WO2013084932A1

WO2013084932A1 - Colorant, colored composition, color filter, and display element

Info

Publication number: WO2013084932A1
Application number: PCT/JP2012/081498
Authority: WO
Inventors: 米田　英司; 江幡　敏; 英徹吉澤; 紫山口; 伊藤　淳史; 泰典川部
Original assignee: Jsr株式会社
Priority date: 2011-12-09
Filing date: 2012-12-05
Publication date: 2013-06-13
Also published as: JPWO2013084932A1; TW201333120A

Abstract

　Provided is a colored composition that can form a green colored layer with favorable color properties. This colored composition contains the following components (A), (B), and (C). (A): a triaryl methane colorant having at least one sulfur-containing aromatic heterocyclic group; (B): a binder resin; and (C): a cross-linking agent.

Description

Colorant, coloring composition, color filter and display element

The present invention relates to a colorant, a coloring composition, a color filter, and a display element. More specifically, the present invention relates to a color used for a transmissive or reflective color liquid crystal display element, solid-state imaging element, organic EL display element, electronic paper, and the like. The present invention relates to a colorant suitably used for producing a filter, a color composition containing the colorant, a color filter including a colored layer formed using the color composition, and a display element including the color filter.

In manufacturing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. (Hereinafter, referred to as “exposure”) and a method of obtaining pixels of each color by development (Patent Documents 1 and 2) are known. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method of obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

In recent years, there has been a strong demand for higher contrast of liquid crystal display elements and higher definition of solid-state imaging elements, and in order to realize these, application of dyes and lake pigments as colorants is being studied. For example, as a coloring composition capable of forming a blue colored layer having excellent chromaticity characteristics, a coloring composition containing a triarylmethane dye, a xanthene dye or the like as a colorant has been proposed. Also known is a method of forming each color pixel pattern of red, green and blue by an ink jet method using a coloring composition containing a dye having one or more polymerizable functional groups as a colorant (Patent Document). 5).

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2004-20897 A

However, in Patent Document 5, pixel patterns of each color including green are formed and resistance evaluation is performed for chemical resistance and weather resistance, and no consideration is given to the chromaticity characteristics of each pixel. Thus, the present condition is that sufficient examination is not made | formed until now about the coloring composition which can be used for formation of the green colored layer which is excellent in chromaticity characteristic. Therefore, development of a coloring composition suitable for producing a green color filter having good chromaticity characteristics is strongly demanded.

Therefore, an object of the present invention is to provide a coloring composition capable of forming a green coloring layer having good chromaticity characteristics, and a coloring agent applicable to the coloring composition. Another object of the present invention is to provide a color filter including a colored layer containing the colorant and a display element including the color filter.

In view of such circumstances, the present inventors have conducted extensive research and found that the above-described problems can be solved by using a green colorant having a specific structure, and the present invention has been completed.

That is, this invention provides the coloring composition containing the following component (A), (B) and (C).
(A) a triarylmethane colorant having one or more sulfur-containing aromatic heterocyclic groups (hereinafter also referred to as “the present colorant”),
(B) binder resin, and (C) cross-linking agent

The present invention also provides a color filter comprising a colored layer containing the present colorant and a display element comprising the color filter. Here, the “colored layer” means each color pixel such as green used for a color filter, a black matrix, a black spacer, and the like.

Furthermore, the present invention provides a triarylmethane colorant having a structure represented by the following formula (1-1) or formula (1-2).

[In Formula (1-1),
a represents an integer of 0 to 4. ;
b represents an integer of 0 to 4. ;
Ar represents a substituted or unsubstituted aromatic hydrocarbon group. ;
R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. ;
R ^p and R ^q each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′, —SO ₃ ^— or a halo group. R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ;
X ¹ and X ² each independently represent a single bond or a substituted or unsubstituted aromatic hydrocarbon group. ;
Y ¹ and Y ² each independently represent a hydrogen atom or a substituted or unsubstituted sulfur-containing aromatic heterocyclic group. ;
However, in the compound, Y ¹ and Y ² are not simultaneously hydrogen atoms. ]

[In Formula (1-2),
a, b, Ar, R ^p , R ^q , X ¹ , X ² , Y ¹ and Y ² are as defined above. ;
X ³ represents a single bond or a substituted or unsubstituted aromatic hydrocarbon group. ;
Y ³ represents a hydrogen atom or a substituted or unsubstituted sulfur-containing aromatic heterocyclic group. ;
However, in the compound, Y ¹ , Y ² and Y ³ are not simultaneously hydrogen atoms. ]

If the colored composition of the present invention is used, a green colored layer having excellent chromaticity characteristics can be formed. Therefore, the colored composition of the present invention is used for the production of various color filters including color filters for display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described components of the colored composition of the present invention.

-(A) Colorant-
The coloring composition of this invention contains this coloring agent as (A) coloring agent.
The colorant is a triarylmethane colorant having one or more sulfur-containing aromatic heterocyclic groups, but is particularly limited as long as it is a triarylmethane compound having one or more sulfur-containing aromatic heterocycles as a substituent. Is not to be done.

First, the sulfur-containing aromatic heterocyclic group which this coloring agent has is demonstrated.
In the present invention, the “sulfur-containing aromatic heterocyclic group” possessed by the coloring agent refers to an aromatic heterocyclic group having at least one sulfur atom as a ring component. The structure of the sulfur-containing aromatic heterocyclic group is an aromatic heterocyclic monocyclic group, an aromatic condensed heterocyclic group formed by condensation of an aromatic heterocyclic monocycle and one or more benzene rings, or the same or An aromatic condensed heterocyclic group formed by condensing two or more different aromatic heterocyclic monocycles is preferable. These sulfur-containing aromatic heterocyclic groups may have a hetero atom (for example, an oxygen atom or a nitrogen atom) other than a sulfur atom in the ring.

Examples of such sulfur-containing aromatic heterocycles include thiophene ring, thiazole ring, thiazine ring, 1,3,4-thiadiazole ring, benzothiophene ring, benzothiazine ring, thienopyrimidine ring, thienothiophene ring, dibenzothiophene ring. And a phenothiazine ring. Of these, a thiophene ring, a benzothiophene ring, and a dibenzothiophene ring are preferable, and a thiophene ring and a benzothiophene ring are particularly preferable.

