TWI542646B - Coloring composition, color filter and display device - Google Patents

Description

Coloring composition, color filter, and display element

The present invention relates to a coloring composition, a color filter, and a display element, and more particularly to a color suitable for use in a transmissive or reflective type color liquid crystal display element, a solid-state imaging element, an organic EL display element, an electronic paper, or the like. A coloring composition of the filter, a color filter including a coloring layer formed using the coloring composition, and a display element including the color filter.

When a color filter is produced using a coloring sensitizing radiation composition, a method is known in which a pigment dispersion type color sensitizing radiation composition is applied onto a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter Each of the color pixels is obtained by the "exposure") and development (Patent Documents 1 to 2). Further, a method is also known in which a photopolymerizable composition in which carbon black is dispersed is formed into a black matrix (Patent Document 3). Further, a method of obtaining a color chromophore by an inkjet method using a pigment-dispersed colored thermosetting composition is known (Patent Document 4).

In order to achieve high luminance and high color purity of display elements, or high definition of solid-state imaging elements, it is known to use dyes as coloring. The agent system is effective. For example, Patent Document 5 proposes to use a triarylmethane dye of a specific structure.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Laid-Open No. 3-53201

[Patent Document 3] Japanese Patent Laid-Open No. Hei 6-35188

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-310706

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2008-304766

However, the triarylmethane dye proposed in Patent Document 5 has insufficient heat resistance, and if it undergoes a heating (post-baking) step such as exposure at 200 ° C or development, the superiority to the chromaticity characteristics of the pigment is lost. From the above background, there is a strong demand for the development of coloring compositions having heat resistance required for the manufacture of color filters.

Therefore, an object of the present invention is to provide a coloring composition excellent in heat resistance. Further, an object of the present invention is to provide a color filter including a coloring layer that maintains excellent chromaticity characteristics, and a display element including the color filter.

The inventors of the present invention have intensively studied and found that the above problem can be solved by using a basic dye having a specific anion moiety as a colorant.

That is, the present invention provides a coloring composition comprising: (A) a compound represented by the following formula (1) (hereinafter also referred to as "specific coloring compound"), (B) a binder resin, and (C) crosslinking. Agent.

X ⁺ (Z _a R ⁰ _b M) ^- (1)

[In the formula (1), X ⁺ represents a cationic chromophore group, Z represents an electron-withdrawing group, R ⁰ represents an alkyl group, an aryl group, a cycloalkyl group or an alkylaryl group, and M represents a nitrogen atom, a phosphorus atom, or a boron atom. When an arsenic atom or a germanium atom has a plurality of Z and R ⁰ respectively, the same may be used. a represents an integer from 1 to 6, b represents an integer from 0 to 5, and a+b is 2, 4 or 6. However, when M is a nitrogen atom, Z has at least one of a cyano group and a halosulfonyl group. ]

Moreover, the present invention provides a color filter comprising a coloring layer containing a compound represented by the above formula (1); and a display element including the color filter. Here, the "colored layer" means a color pixel, a black matrix, a black spacer, or the like used in a color filter.

Further, the present invention provides a coloring agent represented by the following formula (12).

X ⁺ [(CN) ₂ N] ^- (12)

In the formula (12), X ⁺ represents a cationic chromophoric group. ]

When the coloring composition of the present invention containing a specific coloring compound is used, the heat resistance required for the production of the color filter can be sufficiently satisfied. Therefore, even if the high temperature heating step is performed, a coloring layer which maintains excellent chromaticity characteristics can be formed.

Therefore, the coloring composition of the present invention is suitably used for a color filter for a color liquid crystal display element, a color filter for color separation of a solid-state image sensor, a color filter for an organic EL display element, and an electronic paper. The production of various color filters led by color filters.

[Formation of the Invention]

The invention is described in detail below.

Coloring composition

The constituent components of the coloring composition of the present invention will be described below.

- (A) specific coloring compounds -

The coloring composition of the present invention contains a specific coloring compound, that is, a compound represented by the above formula (1). The specific coloring compound is a compound having a maximum molar absorption coefficient of 3,000 or more in the visible light region (380 nm to 780 nm), and triarylsulfonium hexafluorophosphate which is known as a photoacid generator and absorbs ultraviolet rays to generate an acid. different.

In the coloring composition of the present invention, the specific coloring compounds may be used singly or in combination of two or more.

First, (Z _a R ⁰ _b M) ^- in the formula (1) will be explained.

Z is not particularly limited as long as it is an electron-withdrawing group, and examples thereof include a halogen group, a monovalent organic group having a halogen group, a cyano group, a monovalent organic group having a cyano group, and a monovalent group having a nitro group. The organic group, halosulfonyl group, alkanesulfonyl group which may have a halogen group, and the like. When M is a phosphorus atom, a boron atom, an arsenic atom or a ruthenium atom, it is preferably a halogen group, a monovalent organic group having a halogen group, a cyano group, a monovalent organic group having a cyano group, and a nitro group. The organic base of one price. On the other hand, when M is a nitrogen atom, it is preferably Z other than a cyano group or a halosulfonyl group. It is a monovalent organic group having a halogen group and an alkanesulfonyl group which may have a halogen group.

The halogen group may, for example, be a fluorine group, a chlorine group, a bromine group or an iodine group, and is preferably a fluorine group from the viewpoint of heat resistance.

