0 ° to 10 °, more preferably 0 ° to 5 °, particularly preferably 0 ° to 2 °, and most preferably 0 ° to 1 °. is there. The tilt angle on the air interface side is preferably 0 ° to 10 °, more preferably 0 to 5 °, and particularly preferably 0 to 2 °.
The composition of the present invention is
(1) a fluoroaliphatic group-containing compound represented by general formula (10); and (2) a polymerized unit and a general formula of a fluoroaliphatic group-containing monomer represented by general formula (11) or general formula (12) A polymer comprising at least one polymerized unit of an amide group-containing monomer represented by (13);
By including at least one of the above, the tilt angle on the alignment film side in the polarizer using this may be suppressed to 2 ° or less, for example.

Sugars:
Saccharides may be added to the composition of the present invention. By adding saccharides, the degree of association of the dye aggregate can be improved, and as a result, the molecular orientation of the dye can be enhanced.
Examples of saccharides that can be used include monosaccharides, disaccharides, polysaccharides, and sugar derivatives such as sugar alcohols. Among saccharides, those having a hydroxyl group of 2 or more, more preferably 3 or more, and preferably 18 or less, more preferably 12 or less, are preferred from the viewpoint of contributing to molecular association. When the number of hydroxyl groups is within the above range, the interaction with the dye is moderate, there is no precipitation caused by the interaction being too strong, and the orientation can be improved by the moderate interaction, which is preferable.

The molecular weight of the saccharide used is preferably 1,000 or less, more preferably 700 or less. When the molecular weight of the saccharide is within the above range, phase separation from the dye does not occur, and it can contribute to improvement of the orientation of the dye, which is preferable.
Moreover, as carbon number of saccharides to be used, it is 36 or less normally, Preferably it is 24 or less. When the carbon number of the saccharide is within the above range, phase separation from the dye does not occur, and it can contribute to improvement of the orientation of the dye, which is preferable.

Examples of saccharides that can be used in the present invention include monosaccharides, oligosaccharides, and monosaccharide alcohols, and it is preferable to use those having the number of hydroxyl groups and the molecular weight within the above preferred ranges.

Examples of monosaccharides include xylose, ribose, glucose, fructose, mannose, sorbose, and galactose.
Examples of the oligosaccharide include trehalose, kojibiose, nigerose, maltose, maltotriose, isomaltotriose, maltotetraose, isomaltose, sophorose, laminaribiose, cellobiose, gentiobiose, lactose, sucrose, melibiose, lutinose, primiverose, Examples include turanose, panose, isopanose, cellotriose, manninotriose, soratriose, melezitose, planteose, gentianose, umbelliferose, raffinose, and stachyose.
Examples of the sugar alcohol include compounds obtained by reducing the above monosaccharides and oligosaccharides such as threitol, xylitol, ribitol, arabitol, sorbitol, and mannitol.

As the saccharide, xylose, mannose, maltose, maltotriose and arabitol are particularly preferable.

These saccharides and sugar alcohols each have optical isomers, but each of them may be used alone or both may be included in the composition used in the present invention. Moreover, saccharides may be used individually by 1 type in the composition of this invention, and 2 or more types may be used in combination.

In the composition of the present invention, the saccharide content relative to the pigment is preferably in the range of 0.1 to 1 in terms of mass ratio. More preferably, it is 0.2 or more, particularly preferably 0.3 or more, further preferably 0.7 or less, and particularly preferably 0.6 or less. When the saccharide content is in the above range, an effect of improving the association degree of the dye aggregate can be obtained.

Antifungal, antibacterial and fungicides:
You may add the chemical | medical agent which has at least any function of antifungal, antibacterial, and disinfection to the composition of this invention. By adding these additives, the storage stability of the composition can be improved.

The agent having at least one of antifungal, antibacterial, and sterilizing functions as referred to in the present invention is an antifungal ability that suppresses the generation / growth / growth of mold, the bactericidal ability that kills microorganisms, the generation / growth of microorganisms, Any agent may be used as long as it has at least one function of antibacterial ability to suppress proliferation, and known antifungal agents, bactericides and antibacterial agents can be used. However, it is preferable that the optical properties of the anisotropic film prepared using the composition of the present invention are not deteriorated. Examples of the agent having at least one of antifungal, antibacterial and bactericidal functions used in the present invention include, for example, conventional phenolic compounds such as 2,4,4′-trichloro-2′-hydroxydiphenyl, chlorine dioxide and the like. Examples thereof include iodine, such as chlorine and iodine, and quaternary ammonium salt, such as benzalkonium chloride.

In addition, as an active ingredient, 1,2-benzisothiazole-3-one, Proxel BDN, Proxel BD20, Proxel GXL, Proxel LV, Proxel XL, Proxel XL2, Proxel Ultra10 (trade name, manufactured by Avecia) Polyhexylene biguanide hydrochloride as an active ingredient, Proxel IB (Avecia, product name), Dithio-2,2'-bis (benzmethylamide) as an active ingredient, Densil P (Aveci product, Aveci product) ) And the like.
Further, the following compounds are particularly preferable because they exhibit an antibacterial effect particularly in a very small amount.
No. Compound name 2-chloromethyl-5-chloro-3-isothiazolone 2-cyanomethyl-5-chloro-3-isothiazolone 2-hydroxymethyl-5-chloro-3-isothiazolone4. 2- (3-Methylcyclohexyl) -3-isothiazolone 2- (4-Chlorophenyl) -4,5-dichloro-3-isothiazolone 6. 2- (4-Ethylphenyl) -3-isothiazolone 2- (4-Nitrophenyl) -5-chloro-3-isothiazolone 2-chloromethyl-3-isothiazolone9. 2-methoxyphenyl-4-methyl-5-chloro-3-isothiazolone 2-morpholinomethyl-5-chloro-3-isothiazolone These compounds can be synthesized with reference to, for example, Japanese Patent Application Laid-Open No. Hei 2-278, but trade names such as Tribactran (manufactured by Hoechst), etc. Commercial products can also be used.

Moreover, the chemical | medical agent which has at least any one function of antifungal, antibacterial, and disinfection which can be used by this invention can also be used individually or in combination of 2 or more types.
The content of the agent having at least one of antifungal, antibacterial and sterilizing functions in the composition is not particularly limited, but is usually 0.01% by mass or more, preferably 0.001% by mass or more. On the other hand, it is usually 0.5% by mass or less, preferably 0.3% by mass or less. When the amount is within the above range, the agent does not precipitate, phase separation occurs when the dye film is formed, and the addition effect of these agents does not cause optical defects such as point defects and light scattering. Is obtained.

In an embodiment in which the composition of the present invention is used for the production of a polarizing film, an electron-deficient discotic compound and an electron-rich compound are contained in the composition in order to obtain a polarizing film having a high degree of polarization. It is preferable to contain an (Electron-Rich) compound. In the present invention, for example, those described in JP-A-2006-323377 can be used as the electron-deficient discotic compound and the electron-rich compound.

The ratio of the electron-deficient discotic compound is usually 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and usually 50 parts by mass, when the total composition is 100 parts by mass. The range is not more than part by mass, preferably not more than 40 parts by mass. When the content is within the above range, the effect of adding the compound can be obtained without excessively increasing the viscosity when the composition is prepared as a solution.

The ratio of the electron-rich compound is usually 50 parts by mass or less, preferably 40 parts by mass or less when the entire composition is 100 parts by mass. The addition effect of this compound can be acquired, without raising a viscosity too much that it is the said range.

Also, the mass fraction of the electron-deficient discotic compound and the electron-rich compound is usually preferably in the range of 10/90 to 90/10. Outside this range, it is not preferable because the effect of using an electron-deficient discotic compound or an electron-rich compound may not be obtained.

Non-liquid crystalline binder polymer:
The composition of the present invention may contain a non-liquid crystalline polymer as a binder. Examples of non-liquid crystalline polymers include acrylic resins such as polyacrylonitrile, polyacrylic acid esters and polyacrylamide, polyvinyl acetal resins such as polystyrene resin, polyvinyl acetoacetal and polyvinyl butyral, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxy Modified cellulose resins such as propyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose nitrate, etc., cellulose resins such as ethyl hydroxyethyl cellulose and ethyl cellulose, polyurethane resins, polyamide resins, Polyester resin, polycarbonate resin, phenoxy resin, phenol resin , Epoxy resins, various elastomers, and the like. These may be used alone, or may be mixed or copolymerized for use.
As the non-liquid crystalline binder polymer, an acrylic polymer (a resin having an acrylic copolymer or a styrene copolymer as a main chain) is particularly preferable, and it is particularly preferable that the non-liquid crystalline binder polymer is soluble in an organic solvent.