The sulfur-containing aromatic heterocyclic group may have a substituent, and the substituent is preferably an electron donating group. Here, in the present invention, the “electron donating group” means a substituent having an effect of increasing the electron density at a specific position of the sulfur-containing aromatic heterocyclic ring. Specifically, alkyl group, cycloalkyl group, hydroxy group, alkoxy group, phenoxy group, amino group, alkylamino group, dialkylamino group, cycloalkylamino group, dicycloalkylamino group, arylamino group, diarylamino group Acetylamino group, hydroxyl group, halo group, thiol group, alkylthio group, thioether group, heterocyclic group, etc., among them, alkyl group, alkoxy group, amino group, alkylamino group, dialkylamino group, cycloalkyl Examples thereof include an amino group, a dicycloalkylamino group, an arylamino group, a diarylamino group, and a thioether group. Among them, an alkyl group having 1 to 20 carbon atoms and an amino group are preferable, and the amino group may be substituted with one or more alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, or phenyl groups. . Further, these groups may be further substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, an alkoxy group, a thiol group, an amino group, a halo group, or the like as long as the electron donating property is not lost. .

As the alkyl group, an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly 1 to 8 carbon atoms is preferable. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, amyl group, tertiary amyl group, hexyl group, heptyl group, octyl group, An isooctyl group, a tertiary octyl group, a 2-ethylhexyl group, etc. can be mentioned.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
As the alkoxy group, an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly 1 to 8 carbon atoms is preferable. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.
The alkylthio group is preferably an alkylthio group having 1 to 6 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, and a butylthio group.
The thioether group is preferably a thioether group having 1 to 6 carbon atoms, and specific examples thereof include a methylthioether group, an ethylthioether group, a propylthioether group, an isopropylthioether group, and a butylthioether group.
Examples of the alkyl group in the alkylamino group and dialkylamino group include the same alkyl groups having 1 to 20 carbon atoms as described above. Examples of the cycloalkyl group in the cycloalkylamino group and the dicycloalkylamino group include the same cycloalkyl groups having 3 to 8 carbon atoms as described above. The aryl group in the arylamino group and diarylamino group is preferably an aryl group having 6 to 20 carbon atoms, and specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, and an azulenyl group.
Examples of the halo group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
As the heterocyclic group, a monovalent heterocyclic group having 3 to 10 carbon atoms is preferable. Specifically, a pyrrolidinyl group, an imidazolidinyl group, a pyrazolidinyl group, a piperidyl group, a piperidino group, a piperazinyl group, a homopyrerazinyl group, a morpholinyl group, Alicyclic heterocyclic group such as theomorpholinyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, quinolyl group, isoquinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, thienyl group, furyl group, pyranyl group, pyrrolyl group, Examples thereof include aromatic heterocyclic groups such as imidazolyl group, pyrazolyl group, triazoyl group, tetrazolyl group, thiazolyl group, oxazolyl group, indolyl group, indazolyl group, benzoimidazolyl group and purinyl group.

Among them, the sulfur-containing aromatic heterocyclic group is preferably a group obtained by removing one hydrogen atom from thiophene or benzothiophene. The remaining hydrogen atom of the group obtained by removing one hydrogen atom from thiophene or benzothiophene may be substituted with another electron donating group.
As the electron donating group possessed by the sulfur-containing aromatic heterocyclic group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an amino group are particularly preferable. The amino group may be substituted by one or more alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, or phenyl groups.

More preferable examples of the sulfur-containing aromatic heterocyclic group include a group represented by the following formula (2).

[In Formula (2),
s represents 0 or 1. ;
t represents an integer of 0 ≦ t ≦ (2s + 3). ;
R ⁵ independently represents a hydrogen atom, —NR ⁶ R ⁷ , an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. ;
* Indicates a bond. ]

In the above formula (2), s represents 0 or 1.
When s = 0, t represents an integer of 0 to 3, and when s = 1, t represents an integer of 0 to 5, but when s is 0 or 1, t is 0 to An integer of 2 is preferred.
Examples of the alkyl group having 1 to 8 carbon atoms in —NR ⁶ R ⁷ of R ⁵ include the same ones as described above. Of these, an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms is preferable. In addition, examples of the cycloalkyl group having 3 to 8 carbon atoms in —NR ⁶ R ⁷ include the same ones as described above. Of these, a cycloalkyl group having 5 to 6 carbon atoms is preferable. Furthermore, examples of the alkyl group having 1 to 20 carbon atoms in R ⁵ include the same as those described above. Of these, an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms is preferable.

Examples of the preferred colorant in the present invention include a triarylmethane colorant having a structure represented by the following formula (1-1) or formula (1-2). Various structures exist in the structure represented by the following formula (1-1) or formula (1-2). In the present invention, these resonance structures are represented by the following formula (1-1) or formula (1). The structure is equivalent to that represented by (1-2).

In the above formulas (1-1) and (1-2), the aromatic hydrocarbon group for Ar is preferably an arylene group having 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. Specific examples include groups in which two hydrogen atoms have been removed from the arene ring of a benzene ring, naphthalene ring, biphenyl ring, anthracene ring, phenanthrene ring, and azulene ring. Especially, as an aromatic hydrocarbon group in Ar, a phenylene group, a naphthylene group, and an anthrylene group are preferable, and a phenylene group and a naphthylene group are more preferable.
The remaining hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent, and examples of the substituent include an alkyl group having 1 to 8 carbon atoms, —COOR ′, —SO ₃ ⁻ , halo. The group can be mentioned. Here, R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. In addition, the position and number of substituents are arbitrary, and when it has two or more substituents, the substituents may be the same or different. Specific examples of the alkyl group and halo group having 1 to 8 carbon atoms are the same as those described above.

Examples of the alkyl group having 1 to 8 carbon atoms in R ¹ , R ² , R ^p , R ^q and R ′ include the same as those described above. Of these, an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms is preferable.

Examples of the cycloalkyl group having 3 to 8 carbon atoms in R ¹ and R ² are the same as those described above. Of these, a cycloalkyl group having 5 to 6 carbon atoms is preferable.
Examples of the halo group for R ¹ and R ² are the same as those described above.

Among these, as R ¹ and R ² , independently of each other, a hydrogen atom or an alkyl group having 1 to 8 carbon atoms is preferable, and at least one of R ¹ and R ² is an alkyl group having 1 to 8 carbon atoms. More preferably, both R ¹ and R ² are particularly preferably alkyl groups having 1 to 8 carbon atoms.
R ^p and R ^q are preferably independently of each other a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

The aromatic hydrocarbon group for X ¹ to X ³ is preferably an arylene group having 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms, and specific examples thereof include those described above.
The remaining hydrogen atoms of these aromatic hydrocarbon groups may be substituted with a substituent, and examples of the substituent include the same alkyl groups having 1 to 6 carbon atoms as described above. In addition, the position and number of substituents are arbitrary, and when it has two or more substituents, the substituents may be the same or different.
Among these, as X ¹ to X ³ , a single bond or a phenylene group is preferable independently of each other.

The sulfur-containing aromatic heterocyclic group in Y ¹ to Y ³ is as described above.
Among them, Y ¹ to Y ³ are each independently preferably a group obtained by removing one hydrogen atom from thiophene or benzothiophene, and particularly preferably a group represented by the formula (2). Note that the remaining hydrogen atom of the group obtained by removing one hydrogen atom from thiophene or benzothiophene may be substituted with another electron-donating group.

a represents an integer of 0 to 4, preferably 0 or 1.
B represents an integer of 0 to 4, preferably 0 or 1.

In the present invention, among the structures represented by the above formula (1-1) or formula (1-2), the following formula (3-1) or formula (3- Those having the structure represented by 2) are preferred.

[In Formula (3-1),
a, b, R ¹ , R ² , R ^p and R ^q are as defined above. ;
c represents an integer of 0 to 4. ;
e and g each independently represent 0 or 1; ;
f represents an integer of 0 ≦ f ≦ (2e + 3). ;
h represents an integer of 0 ≦ h ≦ (2g + 3). ;
R ⁸ and R ⁹ each independently represent a hydrogen atom, —NR ⁶ R ⁷ , an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, R ⁶ and R ⁷ are as defined above. ;
R ^r represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′, —SO ₃ ^— or a halo group. R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[In Formula (3-2),
a, b, c, e, f, g, h, R ⁸ , R ⁹ , R ^p , R ^q and R ^r are as defined above. ;
j represents 0 or 1; ;
k represents an integer of 0 ≦ k ≦ (2j + 3). ;
R ¹⁰ represents a hydrogen atom, —NR ⁶ R ⁷ , an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, R ⁶ and R ⁷ are as defined above. ]

In the above formulas (3-1) and (3-2), when e = 0, f represents an integer of 0 to 3, and when e = 1, f represents an integer of 0 to 5, In the case where e is 0 or 1, f is preferably an integer of 0 to 2, more preferably 0 or 1.
When g = 0, h represents an integer of 0 to 3, and when g = 1, it represents an integer of 0 to 5. However, when g is 0 or 1, h is 0 to 2. An integer is preferable, and 0 or 1 is more preferable.
When j = 0, k represents an integer from 0 to 3, and when j = 1, k represents an integer from 0 to 5, but when j is 0 or 1, k is from 0 to An integer of 2 is preferable, and 0 or 1 is more preferable.
R ⁸ to R ¹⁰ are each independently preferably a hydrogen atom, —NR ⁶ R ⁷ , an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, and R ⁶ and R ⁷ are Independently of each other, an alkyl group having 1 to 8 carbon atoms is preferred. Specific examples are as described above.

Typical examples of the structure represented by the above formula (1-1), formula (1-2), formula (3-1) or formula (3-2) include, for example, a cation represented by the following formula: Among them, compound a, compound e, compound g, compound h, compound i, compound l, compound n, compound o, compound p, and compound r are preferable, and compound e, compound g, compound h, and compound are particularly preferable. i, Compound l, Compound n, Compound o, Compound p, and Compound r are preferable.

On the other hand, when the coloring agent has a counter ion so as to be electrically neutral, the counter ion is not particularly limited. That is, when the chromophore having a sulfur-containing aromatic heterocyclic group is a cation, examples of the anion moiety of the colorant include a halogen ion, a boron anion, a phosphate anion, a carboxylate anion, a sulfate anion, and an organic sulfonic acid. Anions, nitrogen anions, methide anions and the like can be used as the anion portion of the present colorant.

Examples of halogen ions include fluoride ions, chloride ions, bromide ions, iodide ions, and the like.

Further, as the boron anion, for example, BF ₄ ^-, etc. of the inorganic boron anion;
(CF ₃ ) ₄ B ⁻ , (CF ₃ ) ₃ BF ⁻ , (CF ₃ ) ₂ BF ₂ ⁻ , (CF ₃ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₄ B ⁻ , (C ₂ F ₅ ) ₃ BF ⁻ , (C ₂ F ₅ ) BF ₃ ⁻ , (C ₂ F ₅ ) ₂ BF ₂ ⁻ , (CF ₃ ) (C ₂ F ₅ ) ₂ BF ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , [( CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ⁻ , (CF ₃ C ₆ H ₄ ) ₄ B ⁻ , (C ₆ F ₅ ) ₂ BF ₂ ⁻ , (C ₆ F ₅ ) BF ₃ ⁻ , (C ₆ H ₃ F ₂ ) ₄ B ⁻ , B (CN) ₄ ⁻ , B (CN) F ₃ ⁻ , B (CN) ₂ F ₂ ⁻ , B (CN) ₃ F ⁻ , (CF ₃ ) ₃ B (CN) ⁻ , (CF ₃ ) ₂ B (CN) ₂ ⁻ , (C ₂ F ₅ ) ₃ B (CN) ⁻ , (C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (nC ₃ F ₇ ) ₃ B (CN) ⁻ , (nC ₄ F ₉ ) ₃ B (CN) ⁻ , (nC ₄ F ₉ ) ₂ B (CN) ₂ ⁻ , (nC ₆ F ₁₃ ) ₃ B (CN) ⁻ , (CHF ₂ ) ₃ B (CN) ⁻ , (CHF ₂ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CF ₃ ) ₃ B (CN) ⁻ , (CH ₂ CF ₃ ) ₂ B (CN) ₂ ⁻ , (CH ₂ C ₂ F ₅ ) ₃ B (CN) ⁻ , (CH ₂ C ₂ F ₅ ) ₂ B (CN) ₂ ⁻ , (CH ₂ CH ₂ C ₃ F ₇ ) ₂ B (CN) ₂ ⁻ , (nC ₃ _{_{_{F 7 CH 2) 2 B (}}} CN) 2 -, (C 6 H 5) 3 B (CN) -, tetraphenylborate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl ) Borate, tetrakis (tetrafluorophenyl) borate, tetrakis (pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [ In addition to organic boron anions such as lith (pentafluorophenyl), phenyl] borate and tridecahydride-7,8-dicarboundeborate, JP10-195119, JP2010-094807, JP2006 Examples include boron anions described in JP-A Nos. 243594, 2002-341533, and 08-015521.