For the production of the acrylic polymer, for example, a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. in the production by the radical polymerization method can be easily set by those skilled in the art, and the conditions should be determined experimentally. You can also.

As for specific copolymerization components of the above acrylic polymer, unsaturated carboxylic acid (eg, (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid), aromatic vinyl compound (eg, styrene, α-methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine, N-vinylimidazole, etc.), (meth) acrylic acid alkyl esters (eg, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl) (Meth) acrylate, i-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, etc.), (meth) acrylic acid alkyl aryl ester (eg, benzyl (meth) acrylate, etc.) ), (Meth) acrylic acid substituted alkyl ester Tellurium (eg, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate), carboxylic acid vinyl esters (eg, vinyl acetate and vinyl propionate), vinyl cyanide (eg, (meth) acrylonitrile and α-chloro) Acrylonitrile) and aliphatic conjugated dienes (eg, 1,3-butadiene and isoprene). Of these, unsaturated carboxylic acids, aromatic vinyl compounds, (meth) acrylic acid alkyl esters, (meth) acrylic acid alkyl aryl esters and carboxylic acid vinyl esters are preferred. Here, (meth) acrylic acid is a generic term for acrylic acid and methacrylic acid together, and (meth) acrylate is a generic term for acrylate and methacrylate.
Furthermore, an acrylic polymer having a (meth) acryloyl group in the side chain or a macromonomer (for example, a polystyrene macromonomer, a polymethyl methacrylate macromonomer, a polyethylene glycol mono (meth) acrylate, a polypropylene glycol mono (meth) acrylate, a polyethylene as a copolymerization component) An acrylic graft polymer containing glycol polypropylene glycol mono (meth) acrylate and the like is also preferable.
These can be used alone or in combination of two or more.

1. -3 Aspect of Black Coloring Composition There is no particular limitation on the color tone of the dichroic dye composition of the present invention, and it can be prepared as a coloring composition of various color tones depending on the application. For example, in an embodiment used for the production of a polarizing film, it is preferable to mix two or more dyes so as to obtain a black colored composition. One aspect of the dichroic dye composition of the present invention is a black coloring composition containing a yellow dye, a magenta dye, and a cyan dye, respectively. In this embodiment, the dichroic dye represented by the general formula (I) may be used as a dye having any color tone. Further, the composition of this embodiment may be prepared by using two or more kinds of dichroic dyes represented by the general formula (I) and having different color tones.
In the present specification, a yellow dye means a dye having an absorption maximum wavelength in the range of 400 to 500 nm, and a magenta dye means a dye having an absorption maximum wavelength in the range of 500 to 580 nm. Means a dye having an absorption maximum wavelength in the range of 580 nm to 700 nm. The maximum absorption wavelength can be known by preparing a solution in which a dye is dissolved in an organic solvent and measuring the absorption spectrum of the solution. For example, NMP (N-methylpyrrolidone) is used as the organic solvent.

An example of this embodiment is a black colored composition containing at least one dichroic dye represented by the general formula (III) as a yellow dye.
Another example is a black colored composition containing at least one dichroic dye represented by the general formula (III) as a yellow dye and a cyan dye. The yellow dye represented by the general formula (III) can achieve black color by mixing with a cyan dye. Of course, it may further contain a magenta dye.
Another example is a black coloring composition containing at least one dichroic dye represented by the general formula (IV) as a magenta dye.
In another example of this embodiment, at least one dichroic dye represented by the general formula (III) is used as a yellow dye, and at least one dichroic dye represented by the general formula (IV) is used. A black colored composition containing seeds as magenta dyes.
Although there is no restriction | limiting in particular about the cyan dye utilized in this aspect, In order to raise dichroic ratio, it is preferable that a cyan dye is also a dichroic azo dye which has liquid crystallinity. As the dichroic azo dye having liquid crystallinity, for example, compounds represented by the following general formulas (1) and (2) are preferable.

In the formula, R ¹ to R ⁵ each independently represents a hydrogen atom or a substituent. R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group which may have a substituent. Q ¹ represents an optionally substituted aromatic hydrocarbon group, aromatic heterocyclic group or cyclohexane ring group. L ¹ represents a divalent linking group. A represents an oxygen atom or a sulfur atom.

In the formula, R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group which may have a substituent. Q ² represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent. Q ³ represents an optionally substituted divalent aromatic hydrocarbon group or divalent aromatic heterocyclic group, n represents an integer of 1 to 4, and when n is 2 or more, A plurality of Q ³ may be the same or different.

Among the compounds represented by the general formula (1), particularly preferred are compounds represented by the following general formula (3).

In the formula, R ¹⁰ to R ¹³ each independently represents a hydrogen atom or an alkyl group; R ¹⁴ represents a hydrogen atom or a methyl group; and R ¹⁵ and R ¹⁶ each independently have a substituent. B ¹ represents a nitrogen atom or an optionally substituted carbon atom; L ² represents an azo group, an acyloxy group (—C (═O) O—), an oxycarbonyl group (— OC (= O)-) or an imino group.

Among the compounds represented by the general formula (2), particularly preferred are compounds represented by the following general formula (4).

In the formula, R ¹⁷ to R ²⁰ each independently represents a hydrogen atom or a substituent; R ²¹ and R ²² each independently represents an alkyl group which may have a substituent; B ² represents a nitrogen atom Or represents an optionally substituted carbon atom; m represents 1 or 2, and when m is 2 or more, two R ¹⁷ to R ²⁰ may be the same or different.

Of course, the compound represented by the general formula (I) may be used as the cyan dye.
Moreover, in this embodiment, there is no restriction | limiting in particular about the content ratio of a pigment | dye. Similar amounts will be added.

By using the black composition of this embodiment, the transmitted light when the C light source is used as the light source is 0.28 <x <0.36, 0.28 <y <0.36 in the xy chromaticity diagram. Can be produced. When this condition is satisfied, for example, when the polarizing film is disposed between the liquid crystal layer and the color filter layer in the liquid crystal cell, it is preferable because scattering over the entire visible region caused by the RGB color filter can be suppressed.
The C light source, the xy chromaticity diagram, and how to obtain x and y are described in detail in the JIS Handbook [61] color issued by the Japanese Standards Association and can be referred to.

2. Application of Dichroic Dye Composition of the Present Invention The dichroic dye composition of the present invention can be used for various applications. Since it shows a high dichroic ratio, it is preferably used as a material for forming a polarizing film. Hereinafter, the polarizing film formed from the composition of the present invention will be described.
2. -1 Polarizing Film The present invention also relates to a polarizing film formed from the dichroic dye composition of the present invention. The polarizing film of the present invention transmits arbitrary linearly polarized light and absorbs, reflects, or backscatters polarized light whose plane of polarization is orthogonal to the linearly polarized light; and transmits right or left circularly polarized light and spirals the circularly polarized light. May absorb, reflect, or backscatter circularly polarized light in the reverse direction.
Since the dichroic dye contained in the composition of the present invention exhibits liquid crystallinity, for example, when the composition of the present invention is prepared as a coating liquid and applied to the alignment film surface, the dye molecules are aligned at the interface with the alignment film. The film is oriented at the tilt angle of the film, and is oriented at the tilt angle of the air interface at the interface with air. The dye molecules can be used as a linearly polarizing film by horizontally aligning them and fixing them in the aligned state.

The thickness of the polarizing film of the present invention formed from the above composition is not particularly limited, but is generally preferably 0.01 to 2 μm, and more preferably 0.05 to 2 μm. .
Since the composition of the present invention exhibits a high dichroic ratio, the polarizing film of the present invention comprising the composition has a film thickness in the above range, and can achieve a degree of polarization of 85% or more even if it is relatively thin. . Accordingly, it is particularly useful as a polarizing layer disposed in a liquid crystal cell, for example, in applications where thinning is particularly required. That is, it is particularly useful as a polarizing layer that contributes to reducing the generation of scattered light by depolarizing linearly polarized light entering the cell by a member in the cell such as a color filter layer.

Also. The polarizing film of the present invention may have functional layers such as a transparent resin cured layer, an adhesive layer, and an antireflection layer on the surface thereof.

2. -2 Production method of polarizing film The production method of the polarizing film of the present invention is not particularly limited. An example is as follows.
[1] Step of rubbing or light-irradiating the alignment film formed on the substrate directly or on the substrate [2] Applying the composition of the present invention prepared as a coating solution on the substrate or the alignment film The step of forming a film [3] It is preferable to produce the film by a method including the step of orienting the dye molecules in the composition by evaporating the solvent from the film to form a polarizing film.

Hereinafter, description will be given according to each step [1] to [3].
[1] Alignment treatment step First, an alignment treatment is performed on the surface of the substrate or the surface of the alignment film formed on the substrate. The alignment process includes a rubbing process and a light irradiation process to be described later.
・ Rubbing treatment As described in detail later, the rubbing treatment is performed by rubbing the surface of the substrate or the like in a certain direction with a buff such as cotton cloth or absorbent cotton to form a fine groove parallel to the direction. It is an operation. By applying the composition of the present invention to the rubbing surface, the dye molecules can be finally adsorbed to the surface in an oriented state.

A desired orientation state can be obtained by adjusting the rubbing conditions, for example, the rubbing density. For example, between the rubbing density and the pretilt angle of the alignment film, there is a relationship in which the pretilt angle decreases as the rubbing density increases, and the pretilt angle increases as the rubbing density decreases. As a method for changing the rabin density, a method described in “Liquid Crystal Handbook” (published by Maruzen) can be used. The rubbing density (L) is quantified by the following formula (A).
Formula (A) L = Nl (1 + 2πrn / 60v)
In the formula (A), N is the number of rubbing, l is the contact length of the rubbing roller, r is the radius of the roller, n is the number of rotations (rpm) of the roller, and v is the stage moving speed (second speed).
In order to increase the rubbing density, the rubbing frequency should be increased, the contact length of the rubbing roller should be increased, the radius of the roller should be increased, the rotation speed of the roller should be increased, and the stage moving speed should be decreased, while the rubbing density should be decreased. To do this, you can do the reverse.

-Light irradiation Another example of the above [1] is a step of applying a linearly polarized light or a non-polarized light to a film made of a photoalignment material formed on a substrate to form a photoalignment film.
The linearly polarized light irradiation is an operation for causing a photoreaction in the photo-alignment material. The wavelength of the light to be irradiated varies depending on the photo-alignment material used, and is not particularly limited as long as it is a wavelength necessary for the photoreaction. Preferably, the peak wavelength of light used for light irradiation is 200 nm to 700 nm, and more preferably ultraviolet light having a peak wavelength of light of 400 nm or less.

The light source used for light irradiation is a commonly used light source such as a tungsten lamp, a halogen lamp, a xenon lamp, a xenon flash lamp, a mercury lamp, a mercury xenon lamp, a carbon arc lamp, or various lasers (eg, semiconductor laser, helium). Neon laser, argon ion laser, helium cadmium laser, YAG laser), light emitting diode, cathode ray tube, and the like.

As means for obtaining linearly polarized light, a method using a polarizing plate (eg, iodine polarizing plate, dichroic dye polarizing plate, wire grid polarizing plate), reflection using a prism-based element (eg, Glan-Thompson prism) or Brewster angle A method using a polarizing film or a method using light emitted from a polarized laser light source can be employed. Moreover, you may selectively irradiate only the light of the required wavelength using a filter, a wavelength conversion element, etc.

In the case of linearly polarized light, a method of irradiating light from the top surface or the back surface with respect to the film surface and from a direction perpendicular or oblique to the film surface is employed. The incident angle of the light varies depending on the photo-alignment material, but is, for example, 0 to 90 ° (vertical), preferably 40 to 90.
In the mode of irradiating non-polarized light, a method of irradiating light from an oblique direction is adopted, and the incident angle is 10 to 80 °, preferably 20 to 60, and particularly preferably 30 to 50 °.
The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.

When patterning is necessary, a method of performing light irradiation using a photomask as many times as necessary for pattern creation or a method of writing a pattern by laser beam scanning can be employed.

[2] Coating step This is a step of coating the composition of the present invention prepared as a coating solution on the surface of the substrate or alignment film subjected to the alignment treatment.
As a solvent used for the preparation of the coating solution, an organic solvent is preferable. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, toluene, hexane), alkyl halides (Eg, chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Hydrocarbons, alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

There is no particular limitation on the coating method of the coating solution. It is preferable to use a wet film forming method. Wet deposition methods include Yuji Harasaki, “Coating Engineering”, Asakura Shoten Co., Ltd., published on March 20, 1971, pages 253-277 and “Creation and Application of Molecular Cooperative Materials” supervised by Kunihiro Ichimura, CMC Co., Ltd. Publicly known methods described in Publication, published on March 3, 1998, pages 118 to 149, and the like. In addition, for example, a normal coating method (for example, spin coating method, spray coating method, slit coating method, slit and spin method, wire bar coating method, roll coating method, blade coating method, free span coating method, extrusion coating method, (Direct gravure coating method, reverse gravure coating method, die coating method, ink jet method). Among them, in the present invention, it is preferable to use a slit coating method from the viewpoint of uniformity of alignment and use efficiency of the composition. Hereinafter, the slit coating method will be described as an example.

Slit coating method:
An example of the slit coating method is as follows. A coating liquid of the composition of the present invention is applied to a substrate (for example, a substrate having a length of 800 mm or more on one side) from a slit die of a cast coating machine having a relative moving speed of 50 to 150 mm / sec with the substrate. coating to form a wet coating film having a thickness L ¹ on the substrate surface. Then, if necessary, the solvent is removed to form a pre-baked coating film having a thickness of L ² and prebaked against wet film. At this time, the film thickness L ^{1 of the} wet coating film is preferably 0.1 to 20 μm, and the film thickness L ² of the dry coating film is preferably 0.01 to 2 μm. The gap between the discharge port of the slit die and the substrate surface is in the range of 50 μm to 200 μm.
By applying the coating solution of the composition of the present invention by the above method, a polarizing film having high alignment uniformity can be formed with high productivity even when applied to the surface of a fifth generation glass substrate (1100 mm × 1250 mm), for example. can do.

The temperature at the time of application is preferably 0 ° C. or more and 80 ° C. or less, and the humidity is preferably about 10% RH or more and 80% RH or less.

In addition, when the coating liquid of the composition of the present invention is applied by a wet film forming method, the substrate may be heated or cooled. The temperature of the substrate at this time is preferably 10 ° C. or higher and 60 ° C. or lower. If the upper limit is exceeded, the orientation may be disturbed before drying under reduced pressure, which will be described in detail below, and if it is lower than the lower limit, water droplets may form on the surface of the support, which may hinder coating. The substrate may be heated when the polarizing film applied by the wet film forming method is dried under reduced pressure. The temperature of the substrate at this time is preferably 60 ° C. or lower. If the upper limit is exceeded, the orientation may be disturbed before drying under reduced pressure.

In the above method, a polarizing film may be formed by applying a dye composition on a substrate or alignment film subjected to alignment treatment in one direction at an angle not parallel to the alignment treatment direction on the substrate or alignment film. it can. Furthermore, it is more preferable to apply the dye composition in a direction substantially coinciding with the vertical or horizontal direction of the substrate. Thereby, a polarizing film having no alignment defect and a high degree of polarization can be formed. In addition, after applying the dye composition, it is not necessary to cut out the substrate in order to give the necessary polarization angle, and the productivity is high.

[3] Drying and orientation step Following the above [2] coating step, a step of orienting the dye molecules is carried out by evaporating the solvent from the coating film formed by the [2] coating step.
In this case, the drying temperature is preferably natural drying at room temperature, and it is preferable not to disturb the alignment state of the dye molecules formed by coating (avoid thermal relaxation or the like). In the pressure reduction treatment, it is also preferable to evaporate the solvent and dry at a lower temperature.
The decompression treatment here refers to removing a solvent by evaporating a substrate having a coating film (polarizing film) under reduced pressure conditions. At this time, it is preferable that the substrate having the polarizing film be kept horizontal so that it does not flow from the high part to the bottom part. The shorter the time from the start of application to the pressure reduction treatment of the polarizing film, the better. The time is preferably from 1 second to 30 seconds.