Examples of phosphate anions include inorganic phosphate anions such as HPO ₄ ²⁻ , PO ₄ ³⁻ , and PF ₆ ⁻ ;
(C ₂ F ₅ ) ₂ PF ₄ ⁻ , (C ₂ F ₅ ) ₃ PF ₃ ⁻ , [(CF ₃ ) ₂ CF] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (n− _{_{_{_{C 3 F 7) 2 PF 4}}}} -, (n-C 3 F 7) 3 PF 3 -, (n-C 4 F 9) 3 PF 3 -, (C 2 F 5) (CF 3) 2 PF 3 - [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ⁻ , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ⁻ , (n—C ₄ F ₉ ) ₂ PF ₄ ⁻ , (n—C ₄ F ₉ ) ₃ PF ₃ ⁻ , (C ₂ F ₄ H) (CF ₃ ) ₂ PF ₃ ⁻ , (C ₂ F ₃ H ₂ ) ₃ PF ₃ ⁻ , (C ₂ F ₅ ) (CF ₃ ) ₂ PF ₃ ⁻ , octyl Examples thereof include organic phosphate anions such as phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, and nonylphenyl phosphate anion.

Examples of the carboxylate anion include, for example, CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ^{− and the} like described in JP-A-2009-265641 and JP-A-2008-096680. Mention may be made of acid anions.

Examples of sulfate anions include sulfate anions and sulfite anions.
Examples of the organic sulfonate anion include alkyl sulfonate anions such as methane sulfonic acid, ethane sulfonic acid, trifluoromethane sulfonic acid, and nonafluorobutane sulfonic acid;
In addition to arylsulfonic acid anions such as benzenesulfonic acid, benzenedisulfonic acid ion, p-toluenesulfonic acid, p-trifluoromethylsulfonic acid, pentafluorobenzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid ion, international publication 2011 / 037195 pamphlet, Japanese Patent No. 3736221, and Japanese Patent Application Laid-Open No. 2011-070172.

Examples of the nitrogen anion include [(CN) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ SO ₂ )] ⁻ , and [(CF ₃ SO ₂ ). ₂ N] ⁻ , [(FSO ₂ ) N (CF ₃ CF ₂ SO ₂ )] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₂ CFSO ₂ }] ⁻ , [(FSO ₂ ) N (CF ₃ CF _{_{_{^{2 CF 2 SO 2)] -}}}} , [(FSO 2) N (CF 3 CF 2 CF 2 CF 2 SO 2)] -, [(FSO 2) N {(CF 3) 2 CFCF 2 SO 2}] -, In addition to [(FSO ₂ ) N {CF ₃ CF ₂ (CF ₃ ) CFSO ₂ }] ⁻ , [(FSO ₂ ) N {(CF ₃ ) ₃ CSO ₂ }] ^{− and the} like, JP 2011-133844 A, Examples thereof include nitrogen anions described in JP 2011-116803 A and JP 2010-090341 A.

Examples of the methide anion include (CF ₃ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFSO ₂ ] ₃ C ⁻ , and (CF ₃ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , (CF ₃ CF ₂ CF ₂ CF ₂ SO ₂ ) ₃ C ⁻ , [(CF ₃ ) ₂ CFCF ₂ SO ₂ ] ₃ C ⁻ , [CF ₃ CF ₂ (CF ₃ ) CFSO ₂ ] ₃ C ⁻ , [(CF ₃ ) ₃ CSO ₂ ] ₃ C ⁻ , (FSO ₂ ) ₃ C ^{— and the} like, JP 2011-145540 A, US Pat. No. 5,554,664, JP 2005-309408 A Examples thereof include a methide anion described in JP-A-2004-085657, JP-A-2010-505787, and the like.

The colorant may be a triarylmethane-based lake pigment having a sulfur-containing aromatic heterocyclic group. Lake pigment refers to a soluble dye made into an insoluble pigment by a precipitating agent. Examples of the precipitating agent include barium chloride, calcium chloride, ammonium sulfate, aluminum chloride, aluminum acetate, lead acetate, tannic acid, and katanol. And complex heteropolyacids (phosphotungstic acid, phosphomolybdic acid, phosphotungsten / molybdic acid, silicotungsten molybdic acid, silicotungstic acid, silicomolybdic acid) and the like referred to as tamol and complex acid.

The present colorant can be produced by a known method, and examples thereof include the same methods as in the examples of JP-A-2008-189925. The colorant thus obtained is soluble in various organic solvents including ketones such as cyclohexanone.

The present colorant usually exhibits a green color, but the colored composition of the present invention can further contain another colorant as the colorant together with the present colorant. Other colorants are not particularly limited, and colors and materials can be appropriately selected according to the application.

As the other colorant, any of pigments, dyes other than the present colorant, and natural pigments can be used, but organic pigments and organic dyes are preferable in terms of obtaining pixels with high luminance and color purity. .

As organic pigments, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) names are given. The following organic pigments can be preferably used.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 61: 1, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 133, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 169, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 183, C.I. I. Pigment yellow 191, C.I. I. Pigment yellow 191: 1, C.I. I. Pigment yellow 206, C.I. I. Pigment yellow 209, C.I. I. Pigment yellow 209: 1, C.I. I. Pigment yellow 211, C.I. I. Yellow pigments such as CI Pigment Yellow 212;

C. I. Pigment green 1, C.I. I. Pigment green 4, C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Green pigments such as CI Pigment Green 58.

In the present invention, when a pigment is used as another colorant, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A-2001-108817, and various commercially available resins for dispersing pigments. The organic pigment is preferably used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

In the present invention, when a pigment is used as another colorant, a known dispersant and dispersion aid can be further added. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. A dispersant, a polyester-based dispersant, an acrylic-based dispersant and the like, and examples of the dispersion aid include a pigment derivative and the like.

Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK) And the like as urethane dispersants such as Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol) Co., Ltd.) as a polyethyleneimine dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), etc. as a polyester dispersant, PB821, Adisper PB822, Adisper PB880, Adisper PB881 (or more, Ajinomoto Fine-Techno Co., Ltd.), and the like, can be mentioned, respectively.

Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone.

As organic dyes, the following organic dyes can be preferably used among those having a color index (CI) name.

For example,
C. I. Acid Yellow 11, C.I. I. Direct Yellow 12, C.I. I. Reactive Yellow 2, C.I. I. Moldant Yellow 5, C.I. I. Acid Yellow 3, C.I. I. Acid Yellow 1, C.I. I. Basic Yellow 4, C.I. I. Solvent Yellow 33, C.I. I. Disperse Yellow 64, C.I. I. Disperse Yellow 42, C.I. I. Yellow dyes such as Solvent Yellow 179 and Disperse Yellow 201;
C. I. Direct Green 59, C.I. I. Direct Green 28, C.I. I. Green dye such as Acid Green 25.

The colored composition of the present invention is usually used for the formation of a green pixel. In that case, (A) as a colorant, together with the present colorant, as other colorants, a green pigment, a green dye, a yellow pigment and a yellow dye. It is preferable to contain at least one selected from the group consisting of: In this case, the content of the present colorant is preferably from 0.1 to 80% by mass, more preferably from 1 to 80% by mass, still more preferably from 5 to 70% by mass, particularly from 20 to 60%, based on all colorants. Mass% is preferred.

In the present invention, other colorants can be used alone or in admixture of two or more.

The content of the colorant (A) is usually 5 to 70% by mass, preferably 5 to 70% by mass in the solid content of the coloring composition from the viewpoint of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Here, solid content is components other than the solvent mentioned later.

-(B) Binder resin-
Although it does not specifically limit as (B) binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). And a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as “unsaturated monomer (b2)”). .

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like. Here, (meth) acrylic acid is a concept including methacrylic acid and acrylic acid.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (degree of polymerization 2 To 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) ) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic acid esters such as (meth) acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate and polysiloxane.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. More preferably, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Can be mentioned.

In the present invention, for example, JP-A-5-19467, JP-A-6-3030212, JP-A-7-207211, JP-A-09-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter abbreviated as GPC; elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably Is 3,000 to 50,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3. .0. In addition, Mn here says the number average molecular weight of polystyrene conversion measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method. For example, it is disclosed in JP2003-222717A, JP2006-259680A, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

In the present invention, the binder resins can be used alone or in admixture of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(C) Crosslinking agent-
In the present invention, (C) a crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (C) crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

In addition, examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate includes at least one selected from bisphenol A di (meth) acrylate, ethylene oxide and propylene oxide modified by at least one selected from ethylene oxide and propylene oxide. Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide. Dipentaerythritol modified with at least one selected from dipentaerythritol penta (meth) acrylate, ethylene oxide and propylene oxide modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Examples include hexa (meth) acrylate.

Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and is a concept including melamine, benzoguanamine or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′. , N′-tetra (alkoxymethyl) benzoguanamine, N, N, N ′, N′-tetra (alkoxymethyl) glycoluril, and the like.

Among these crosslinking agents, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, polyfunctional urethanes ( (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N′— Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, and obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In the present invention, the crosslinking agent (C) can be used alone or in admixture of two or more.

In the present invention, the content of the (C) crosslinking agent is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass, with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the content of the crosslinking agent is too large, when the coloring composition of the present invention is imparted with alkali developability, the alkali developability is deteriorated, and the soil or film on the unexposed portion of the substrate or on the light shielding layer is deteriorated. There is a tendency for the rest to occur easily.

-Photopolymerization initiator-
The coloring composition of the present invention can contain a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of (C) a crosslinking agent upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray.

Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds, and the like.

In the present invention, the photopolymerization initiators can be used alone or in admixture of two or more. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and the like can be mentioned.

In addition, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in terms of improving sensitivity. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, etc. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine compounds having a halomethyl group, such as toxistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Specific examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. As commercially available O-acyloxime compounds, NCI-831, NCI-930 (manufactured by ADEKA Corporation) and the like can also be used.

In the present invention, when using a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound, a sensitizer can be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the (C) cross-linking agent. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components optionally added, but is usually prepared as a liquid composition by blending a solvent. As the solvent, as long as the components (A) to (C) and other components constituting the colored composition are dispersed or dissolved and do not react with these components and have appropriate volatility, the solvent is appropriately used. You can choose to use.

Among such solvents, for example
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxypropionic acid Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl Pioneto acetate n- butyl acetate i- butyl, formic acid n- amyl acetate, i- amyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
In this invention, a solvent can be used individually or in mixture of 2 or more types.

The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the coloring composition is preferably 5 to 50% by mass, and preferably 10 to 40% by mass. More preferred. By setting it as such an aspect, the coloring agent dispersion liquid with favorable dispersibility and stability and the coloring composition with favorable coating property and stability can be obtained.

-Additive-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitors: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

The coloring composition of the present invention can be prepared by an appropriate method. Examples of the preparation method include the methods disclosed in JP 2008-58642 A, JP 2010-132874 A, and the like. be able to. When both a dye and a pigment are used as the colorant, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, the dye solution that has passed through the first filter is passed through the first filter. Alternatively, it is possible to employ a method of preparing by mixing with a separately prepared pigment dispersion and passing the obtained colored composition through a second filter. In addition, the dye, the above components (B) to (C), and other components to be used as necessary are dissolved in a solvent, and the obtained solution is passed through the first filter, and then the first filter is passed through. You may employ | adopt the method prepared by mixing the solution which passed through with the pigment dispersion liquid prepared separately, and passing the obtained coloring composition through a 2nd filter. Also, after passing the dye solution through the first filter, the dye solution that has passed through the first filter, the above components (B) to (C), and other components to be used as necessary are mixed and dissolved. The obtained solution is passed through a second filter, and the solution that has passed through the second filter is further mixed with a separately prepared pigment dispersion, and the resulting colored composition is passed through a third filter. The method of doing can also be employ | adopted.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, a green liquid-sensitive liquid composition of the present invention containing the coloring agent is applied on the substrate, and then prebaked to evaporate the solvent to form a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which green pixel patterns are arranged in a predetermined arrangement.