As the decompression method, for example, the following methods can be mentioned. The polarizing film obtained by applying the coating liquid is put into a reduced pressure processing apparatus together with the substrate and subjected to a reduced pressure process. For example, a decompression processing apparatus as shown in FIGS. 9 and 10 of JP-A-2006-201759 can be used. Details of the decompression processing apparatus are described in JP-A No. 2004-169975.

As the conditions for the decompression treatment, the pressure in the system where the polarizing film is present is preferably 2 × 10 ⁴ Pa or less, more preferably 1 × 10 ⁴ Pa or less, and particularly preferably 1 × 10 ³ Pa or less. Further, it is preferably ¹ Pa or more, more preferably 1 × 10 ¹ Pa or more. Usually, the pressure finally reached in the system is preferably as described above. If the upper limit is exceeded, drying may not be possible and the orientation may be disturbed. If the lower limit is not reached, drying may be too rapid and defects may occur.
The decompression time is preferably 5 seconds or more and 180 seconds or less. If the upper limit is exceeded, the polarizing film cannot be dried rapidly before orientation relaxation, and the orientation may be disturbed. If the lower limit is not reached, drying may not be possible and the orientation may be disturbed.
Further, the temperature in the system during the decompression treatment is preferably 10 ° C. or more and 60 ° C. or less. If the upper limit is exceeded, convection may occur during drying and non-uniformity may occur in the polarizing film, and if the lower limit is not reached, drying may not be possible and orientation may be disturbed.

In addition, when the dye molecules are aligned after drying the film and removing the solvent, the substrate may be heated in order to promote the alignment. The temperature of the substrate at this time is preferably 50 ° C. or higher and 200 ° C. or lower, and particularly preferably 70 ° C. or higher and 180 ° C. or lower. In order to lower the orientation temperature, an additive such as a plasticizer may be used in combination with the dye composition.

[4] Curing step [3] A polarizing film can be obtained by carrying out drying and orientation steps, but it is preferable to further carry out the curing step because the film strength is improved.
For example, in an embodiment in which the composition contains a non-liquid crystalline polymerizable polyfunctional monomer, the dye is oriented, and then polymerized and cured by light irradiation (preferably ultraviolet irradiation) or heating, or a combination thereof. Is preferred.

[5] Step of adding functional layer, etc. The polarizing film of the present invention can be formed by carrying out the above [1] to [3] and optionally [4].
Further, a transparent resin cured layer, an adhesive layer, an antireflection layer, or the like may be formed on the surface of the polarizing film.
The transparent resin cured layer can be formed by applying a coating liquid of the curable transparent resin composition on the surface of the polarizing film and curing it. As a coating solvent used for preparing the coating solution, a liquid having a boiling point of 60 to 170 ° C. is preferably used. Specifically, water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate, ethyl acetate, propyl acetate) , Butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (Eg, benzene, toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy) 2-propanol) and the like. Of these, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol and butanol are preferred, and particularly preferred dispersion media are methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and ethanol.
The amount of the solvent used is preferably such that the solid content concentration of the curable transparent resin composition is 2 to 50% by mass, and more preferably 3 to 40% by mass.
The application method of the polarizing film can be used for the application of the coating liquid of the curable transparent resin composition.

Next, the coating film is cured to form a transparent resin cured layer. Curing is preferably performed by ultraviolet irradiation.

2. -3 Materials Used for Production of Polarizing Film Next, materials other than the polarizing film such as the alignment film obtained by the above method will be described.
Alignment film:
The orientation film that can be used for the production of the polarizing film of the present invention may be any layer as long as it can impart a desired orientation to the dye molecules provided on the orientation film. For example, rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or an organic compound (eg, ω-tricosanoic acid, disilane) by the Langmuir-Blodgett method (LB film) It can be provided by means such as the accumulation of octadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known. Among these, from the viewpoint of easy control of the pretilt angle of the alignment film, an alignment film formed by rubbing the surface of the polymer film is preferable, and from the viewpoint of alignment uniformity, a photo-alignment material A photo-alignment film formed by irradiating the film with light is preferable.

As a polymer used for the alignment film formed by the rubbing treatment, there are many literatures, and many commercially available products can be obtained. For example, polyvinyl alcohol or polyimide and derivatives thereof are preferably used. For the alignment film, reference can be made to the description on page 43, line 24 to page 49, line 8 of WO01 / 88574A1.
The thickness of the alignment film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

As a photo-alignment material used for an alignment film formed by light irradiation, there are many references. Specifically, JP-A-2006-285197, JP-A-2007-76839, JP-A-2007-138138, JP-A-2007-94071, JP-A-2007-121721, JP-A-2007-140465. Azo compounds described in JP-A No. 2007-156439, JP-A No. 2007-133184, JP-A No. 2009-109831, JP-A No. 3888848, and JP-A No. 4151746; Aromatic ester compounds described; maleimide and / or alkenyl-substituted nadiimide compounds having a photoalignment unit described in JP-A Nos. 2002-265541 and 2002-31703; Patents 4205195 and 4205198 The photocrosslinkable silane derivative described above; It is mentioned as examples are preferred; 2003-520878, JP-T-2004-529220, JP-photocrosslinkable polyimide, polyamide, or esters described in Japanese Patent No. 4162850. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, or esters.

Transparent resin cured layer:
As described above, the polarizing film of the present invention may have a transparent resin cured layer on the surface thereof. This layer is provided in order to impart physical strength, durability, or optical properties to the polarizing film. The thickness of the transparent resin cured layer is preferably in the range of 1 to 30 μm, and particularly preferably 1 to 10 μm.
The transparent resin cured layer is preferably formed by a crosslinking reaction or a polymerization reaction of an ionizing radiation curable compound. The transparent resin cured layer in the present invention is obtained by applying a coating composition containing an ionizing radiation curable polyfunctional monomer or polyfunctional oligomer on the surface of the polarizer, and crosslinking reaction or polymerization reaction of the polyfunctional monomer or polyfunctional oligomer. Can be formed.
The functional group of the ionizing radiation-curable polyfunctional monomer or polyfunctional oligomer is preferably a light, electron beam, or radiation polymerizable group, and among them, a photopolymerizable functional group is preferable.
Examples of the photopolymerizable functional group include unsaturated polymerizable functional groups such as a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Among them, a (meth) acryloyl group is preferable. Moreover, inorganic fine particles can also be contained.

As a specific example of a photopolymerizable polyfunctional monomer having a photopolymerizable functional group,
(Meth) acrylic acid diesters of alkylene glycol such as neopentyl glycol acrylate, 1,6-hexanediol (meth) acrylate, propylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyoxyalkylene glycols such as triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate;
(Meth) acrylic acid diesters of polyhydric alcohols such as pentaerythritol di (meth) acrylate;
(Meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxy-diethoxy) phenyl} propane and 2-2bis {4- (acryloxy-polypropoxy) phenyl} propane ;
Etc.
Furthermore, epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates are also preferably used as the photopolymerizable polyfunctional monomer.

Of these, esters of polyhydric alcohol and (meth) acrylic acid are preferred. More preferably, a polyfunctional monomer having 3 or more (meth) acryloyl groups in one molecule is preferable. Specifically, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, 1,2,4-cyclohexanetetra (meth) acrylate, pentaglycerol triacrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol tri (meth) acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol triacrylate, tripentaerythritol hexatriacrylate, etc. Is mentioned. Two or more polyfunctional monomers may be used in combination.

As a polymerization initiator used for formation of the said transparent resin cured layer, a photoinitiator is preferable. As the photopolymerization initiator, a photoradical polymerization initiator and a photocationic polymerization initiator are preferable, and a photoradical polymerization initiator is particularly preferable.
Examples of the photo radical polymerization initiator include acetophenones, benzophenones, Michler's benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, and thioxanthones.
Commercially available photo radical polymerization initiators include Kayacure (DETX-S, BP-100, BDDK, CTX, BMS, 2-EAQ, ABQ, CPTX, EPD, ITX, QTX, BTC, manufactured by Nippon Kayaku Co., Ltd. MCA, etc., all trade names), Irgacure (651, 184, 127, 500, 907, 369, 1173, 2959, 4265, 4263 etc., all trade names) manufactured by Ciba Specialty Chemicals Co., Ltd., Sartomer Examples include Esacure (KIP100F, KB1, EB3, BP, X33, KT046, KT37, KIP150, TZT, all of which are trade names).