Subsequently, each radiation-sensitive colored composition of red or blue is used, and the radiation-sensitive colored composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the red pixel array and blue Are sequentially formed on the same substrate. Thereby, a color filter in which a pixel array of three primary colors of green, red, and blue is arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above. In the first method for producing a color filter, at least the green pixel array of the green, red, and blue pixel arrays may be a colored layer formed using the colored composition of the present invention. .

The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation coloring composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

When applying the radiation-sensitive coloring composition to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

Pre-baking is usually performed by a combination of vacuum drying and heat drying. The drying under reduced pressure is usually performed until reaching 50 to 200 Pa. The conditions for heat drying are usually 70 to 110 ° C. and about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples thereof include a light source, a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. An ultraviolet LED can also be used as the exposure light source. The wavelength is preferably radiation in the range of 190 to 450 nm.

In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-. An aqueous solution of undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723, JP-A-2000-310706, etc. can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a green liquid composition of the thermosetting coloring composition of the present invention containing the coloring agent is discharged into the formed partition wall by an ink jet apparatus, and then prebaked to evaporate the solvent. Next, the coating film is exposed as necessary, and then cured by post-baking to form a green pixel pattern.

Next, red and blue thermosetting coloring compositions are used, and a red pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of green, red and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above. In the second method for producing a color filter, at least the green pixel array of the green, red, and blue pixel arrays may be a colored layer formed using the colored composition of the present invention. .

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a radiation-sensitive colored composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Display element The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.
The color liquid crystal display element provided with the color filter of the present invention may be a transmissive type or a reflective type, and can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display device including the color filter of the present invention can include a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

The color liquid crystal display device having the color filter of the present invention includes a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, an IPS (In-Planes Switching) type, a VA (Vertical Alignment) type, and an OCB (Optic Optical An appropriate liquid crystal mode such as a birefringence type can be applied.

In addition, the organic EL display element including the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.
In addition, the electronic paper including the color filter of the present invention can have an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of this coloring agent>
Synthesis example 1
A stir bar was added and N-ethyl-1-naphthylamine 9.0 g (54 mmol), DMF 5.7 g, and toluene 90 mL were charged into a 200 mL three-necked flask previously purged with nitrogen, and 9.6 g of phosphorus oxychloride was added dropwise under ice cooling. did. After stirring at the same temperature for 30 minutes, the temperature was raised to room temperature and stirring was continued for another 2 hours. Next, the obtained reaction mixture was washed successively with a 10% strength by weight aqueous sodium hydroxide solution, 5% strength by weight hydrochloric acid and ion-exchanged water, and the organic layer was concentrated under reduced pressure using a rotary evaporator to obtain 9.0 g of a brown viscous liquid. Obtained. As a result of ¹ H-NMR analysis, it was confirmed that the obtained product was 4-formyl-N-ethyl-1-naphthylamine represented by the following formula (A1).

Synthesis example 2
To a 300 mL eggplant-shaped flask containing a stirrer, 8.8 g of 4-formyl-N-ethyl-1-naphthylamine obtained in Synthesis Example 1, 14.15 g of 2-phenylthiophene, and 130 mL of ion-exchanged water were added. To this mixture, 9.53 g of concentrated sulfuric acid was added at room temperature, and the mixture was stirred at 100 ° C. for 24 hours under a nitrogen stream. After cooling to room temperature, the reaction mixture was added to 220 mL of ice water, stirred for 30 minutes and allowed to stand overnight. The precipitated solid was collected by suction filtration and washed thoroughly with water. The obtained solid was reslurried in diisopropyl ether, stirred, collected by filtration, and dried under reduced pressure at 50 ° C. to obtain 14.4 g of a solid. ¹ H-NMR analysis confirmed that the obtained solid was a compound represented by the following formula (A2).

Synthesis example 3
To a 200 mL eggplant-shaped flask containing a stirrer, 14.4 g of the compound represented by the formula (A2) obtained in Synthesis Example 2, 45 mL of ethanol and 5.42 g of chloranil were added and stirred at 70 ° C. for 2 hours. After cooling to room temperature, insoluble matters were removed by filtration, and the filtrate was concentrated under reduced pressure using a rotary evaporator. The obtained solid was dried under reduced pressure to obtain 18.7 g of a green solid. ^{By 1} H-NMR and MS spectrum analysis, it was confirmed that the obtained green solid was a compound represented by the following formula (A3). This compound is referred to as a colorant (A-1).

Synthesis example 4
Into a 300 mL eggplant-shaped flask containing a stir bar, 8.8 g of 4-formyl-N-ethyl-1-naphthylamine obtained in Synthesis Example 1, 15.4 g of 2-phenyl-5-methylthiophene, and 130 mL of ion-exchanged water Was added. To this mixture, 9.53 g of concentrated sulfuric acid was added at room temperature, and the mixture was stirred at 100 ° C. for 24 hours under a nitrogen stream. After cooling to room temperature, the reaction mixture was added to 220 mL of ice water, stirred for 30 minutes and allowed to stand overnight. The precipitated solid was collected by suction filtration and washed thoroughly with water. The obtained solid was reslurried in diisopropyl ether, stirred, collected by filtration, and dried under reduced pressure at 50 ° C. to obtain 15.2 g of a solid. ¹ H-NMR analysis confirmed that the obtained solid was a compound represented by the following formula (A4).

Synthesis example 5
To a 200 mL eggplant-shaped flask containing a stirrer, 15.2 g of the compound represented by the formula (A4) obtained in Synthesis Example 4, 50 mL of ethanol and 5.8 g of chloranil were added and stirred at 70 ° C. for 2 hours. After cooling to room temperature, insoluble matters were removed by filtration, and the filtrate was concentrated under reduced pressure using a rotary evaporator. The obtained solid was dried under reduced pressure to obtain 17.2 g of a green solid. ^{From 1} H-NMR and MS spectra, it was confirmed that the obtained solid was a compound represented by the following formula (A5). This compound is referred to as a colorant (A-2).

Synthesis Example 6
A stir bar was added, 8.7 g (37.2 mmol) of p-dibromobenzene and 132 mL of THF were charged into a 300 mL three-necked flask previously purged with nitrogen, cooled to −78 ° C., and then 2.5 mol / L n-butyllithium hexane. 13.5 mL (33.8 mmol) of the solution was added and stirred for 1 hour.
Next, another nitrogen-substituted 300 mL three-necked flask was charged with 1.02 mL (8.5 mmol) of ethyl carbonate and 3 mL of THF, cooled to −78 ° C., then added with the above reaction solution, and allowed to warm naturally to room temperature for 3 hours. Stir. Thereafter, 50 mL of a saturated aqueous ammonium chloride solution was added and stirred for about 5 minutes, and then transferred to a separatory funnel, and the organic layer was extracted with 100 mL of ethyl acetate. Thereafter, the organic layer was washed with 50 mL of saturated saline, dried using magnesium sulfate, and then concentrated under reduced pressure using a rotary evaporator. The obtained viscous liquid was isolated and purified by silica gel chromatography (5% ethyl acetate in hexane) to obtain 3.38 g (yield 80%) of a viscous solid. As a result of ¹ H-NMR analysis, it was confirmed that the obtained product was a compound represented by the following formula (A6).

Synthesis example 7
In a 100 mL three-necked flask purged with nitrogen in advance, 0.30 g (0.6 mmol) of the compound represented by the formula (A6), 0.27 g (2.1 mmol) of 2-thiopheneboronic acid, tetrakistriphenylphosphine palladium (0) 0 0.07 g (0.1 mmol), 0.50 g (3.6 mmol) of potassium carbonate and 15 mL of DMF were charged, and the mixture was heated and stirred at 120 ° C. After 5 hours, the mixture was cooled to room temperature, 70 mL of water and 50 mL of ethyl acetate were added, the organic layer was extracted, dried over magnesium sulfate, and then concentrated under reduced pressure using a rotary evaporator. The resulting viscous solid was isolated and purified by silica gel chromatography (5% ethyl acetate in hexane) to obtain 0.15 g (yield 50%) of a white solid. As a result of ¹ H-NMR analysis, it was confirmed that the obtained product was a compound represented by the following formula (A7).

Synthesis example 8
0.10 g (0.2 mmol) of the compound represented by the formula (A7) and 3 mL of chloroform were charged into a 50 mL eggplant flask, stirred, 0.06 g (0.2 mmol) of trifluoromethanesulfonimide was added, and the mixture was stirred for 30 minutes. Thereafter, the reaction solution was transferred to a separatory funnel, and the organic layer was washed twice with 10 mL of water. The organic layer was dried over magnesium sulfate and then concentrated under reduced pressure using a rotary evaporator to give 0.15 g of a compound (yield 99.9). %). As a result of ¹ H-NMR analysis, it was confirmed that the obtained compound was a compound represented by the following formula (A8). This compound is referred to as a colorant (A-4).

Synthesis Example 9
Compound (A9) was synthesized in the same manner as in Synthesis Example 7, except that 5-methylthiopheneboronic acid was used instead of 2-thiopheneboronic acid in Synthesis Example 7. Next, in Synthesis Example 8, a compound was synthesized in the same manner as in Synthesis Example 8 except that Compound (A9) was used instead of the compound represented by Formula (A7). The obtained compound is defined as a colorant (A-5).

Synthesis Example 10
Compound (A10) was synthesized in the same manner as in Synthesis Example 7, except that 5-methoxythiopheneboronic acid was used instead of 2-thiopheneboronic acid in Synthesis Example 7. Next, in Synthesis Example 8, a compound was synthesized in the same manner as in Synthesis Example 8 except that Compound (A10) was used instead of the compound represented by Formula (A7). The obtained compound is defined as a colorant (A-6).

Synthesis Example 11
Compound (A11) was synthesized in the same manner as in Synthesis Example 7, except that 5-dimethylaminothiopheneboronic acid was used instead of 2-thiopheneboronic acid in Synthesis Example 7. Next, in Synthesis Example 8, a compound was synthesized in the same manner as in Synthesis Example 8 except that Compound (A11) was used instead of the compound represented by Formula (A7). The obtained compound is defined as a colorant (A-7).

Synthesis Example 12
A colorant was synthesized in the same manner as in Synthesis Example 8, except that potassium tetracyanoborate was used in place of trifluoromethanesulfonimide in Synthesis Example 8, and the compound was confirmed to be the target compound by ¹ H-NMR measurement. . The obtained compound is defined as a colorant (A-8).

Synthesis Example 13
A colorant was synthesized in the same manner as in Synthesis Example 8 except that potassium trifluoromethanesulfonate was used instead of trifluoromethanesulfonimide in Synthesis Example 8, and the target compound was confirmed by ¹ H-NMR measurement. did. The obtained compound is defined as a colorant (A-9).

Synthesis Example 14
A coloring agent was synthesized in the same manner as in Synthesis Example 8 except that tris (trifluoromethylsulfonyl) methidocesium was used in place of trifluoromethanesulfonimide in Synthesis Example 8, and the compound was the target compound by ¹ H-NMR measurement. It was confirmed. The obtained compound is defined as a colorant (A-10).

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by weight of CI Pigment Green 58, 12.5 parts by weight (BYK) manufactured by BYK-LPN21116 as a dispersant (solid content concentration 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent Then, it was processed by a bead mill to prepare a green pigment dispersion (a-1).

<Preparation of dye solution>
Preparation Example 2
15 parts by weight of the colorant (A-1) and 85 parts by weight of cyclohexanone as a solvent were mixed to prepare a green dye solution (A-1).

Preparation Example 3
A green dye solution (A-2) was prepared in the same manner as in Preparation Example 2, except that the colorant (A-2) was used instead of the colorant (A-1) in Preparation Example 2.

Preparation Example 4
Instead of the colorant (A-1) in Preparation Example 2, C.I. I. A yellow dye solution (A-3) was prepared in the same manner as in Preparation Example 2, except that Basic Yellow 11 was used.

Preparation Examples 5 to 11
A green dye solution (A-4) was prepared in the same manner as in Preparation Example 2 except that the colorants (A-4) to (A-10) were used in place of the colorant (A-1) in Preparation Example 2. To (A-10) were prepared.

<(B) Synthesis of binder resin>
Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 2-ethylhexyl methacrylate 23 parts by mass, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono (2-acryloyloxyethyl) and 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) The solution was added dropwise over a period of time and polymerized for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The obtained binder resin had Mw of 12,200 and Mn of 6,500. This binder resin is referred to as “binder resin (B1)”.