In particular, photocleavable photoradical polymerization initiators are preferred. The photocleavable photoradical polymerization initiator is described in the latest UV curing technology (P.159, issuer; Kazuhiro Takasawa, publisher; Technical Information Association, published in 1991).
Examples of commercially available photocleavable photoradical polymerization initiators include Irgacure (651, 184, 127, 907, trade names) manufactured by Ciba Specialty Chemicals.

The photopolymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the curable resin.
In addition to the photopolymerization initiator, a photosensitizer may be used. Specific examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine, Michler's ketone and thioxanthone.
Examples of commercially available photosensitizers include KAYACURE (DMBI, EPA, both trade names) manufactured by Nippon Kayaku Co., Ltd.
The photopolymerization reaction is preferably carried out by UV irradiation after the application of the high refractive index layer and drying.

The transparent resin cured layer may be added with an oligomer or polymer having a mass average molecular weight of 500 or more, or both for imparting brittleness.
Examples of the oligomer and polymer include (meth) acrylate-based, cellulose-based, and styrene-based polymers, urethane acrylate, and polyester acrylate. Preferable examples include poly (glycidyl (meth) acrylate) and poly (allyl (meth) acrylate) having a functional group in the side chain.

The total amount of oligomer and polymer in the transparent resin cured layer is preferably 5 to 80% by mass, more preferably 25 to 70% by mass, and particularly preferably 35 to 65% by mass with respect to the total mass of the resin layer. It is.

The strength of the transparent resin cured layer is preferably H or more, more preferably 2H or more, and most preferably 3H or more in a pencil hardness test according to JIS K5400.
Further, in the Taber test according to JIS K5400, the smaller the wear amount of the test piece before and after the test, the better.
In the formation of the transparent resin cured layer, when the ionizing radiation curable compound is formed by a crosslinking reaction or a polymerization reaction, the crosslinking reaction or the polymerization reaction is preferably performed in an atmosphere having an oxygen concentration of 10% by volume or less. . By forming in an atmosphere having an oxygen concentration of 10% by volume or less, a transparent resin cured layer excellent in physical strength and durability can be formed, which is preferable.
Preferably, it is formed by a crosslinking reaction or polymerization reaction of an ionizing radiation curable compound in an atmosphere having an oxygen concentration of 6% by volume or less, more preferably an oxygen concentration of 4% by volume or less, particularly preferably an oxygen concentration of 2 Volume% or less, most preferably 1 volume% or less. As a method of reducing the oxygen concentration to 10% by volume or less, it is preferable to replace the atmosphere (nitrogen concentration of about 79% by volume, oxygen concentration of about 21% by volume) with another gas, particularly preferably replacement with nitrogen (nitrogen purge). It is to be.

substrate:
The polarizing film of the present invention may be formed on a substrate.
As the substrate, for example, a non-alkali glass, soda glass, pyrex (registered trademark) glass, quartz glass, a solid-state image sensor used for a liquid crystal display element, an OLED element, etc., for example, a silicon substrate, etc. And a plastic substrate, and those obtained by attaching a transparent conductive film, a color filter film, an electrode, and a TFT to them. On these substrates, usually, a black matrix for isolating each pixel may be formed, or a transparent resin layer may be provided for promoting adhesion.
It is also preferable that the plastic substrate has a gas barrier layer and / or a solvent resistant layer on the surface thereof.

The light transmittance of the substrate used in the present invention is preferably 80% or more. The plastic substrate is preferably an optically isotropic polymer film. As specific examples and preferred embodiments of the polymer, the description in paragraph [0013] of JP-A-2002-22294 can be applied. Further, even a conventionally known polymer such as polycarbonate or polysulfone that easily develops birefringence is used by reducing the expression by modifying the molecule described in International Publication WO00 / 26705. You can also.

3. TECHNICAL FIELD The present invention relates to a liquid crystal cell having the polarizing film of the present invention inside. More specifically, the present invention relates to a liquid crystal cell having a pair of substrates and a liquid crystal layer, a color filter layer, and the polarizing film of the present invention disposed therebetween. The polarizing film of the present invention will be used, for example, as a polarizing layer that contributes to reducing the depolarization of linearly polarized light entering the cell and the generation of scattered light. In order to sufficiently exhibit this function, it is preferable to dispose the polarizing film of the present invention between the color filter layer and the liquid crystal layer.

The polarizing film of the present invention can be directly formed on the surface of a color filter substrate, for example, by the above method. Alternatively, the transfer material described below may be used for transfer. That is, an example of a method for producing a liquid crystal cell using the polarizing film of the present invention includes a method including forming the polarizing film by transferring it from a transfer material. By forming a polarizing film using a transfer material, the number of steps can be reduced, and a cell and a display device with good display characteristics can be manufactured by a simple method.

Hereinafter, a transfer material useful for forming the polarizing film in a liquid crystal display device, particularly in a liquid crystal cell, will be described.
3. -1 Transfer Material The transfer material that can be used in the present invention has at least a support and a polarizing film. Furthermore, it is preferable to have at least one photosensitive resin layer on the polarizing film. The photosensitive resin layer is useful because it facilitates the transfer of the polarizing film even when the process such as patterning is not performed. Further, for example, between the support and the polarizing film, there may be a layer for controlling mechanical properties such as cushioning for absorbing irregularities on the counterpart substrate side during transfer, or for imparting irregularity followability. Alternatively, a layer functioning as an alignment layer for controlling the alignment of the dye of the polarizing film may be disposed, or both layers may be provided. Moreover, you may provide the protective layer which can peel on the outermost surface for the objectives, such as surface protection of the photosensitive resin layer.

The support used for the above transfer material may be transparent or opaque and is not particularly limited. Examples of the polymer constituting the support include cellulose ester (eg, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose acetate butyrate), polyolefin (eg, norbornene-based polymer), poly (Meth) acrylic acid esters (eg, polymethyl methacrylate), polycarbonate, polyester and polysulfone are included. For the purpose of inspecting optical properties in the production process, the transparent support is preferably a transparent and low birefringent material, and cellulose ester and norbornene are preferred from the viewpoint of low birefringence. As a commercially available norbornene-based polymer, Arton (manufactured by JSR Co., Ltd.), Zeonex, Zeonore (manufactured by Nippon Zeon Co., Ltd.), or the like can be used. Inexpensive polycarbonate, polyethylene terephthalate, and the like are also preferably used.

The polarizing film is formed on the support by a method using the coating. Alternatively, an alignment film may be formed on the support, and a polarizing film may be formed thereon by coating. Note that the polarizing film included in the transfer material does not need to satisfy the optical characteristics sufficient for the polarization performance. For example, the polarization performance is expressed or changed through the exposure process performed in the transfer process, and the final film is obtained. In particular, the polarizing film may exhibit a polarizing performance necessary for the polarizing film.

Photosensitive resin layer:
The transfer material preferably has a photosensitive resin layer. The photosensitive resin layer is made of a photosensitive resin composition, and the photosensitive resin layer includes at least (1) an alkali-soluble resin, (2) a monomer or an oligomer, and (3) a photopolymerization initiator or photopolymerization. It is preferable to form from the resin composition containing an initiator system.

(1) Alkali-soluble resin The alkali-soluble resin (hereinafter sometimes simply referred to as “binder”) is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc. Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Further, as particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate, (meth) acrylic acid and other monomers And a multi-component copolymer. The binder polymer having these polar groups may be used alone or in the state of a composition used in combination with a normal film-forming polymer, and contained in the total solid content of the photosensitive resin composition. The amount is generally 20 to 50% by mass, preferably 25 to 45% by mass.

(2) Monomer or oligomer The monomer or oligomer used in the photosensitive resin layer is preferably a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization by light irradiation. . Examples of such monomers and oligomers include compounds having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) ) Acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034 and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in Japanese Patent Publication No. 52-30490; polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and methacrylates.
Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.
These monomers or oligomers may be used alone or in admixture of two or more. The content of the photosensitive resin composition with respect to the total solid content is generally 5 to 50% by mass, and 10 to 40% by mass. % Is preferred.