<Preparation and evaluation of coloring composition>
Example 1
9.3 parts by mass of dye solution (A-1) as colorant 1, 11.5 parts by mass of dye solution (A-3) as colorant 2, 9.9 parts by mass of binder resin (B1) solution as binder resin, cross-linking 15.4 parts by mass of M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as a polymerization agent, and 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, trade name: IRGACURE 369) 1.8 parts by mass and NCI-930 (manufactured by ADEKA) 0.1 part by mass F-554 (manufactured by DIC Corporation) 0.2 parts by mass and cyclohexanone as a solvent are mixed, and the solid content is concentrated The green colored composition of 20 wt% was prepared.

Evaluation of Chromaticity Characteristics The obtained colored composition was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200 ° C. for 30 minutes to form a green cured film for evaluation. The film thickness of the obtained green cured film was measured using an alpha step IQ manufactured by KLA-Tencor.
Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate values (x, y) and stimuli in the CIE color system with a C light source and a 2-degree field of view for the three green cured films obtained The value (Y) was measured. From the measurement result, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.59 were obtained. The evaluation results are shown in Table 1. It can be said that the higher the stimulus value (Y), the higher the luminance, and the thinner the film thickness, the greater the coloring power of the colorant.

Examples 2 to 9 and Comparative Example 1
In Example 1, a green coloring composition was prepared in the same manner as in Example 1 except that the types and blending amounts of Colorant 1 and Colorant 2 were changed as shown in Table 1. Then, the obtained colored composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Claims

A coloring composition containing the following components (A), (B) and (C).
(A) a triarylmethane colorant having one or more sulfur-containing aromatic heterocyclic groups,
(B) binder resin, and (C) cross-linking agent
The triarylmethane colorant having the one or more sulfur-containing aromatic heterocyclic groups has a structure represented by the formula (1-1) or the formula (1-2). Coloring composition.

[In Formula (1-1),
a represents an integer of 0 to 4. ;
b represents an integer of 0 to 4. ;
Ar represents a substituted or unsubstituted aromatic hydrocarbon group. ;
R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. ;
R p and R q each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′, —SO 3 — or a halo group. R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ;
X 1 and X 2 each independently represent a single bond or a substituted or unsubstituted aromatic hydrocarbon group. ;
Y 1 and Y 2 each independently represent a hydrogen atom or a substituted or unsubstituted sulfur-containing aromatic heterocyclic group. ;
However, in the compound, Y 1 and Y 2 are not simultaneously hydrogen atoms. ]

[In Formula (1-2),
a, b, Ar, R p , R q , X 1 , X 2 , Y 1 and Y 2 are as defined above. ;
X 3 represents a single bond or a substituted or unsubstituted aromatic hydrocarbon group. ;
Y 3 represents a hydrogen atom or a substituted or unsubstituted sulfur-containing aromatic heterocyclic group. ;
However, in the compound, Y 1 , Y 2 and Y 3 are not simultaneously hydrogen atoms. ]
The sulfur-containing aromatic heterocyclic group is a group obtained by removing one hydrogen atom from thiophene or benzothiophene, and the remaining hydrogen atom of the group may be substituted with another electron-donating group The coloring composition according to claim 1 or 2, wherein
The colored composition according to any one of claims 1 to 3, wherein the sulfur-containing aromatic heterocyclic group is a group represented by the following formula (2).

[In Formula (2),
s represents 0 or 1. ;
t represents an integer of 0 ≦ t ≦ (2s + 3). ;
R 5 independently represents a hydrogen atom, —NR 6 R 7 , an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, R 6 and R 7 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. ;
* Indicates a bond. ]
The triarylmethane colorant having one or more sulfur-containing aromatic heterocyclic groups has a structure represented by the formula (3-1) or the formula (3-2). The coloring composition of any one of these.

[In Formula (3-1),
a, b, R 1 , R 2 , R p and R q are as defined above. ;
c represents an integer of 0 to 4. ;
e and g each independently represent 0 or 1; ;
f represents an integer of 0 ≦ f ≦ (2e + 3). ;
h represents an integer of 0 ≦ h ≦ (2g + 3). ;
R 8 and R 9 each independently represent a hydrogen atom, —NR 6 R 7 , an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, R 6 and R 7 are as defined above. ;
R r represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′, —SO 3 — or a halo group. R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

[In Formula (3-2),
a, b, c, e, f, g, h, R 8 , R 9 , R p , R q and R r are as defined above. ;
j represents 0 or 1; ;
k represents an integer of 0 ≦ k ≦ (2j + 3). ;
R 10 represents a hydrogen atom, —NR 6 R 7 , an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. However, R 6 and R 7 are as defined above. ]
6. The colored composition according to claim 1, further comprising at least one selected from the group consisting of a green pigment, a green dye, a yellow pigment, and a yellow dye as the colorant (A).
A color filter comprising a colored layer containing a triarylmethane colorant having one or more sulfur-containing aromatic heterocyclic groups.
A display element comprising the color filter according to claim 7.
A triarylmethane colorant having a structure represented by the following formula (1-1) or formula (1-2).

[In Formula (1-1),
a represents an integer of 0 to 4. ;
b represents an integer of 0 to 4. ;
Ar represents a substituted or unsubstituted aromatic hydrocarbon group. ;
R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. ;
R p and R q each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —COOR ′, —SO 3 — or a halo group. R ′ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ;
X 1 and X 2 each independently represent a single bond or a substituted or unsubstituted aromatic hydrocarbon group. ;
Y 1 and Y 2 each independently represent a hydrogen atom or a substituted or unsubstituted sulfur-containing aromatic heterocyclic group. ;
However, in the compound, Y 1 and Y 2 are not simultaneously hydrogen atoms. ]

[In Formula (1-2),
a, b, Ar, R p , R q , X 1 , X 2 , Y 1 and Y 2 are as defined above. ;
X 3 represents a single bond or a substituted or unsubstituted aromatic hydrocarbon group. ;
Y 3 represents a hydrogen atom or a substituted or unsubstituted sulfur-containing aromatic heterocyclic group. ;
However, in the compound, Y 1 , Y 2 and Y 3 are not simultaneously hydrogen atoms. ]
The green triarylmethane colorant according to claim 9.