(3) Photopolymerization initiator or photopolymerization initiator system As the photopolymerization initiator or photopolymerization initiator system used in the photosensitive resin layer, a vicinal poly disclosed in US Pat. No. 2,367,660 is used. Ketaldonyl compounds, acyloin ether compounds described in US Pat. No. 2,448,828, aromatic acyloin compounds substituted with α-hydrocarbons described in US Pat. No. 2,722,512, US Pat. No. 3,046,127 And a polynuclear quinone compound described in U.S. Pat. No. 2,951,758, a combination of a triarylimidazole dimer described in U.S. Pat. No. 3,549,367 and a p-aminoketone, and a benzoin described in JP-B-51-48516. Thiazole compounds and trihalomethyl-s-triazine compounds, US Pat. No. 4,239,850 The listed trihalomethyl - triazine compound include a trihalomethyl oxadiazole compounds described in U.S. Pat. No. 4,212,976. In particular, trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer are preferable.
In addition, “polymerization initiator C” described in JP-A-11-133600 can also be mentioned as a preferable example.
These photopolymerization initiators or photopolymerization initiator systems may be used singly or as a mixture of two or more, but it is particularly preferable to use two or more. When at least two kinds of photopolymerization initiators are used, display characteristics, particularly display unevenness, can be reduced.
The content of the photopolymerization initiator or photopolymerization initiator system with respect to the total solid content of the photosensitive resin composition is generally 0.5 to 20% by mass, and preferably 1 to 15% by mass.

Other layers:
It is preferable to form a thermoplastic resin layer between the support and the polarizing film of the transfer material in order to control the mechanical properties and the unevenness followability. The component used in the thermoplastic resin layer is preferably an organic polymer substance described in JP-A-5-72724, and is a polymer softening point according to the Viker Vicat method (specifically, American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less. Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.

In the transfer material, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity. The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.

The thermoplastic resin layer and the intermediate layer can also be used as the alignment layer. In particular, polyvinyl alcohol and polyvinyl pyrrolidone preferably used for the intermediate layer are also effective as an alignment layer, and it is preferable that the intermediate layer and the alignment layer are made into one layer.

It is preferable to provide a thin protective film on the resin layer in order to protect it from contamination and damage during storage. The protective film may be made of the same or similar material as the temporary support, but must be easily separated from the resin layer. As the protective film material, for example, silicon paper, polyolefin or polytetrafluoroethylene sheet is suitable.

The polarizing film and the photosensitive resin layer, and the alignment layer, the thermoplastic resin layer, and the intermediate layer formed as desired can be formed by the same method as the polarizing film forming method. Two or more layers may be applied simultaneously. The methods of simultaneous application are described in US Pat. Nos. 2,761,791, 2,941,898, 3,508,947, and 3,526,528 and Yuji Harasaki, Coating Engineering, page 253, Asakura Shoten (1973).

3. -2 Forming method of polarizing film using transfer material:
The method for transferring the transfer material on the substrate in the present invention is not particularly limited, and the method is not particularly limited as long as the polarizing film and the photosensitive resin layer can be simultaneously transferred onto the substrate. For example, the transfer material referred to in the present invention formed in a film shape is attached by pressing or thermocompression bonding with a roller or flat plate heated and / or pressurized using a laminator with the photosensitive resin layer side facing the substrate surface side. be able to. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From this point of view, it is preferable to use the method described in JP-A-7-110575. Thereafter, the support may be peeled off, and another layer such as an electrode layer may be formed on the surface of the polarizing film exposed by peeling.

There is no particular limitation on the substrate that is a transfer material to which the transfer material is transferred. For example, a soda glass plate having a silicon oxide film on the surface, a known glass plate such as a low expansion glass, a non-alkali glass, a quartz glass plate, or a plastic film can be used. The material to be transferred may be one in which a layer such as a color filter is provided on a transparent substrate. Moreover, the material to be transferred can be well adhered to the photosensitive resin layer by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used. Although not particularly limited, the thickness of the substrate is generally preferably 700 to 1200 μm.
Instead of providing an adhesive layer on the polarizing film, an adhesive layer may be provided on the transfer material.

4). TECHNICAL FIELD The present invention relates to a display device having at least the polarizing film of the present invention. The display device of the present invention may be, for example, a TN, STN, VA, ECB, IPS, or OCB mode transmissive, reflective, or transflective liquid crystal display device; and an OLED.
Particularly preferred is a display device in which the polarizing film of the present invention is disposed on the inner surface side of the substrate (so-called in-cell polarizing film), and particularly preferred is a laminate of the polarizing film of the present invention on a color filter substrate. It is a display device.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these. Hereinafter, “part” means “part by mass”, and “%” means “% by mass”.
In the following examples, the measurement of optical characteristics of the light absorption anisotropic film was performed as follows.
<Dichroic ratio>
The dichroic ratio was calculated by the following equation after measuring the absorbance of the light-absorbing anisotropic film with a spectrophotometer in which an iodine-type polarizing element was arranged in the incident optical system.
Dichroic ratio (D) = Az / Ay
Az: Absorbance with respect to polarized light in the absorption axis direction of the light absorption anisotropic film Ay: Absorbance with respect to polarization in the polarization axis direction of the light absorption anisotropic film

[Example 1: Synthesis example of dichroic dye A-2]
A dichroic dye A-2 having the following structure was synthesized according to the following scheme.

Synthesis of Compound 1:
A solution of 10.0 parts of 4-aminobenzoic acid in 130 ml of 2.8N aqueous hydrochloric acid and ice-cooled to 0 ° C. was obtained by dissolving 5.53 parts of sodium nitrite in 20 ml of water at 5 ° C. While maintaining the following temperature, it was added little by little. After stirring for about 1 hour while maintaining the temperature and confirming the formation of the diazonium salt, 16.3 parts of m-toluidine was dissolved in 150 ml of methanol, and the temperature of 5 ° C. or lower was added to the solution cooled to 0 ° C. with ice. It was dripped little by little while keeping. After completion of dropping, the reaction solution was warmed to room temperature and neutralized with sodium hydroxide. The precipitated product was filtered, suspended and washed with acetonitrile, and dried. After drying, 13.2 parts of compound 1 were obtained.

Synthesis of compound 2:
10.0 parts of Compound 1 was dissolved in a mixed acid solvent of 16.3 ml of hydrochloric acid, 40 ml of acetic acid and 60 ml of propionic acid, and this was ice-cooled to 0 ° C., while 2.97 parts of sodium nitrite was dissolved in 10 ml of water. What was dissolved was added little by little while keeping the temperature of 5 ° C. or less. After stirring for about 1 hour while maintaining the temperature and confirming the formation of the diazonium salt, 5.84 parts of N, N-diethylaniline was dissolved in 150 ml of methanol and cooled to 0 ° C with ice at 5 ° C or less. The solution was added dropwise little by little while maintaining the temperature. After completion of the dropping, the reaction solution was warmed to room temperature, and 116 ml of water was added dropwise thereto. After neutralizing the reaction solution with sodium hydrogen carbonate, the precipitated product was filtered, washed with water and methanol, and dried. After drying, 11.0 parts of compound 2 were obtained.

Synthesis of dichroic dye A-2:
1.00 part of Compound 2 was dissolved in 10 ml of THF, 0.28 part of methanesulfonyl chloride was added, and this was cooled to -5 ° C. A solution prepared by dissolving 0.32 parts of DIPEA (diisopropylethylamine) in 2 ml of THF was added dropwise little by little while maintaining a temperature of 0 ° C. or lower. This reaction solution was added dropwise little by little while maintaining a temperature of 0 ° C. or less in a solution of 0.36 parts of 4-butylphenol and 0.32 parts of DIPEA in 5 ml of THF. The reaction solution was warmed to room temperature, and 20 ml of water and 20 ml of methanol were added. The precipitated crystals were filtered, washed with methanol, and dried to obtain 0.80 part of A-2. Λmax of A-2 in the N-methylpyrrolidone solvent was 522.9 nm. That is, it was a magenta dye.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: 8.35 (d, 2H), 8.03 (d, 2H), 7.89 (d, 2H), 7.80 (m, 2H), 7.75 (d, 1H), 7.25 (d, 2H), 7.12 (d, 2H), 6.73 (d, 2H), 3.47 (q, 4H), 2.82 (s , 3H), 2.64 (t, 2H), 1.60 (m, 2H), 1.38 (m, 2H), 1.25 (t, 6H), 0.92 (t, 3H). It was.
A-2 has liquid crystallinity, and a nematic phase was confirmed in the range of 178 ° C. to 244 ° C. Moreover, it was confirmed that it was a dichroic dye by observation with a polarizing microscope.

[Example 2: Synthesis example of dichroic dye A-9]
A dichroic dye A-9 having the following structure was synthesized according to the following synthesis scheme.

Synthesis of compound 3:
Dissolve 12.1 parts of 4-aminobenzaldehyde in 85 ml of 3.5N aqueous hydrochloric acid and cool it to 0 ° C with ice, and dissolve 5 parts of sodium nitrite in 20 ml of water at 5 ° C or less. Was added little by little while maintaining the temperature. After stirring for about 1 hour while maintaining the temperature and confirming the formation of the diazonium salt, the insoluble material was filtered off, and 11.8 parts of m-toluidine was dissolved in 80 ml of methanol and cooled to 0 ° C with ice. The solution was added dropwise little by little while maintaining a temperature of 5 ° C. or lower. After completion of the dropwise addition, the reaction solution was warmed to room temperature, the precipitated product was filtered, suspended and washed with methanol, and dried. After drying, 15.0 parts of compound 3 were obtained.

Synthesis of compound 4:
5.51 parts of Compound 3 was dissolved in a mixed acid solvent of 5.0 ml of hydrochloric acid, 28 ml of acetic acid, and 14 ml of water, and 1.52 parts of sodium nitrite was dissolved in 5 ml of water against this which was ice-cooled to 0 ° C. The resulting mixture was added little by little while maintaining the temperature of 5 ° C. or lower. The mixture was stirred for about 1 hour while maintaining the temperature. After confirming the formation of the diazonium salt, the insoluble matter was filtered off, 2.98 parts of N, N-diethylaniline was dissolved in 100 ml of methanol, and cooled to 0 ° C. with ice. The solution was added dropwise little by little while maintaining a temperature of 5 ° C. or lower. After completion of the dropwise addition, the reaction solution is warmed to room temperature, and 100 ml of water is added dropwise thereto. After neutralizing the reaction solution with sodium hydrogen carbonate, the precipitated product was filtered, washed with water and methanol, and dried. After drying, 6.30 parts of compound 4 were obtained.
Synthesis of dichroic dye A-9:
1.00 part of Compound 4 was dissolved in 10 ml of toluene, 0.34 part of 4-propylaniline and a catalytic amount of paratoluenesulfonic acid were added, and the mixture was stirred under reflux for 3 hours. The reaction solution was returned to room temperature, 30 ml of methanol was added, the precipitated crystals were filtered, washed with methanol, and dried to obtain 0.92 parts of A-9.
Λmax of A-9 in N-methylpyrrolidone solvent was 521.0 nm. That is, it was a magenta dye.
The details of ¹ H-NMR (CDCl ₃ ) are 8.53 (s, 1H), 8.03 (t, 4H), 7.85 (d, 2H), 7.80 (m, 2H), 7.71 (d, 1H), 7.22 (d, 2H), 6.72 (d, 2H), 3.47 (q, 4H), 2.82 (s, 3H), 2.61 (t , 2H), 1.65 (m, 2H), 1.23 (t, 6H), and 0.96 (t, 3H).
A-9 has liquid crystallinity, and a nematic phase was confirmed in the range of 168 ° C. to 288 ° C. Moreover, it was confirmed that it was a dichroic dye by observation with a polarizing microscope.

[Example 3: Synthesis example of dichroic dye A-26]

A dichroic dye A-26 having the following structure was synthesized according to the following synthesis scheme.

Synthesis of compound 5:
A solution of 10.0 parts of 4-aminobenzoic acid in 130 ml of 2.8N aqueous hydrochloric acid and ice-cooled to 0 ° C. was obtained by dissolving 5.53 parts of sodium nitrite in 20 ml of water at 5 ° C. While maintaining the following temperature, it was added little by little. After stirring for about 1 hour while maintaining the temperature and confirming the formation of the diazonium salt, 1.09 parts of N, N-diethylaniline was dissolved in 150 ml of methanol and cooled to 0 ° C with ice at 5 ° C or less. The solution was added dropwise little by little while maintaining the temperature. After completion of the dropping, the reaction solution was warmed to room temperature, and 116 ml of water was added dropwise thereto. After neutralizing the reaction solution with sodium hydrogen carbonate, the precipitated product was filtered, washed with water and methanol, and dried. After drying, 21.0 parts of compound 5 were obtained.

Synthesis of compound 6:
Dissolve 5.00 parts of 4-aminopyridine in 25 ml of 85% aqueous phosphoric acid solution, and add 4.03 parts of sodium nitrite little by little while maintaining the temperature at 5 ° C or lower with respect to what was ice-cooled to 0 ° C. did. After stirring for about 1 hour while maintaining the temperature and confirming the formation of the diazonium salt, 5.74 parts of orthocresol was dissolved in 5.0N aqueous sodium hydroxide solution and cooled to 5 ° C with ice at 30 ° C. The solution was dropped little by little while maintaining the following temperature. 220 ml of water was added to the reaction solution, neutralized with hydrochloric acid, and extracted with ethyl acetate. The extract was dried over sodium sulfate, concentrated, suspended and washed with acetonitrile, and 3.80 parts of compound 6 was obtained.

Synthesis of dichroic dye A-26:
1.00 part of Compound 5 was dissolved in 10 ml of THF, 0.38 part of methanesulfonyl chloride was added, and this was cooled to -5 ° C. What melt | dissolved 0.43 part DIPEA in 2 ml THF here was dripped little by little, keeping the temperature of 0 degrees C or less. This reaction solution was added dropwise little by little while maintaining a temperature of 0 ° C. or lower in a solution obtained by dissolving 0.72 parts of Compound 6 and 0.43 parts of DIPEA in 5 ml of THF. The reaction solution was warmed to room temperature, and 20 ml of water and 20 ml of methanol were added. The precipitated crystals were filtered, washed with methanol, and dried to obtain 0.75 part of A-26.
Λmax of A-26 in N-methylpyrrolidone solvent was 478.0 nm. That is, it was a yellow dye.
The details of ¹ H-NMR (CDCl ₃ ) are 8.80 (d, 2H), 8.32 (d, 2H), 7.91 (t, 6H), 7.70 (d, 2H), 7.37 (d, 1H), 6.74 (d, 2H), 3.47 (q, 4H), 2.37 (s, 3H), 1.25 (t, 6H).
A-26 has liquid crystallinity, and a nematic phase was confirmed in the range of 170 ° C. to 200 ° C. when the temperature was lowered. Moreover, it was confirmed that it was a dichroic dye by observation with a polarizing microscope.

Other compound examples can be synthesized by the same method as described above.
The following shows the behavior of λmax in the N-methylpyrrolidone solvent of the compound example and the change in the liquid crystal layer by observation with a polarizing microscope.

[Example 4]
1 part by mass of dichroic dye A-2 was added to 99 parts by mass of chloroform, dissolved by stirring and filtered to obtain a dichroic dye composition coating solution. Next, the coating solution was applied onto an alignment film formed on a glass substrate and rubbed, and then the film was naturally dried at room temperature to form a film. The following polyvinyl alcohol was used as the alignment film.

The dichroic ratio obtained from the absorbance (Az) for polarized light having a vibration plane in the absorption axis direction in the plane of the film and the absorbance (Ay) for polarized light having a vibration plane in the direction of the polarization axis in the film plane ( D) was 18. That is, it was found that the obtained film had light absorption anisotropy and could function as a polarizing film.

[Example 5]
1 part by mass of dichroic dye A-9 was added to 99 parts by mass of chloroform, dissolved by stirring and filtered to obtain a dichroic dye composition coating solution. Using this coating solution, a film was prepared in the same manner as in Example 4.
The dichroic ratio obtained from the absorbance (Az) with respect to polarized light having a vibration plane in the in-plane absorption axis direction and the absorbance (Ay) with respect to polarized light having a vibration plane in the direction of the polarization axis in the film ( D) was 58. That is, it was found that the obtained film had light absorption anisotropy and could function as a polarizing film.

[Example 6]
Add 0.5 parts by weight of dichroic dye A-9 and 0.5 parts by weight of dichroic dye A-26 to 99 parts by weight of chloroform, stir and dissolve, and filter to obtain a dichroic dye composition coating solution. Obtained. Using this coating solution, a film having a thickness of 0.05 to 0.2 μm was produced in the same manner as in Example 4.
The dichroic ratio obtained from the absorbance (Az) with respect to polarized light having a vibration plane in the in-plane absorption axis direction and the absorbance (Ay) with respect to polarized light having a vibration plane in the direction of the polarization axis in the film ( D) was 37. That is, it was found that the obtained film had light absorption anisotropy and could function as a polarizing film.

[Example 7]
Add 0.3 parts by weight of dichroic dye A-9, 0.3 parts by weight of dichroic dye A-26, and 0.4 parts by weight of dichroic dye B below to 99 parts by weight of chloroform, and dissolve with stirring. After filtration, a dichroic dye composition coating solution was obtained. The dichroic dye B has an absorption maximum wavelength in NMP of 615.0 nm, that is, a cyan dye, has a nematic phase in the range of 209 ° C. to 227 ° C., and is observed with a polarizing microscope. Was confirmed to be a dichroic dye.
Using this coating solution, a film was prepared in the same manner as in Example 4. Two colors obtained from the absorbance (Az) with respect to the polarized light having the vibration plane in the absorption axis direction within the film surface and the absorbance (Ay) with respect to the polarized light having the vibration plane in the polarization axis direction within the surface of the obtained film. The ratio (D) was 28. That is, it was found that the obtained film had light absorption anisotropy and could function as a polarizing film.
Further, the obtained light absorption anisotropic film has a black hue, and the transmitted light spectrum using the C light source as the light source has x = 0.29, y = 0. A value of 32 was indicated.

[Example 8]
To 99 parts by mass of chloroform, 0.4 part by mass of dichroic dye A-26 and 0.6 part by mass of dichroic dye B were added, dissolved by stirring, and filtered to obtain a dichroic dye composition coating solution. . Using this coating solution, a film having a thickness of 0.05 to 0.2 μm was produced in the same manner as in Example 4.
The dichroic ratio obtained from the absorbance (Az) with respect to polarized light having a vibration plane in the in-plane absorption axis direction and the absorbance (Ay) with respect to polarized light having a vibration plane in the direction of the polarization axis in the film ( D) was 28. That is, it was found that the obtained film had light absorption anisotropy and could function as a polarizing film.
Further, the obtained light absorption anisotropic film has a black hue, and the transmitted light spectrum using the C light source as the light source is x = 0.32, y = 0. A value of 34 was shown.

[Comparative Example 1]
The dichroic ratio was similarly measured for a film formed from a composition containing a liquid crystal material and a dichroic dye described in JP-T-2007-536415. The film thickness was 2-8 μm. As a result, it was found that the dichroic ratio of this comparative example film was 13, which was much lower than that of the example of the present invention.

[Comparative Example 2]
In 99 parts by mass of chloroform, an azo dye No. 1 described in JP-A-11-305036 was prepared. 1 part by mass of (6) was added, and after stirring and dissolving, the mixture was filtered to obtain a dichroic dye composition coating solution. Using this coating solution, a film having a thickness of 0.05 to 0.2 μm was produced in the same manner as in Example 4. The dye had nematic liquid crystal properties, but crystallization occurred on the alignment film and did not show anisotropy.

Claims

Dichroic dye composition containing at least one dichroic dye having liquid crystallinity represented by the following general formula (I):

In the formula, each of Ar 1 to Ar 4 represents an aromatic hydrocarbon group, an aromatic heterocyclic group and a cyclohexane ring group, each of which may have a substituent; L 1 and L 2 are an azo group and an ester group, respectively. Represents an imino group or a vinylene group, provided that L 1 and L 2 are not both azo groups.
The dichroic dye composition according to claim 1, which contains substantially no liquid crystalline non-colored material.
The dichroic dye composition according to claim 1 or 2, wherein at least one of the dichroic dyes represented by the general formula (I) is a compound represented by the following general formula (II):

Wherein, L 11 and L 12 are each, azo group, an ester group, an imino group, or a vinylene group, provided that never L 11 and L 12 is an azo group together; R 11 ~ R 15 each Represents a hydrogen atom or a substituent, and R 11 and R 13 may form a ring with each other; A 1 represents a substituted or unsubstituted carbon atom or a nitrogen atom.
It contains at least two dichroic dyes having liquid crystallinity represented by the general formula (II), and at least one of the two or more dichroic dyes is L 11 in the formula (II). The dichroic dye composition according to claim 3, wherein is a compound having an azo group.
The dichroic dye according to any one of claims 1 to 4, wherein at least one of the dichroic dyes represented by the general formula (I) is a compound represented by the following general formula (III): Composition:

In the formula, L 21 represents an ester group, an imino group, or a vinylene group; L 22 represents an azo group, an ester group, an imino group, or a vinylene group; R 21 to R 25 each represent a hydrogen atom or a substituent. R 21 and R 23 may form a ring with each other; A 2 represents a substituted or unsubstituted carbon atom or a nitrogen atom.
The dichroic dye according to any one of claims 1 to 5, wherein at least one of the dichroic dyes represented by the general formula (I) is a compound represented by the following general formula (IV): Composition:

Represents wherein, L 31 is an imino group, or a vinylene group; R 31 ~ R 35 each represents a hydrogen atom or a substituent, R 31 and R 33 may form a mutually ring; A 3 is a substituted Alternatively, it represents an unsubstituted carbon atom or a nitrogen atom.
R 11 , R 12 , R 21 , R 22 , R 31 and R 32 are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R 13 , R 23 and R 33 are each a hydrogen atom R 14 , R 24 , R 34 , R 15 , R 25 and R 35 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a plurality of heteroatoms having 1 to 6 carbon atoms. An alkoxy group which may contain; a carbon atom in which A 1 , A 2 and A 3 may contain a nitrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a plurality of heteroatoms; 7. The dichroic dye composition according to claim 4, which is a carbon atom substituted with an alkoxy group having 1 to 6 atoms, a cyano group, or a substituted amino group.
The dichroism according to any one of claims 1 to 7, comprising at least one dichroic dye having liquid crystallinity represented by the general formula (I) as a magenta dye and / or a yellow dye. Dye composition.
The dichroic dye composition according to claim 8, comprising at least one compound represented by formula (III) according to claim 5 as a yellow dye.
The dichroic dye composition according to claim 8 or 9, which contains at least one compound represented by formula (IV) according to claim 6 as a magenta dye.
The dichroic dye composition according to any one of claims 1 to 10, further comprising at least one dichroic azo dye having liquid crystallinity as a cyan dye.
A polarizing film comprising the dichroic dye composition according to any one of claims 1 to 11.
The polarizing film according to claim 12, which is formed by coating.
The polarizing film according to claim 13, wherein transmitted light when a C light source is used as the light source satisfies 0.28 <x <0.36 and 0.28 <y <0.36 in the xy chromaticity diagram.
A liquid crystal cell comprising a pair of substrates, a liquid crystal layer, a color filter layer, and the polarizing film according to any one of claims 12 to 14 disposed therebetween.
The liquid crystal cell according to claim 15, wherein the polarizing film is provided between the color filter layer and the liquid crystal layer.
A display device comprising the polarizing film according to any one of claims 12 to 14.
A liquid crystal display device comprising the liquid crystal cell according to claim 15.
A dichroic dye having liquid crystallinity represented by the following general formula (III):

In the formula, L 21 represents an ester group, an imino group, or a vinylene group; L 22 represents an azo group, an ester group, an imino group, or a vinylene group; R 11 to R 15 each represent a hydrogen atom or a substituent. R 11 and R 13 may form a ring with each other; A 2 represents a substituted or unsubstituted carbon atom or a nitrogen atom.
R 21 and R 22 are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R 23 is a hydrogen atom; R 24 and R 25 are a hydrogen atom and 1 carbon atom, respectively. An alkyl group having 6 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, which may contain a plurality of heteroatoms; A 2 is a nitrogen atom, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms The dichroic dye according to claim 19, which is a carbon atom substituted with an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a substituted amino group, which may contain a group or a plurality of heteroatoms.
A dichroic dye having liquid crystallinity represented by the following general formula (IV):

Represents wherein, L 31 is an imino group, or a vinylene group; R 31 ~ R 35 each represents a hydrogen atom or a substituent, R 31 and R 33 may form a mutually ring; A 3 is a substituted Alternatively, it represents an unsubstituted carbon atom or a nitrogen atom.
R 31 and R 32 are each a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R 33 is a hydrogen atom; R 34 and R 35 are each a hydrogen atom, 1 to An alkyl group having 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms which may contain a plurality of heteroatoms; A 3 is a nitrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms The dichroic dye according to claim 21, which is a carbon atom substituted with an alkoxy group having 1 to 6 carbon atoms, a cyano group, or a substituted amino group, which may contain a plurality of heteroatoms.