The monovalent organic group having a halogen group is not particularly limited, and examples thereof include a monovalent halogenated hydrocarbon group, and the halogenated hydrocarbon group may have a substituent other than a halogen group.

The hydrocarbon group which becomes the skeleton of the halogenated hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an alkylaryl group, more preferably an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a carbon number of 6 An aryl group of ~14 and an alkylaryl group having 7 to 20 carbon atoms.

The alkyl group may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group, an isobutyl group, and a pentyl group. Base, third amyl, hexyl, heptyl, octyl, isooctyl, trioctyl, 2-ethylhexyl and the like.

Further, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

The alkylaryl group may, for example, be a group in which an aryl group having 6 to 14 carbon atoms is substituted with an alkyl group having 1 to 8 carbon atoms.

As the halogen group in the halogenated hydrocarbon group, a fluorine group is preferred. The halogen group may partially or completely replace one of the hydrogen atoms of the hydrocarbon group, particularly a hydrogen atom of the hydrocarbon group, preferably 80 mol% or more, more preferably 90% by mole or more, particularly preferably 100 mol%, and a halogen group. It is better. Thereby, heat resistance can be further improved.

The monovalent organic group having a cyano group is not particularly limited, and examples thereof include a monovalent hydrocarbon group substituted with a cyano group, and a monovalent hydrocarbon group may also be used. There are substituents other than cyano. The monovalent hydrocarbon group is preferably an aryl group, and particularly preferably a phenyl group.

The organic group having a valence of a nitro group is not particularly limited, and examples thereof include a monovalent hydrocarbon group substituted with a nitro group, and a monovalent hydrocarbon group may have a substituent other than a nitro group. The monovalent hydrocarbon group is preferably an aryl group, and particularly preferably a phenyl group.

The alkanesulfonyl group which may have a halogen group is not particularly limited, and an alkanesulfonyl group or a halogenated alkanesulfonyl group can be suitably used. The alkyl group which is a skeleton of the alkanesulfonyl group and the halogenated alkanesulfonyl group may be linear or branched, and the carbon number is preferably from 1 to 8. Specific examples of the alkyl group include the same as those in the halogenated hydrocarbon group.

Further, as the halogen group in the halogenated alkanesulfonyl group, a fluorine group is preferred. The halogen group may be a part or all of a hydrogen atom of the hydrocarbon group, but from the viewpoint of heat resistance, the hydrogen atom of the hydrocarbon group is preferably 80 mol% or more, more preferably 90% or more, and particularly preferably 100 mol. It is preferred that the ear % is substituted with a halogen group.

The halosulfonyl group may, for example, be an FSO ₂ group, a ClSO ₂ group, a BrSO ₂ group or an ISO ₂ group, and is preferably an FSO ₂ group.

In the present invention, when Z and M are a phosphorus atom, a boron atom, an arsenic atom or a ruthenium atom, a halogen group, a monovalent halogenated hydrocarbon group which may have a substituent other than a halogen group, a cyano group, and particularly preferably a fluorine group are preferable. , cyano, fluorinated alkyl, fluorinated aryl or fluorinated alkaryl. a perfluoroalkyl group having 1 to 6 (more preferably 1 to 4) carbon atoms in the fluorinated alkyl group and a perfluoroaryl group having 6 to 14 carbon atoms (more preferably 6 to 10) in the fluorinated aryl group. Further, each of the perfluoroalkylaryl groups having 7 to 20 (more preferably 7 to 16) carbon atoms in the fluorinated alkylaryl group is preferred. Specific examples thereof include, for example, a CF ₃ group, a CF ₃ CF ₂ group, a (CF ₃ ) ₂ CF group, a CF ₃ CF ₂ CF ₂ group, a CF ₃ CF ₂ CF ₂ CF ₂ group, and a (CF ₃ ) ₂ group. CFCF ₂ group, CF ₃ CF ₂ (CF ₃ )CF group, (CF ₃ ) ₃ C group, pentafluorophenyl group, phenyl group substituted with CF ₃ group, and the like.

On the other hand, when M is a nitrogen atom, Z other than a cyano group or a halosulfonyl group is preferably a halogenated alkanesulfonyl group, and particularly preferably a fluorinated alkanesulfonyl group. Specific examples thereof include a CF ₃ SO ₂ group, a CF ₃ CF ₂ SO ₂ group, a (CF ₃ ) ₂ CFSO ₂ group, a CF ₃ CF ₂ CF ₂ SO ₂ group, and a CF ₃ CF ₂ CF ₂ CF ₂ SO group. ₂ base, (CF ₃ ) ₂ CFCF ₂ SO ₂ group, CF ₃ CF ₂ (CF ₃ )CFSO ₂ group, (CF ₃ ) ₃ CSO ₂ group, and the like.

R ⁰ represents an alkyl group, an aryl group, a cycloalkyl group or an alkylaryl group, and examples thereof include the same ones as the alkyl group, the aryl group, the cycloalkyl group and the alkaryl group in the above-mentioned halogenated hydrocarbon group.

M represents a nitrogen atom, a phosphorus atom, a boron atom, an arsenic atom or a ruthenium atom, but from the viewpoint of safety, a nitrogen atom, a phosphorus atom or a boron atom is preferred. Further, a+b represents 2, 4 or 6, but when M is a nitrogen atom, a+b is 2, when M is a boron atom, a+b is 4, and M is a phosphorus atom, an arsenic atom or a ruthenium atom, a +b is 6.

a represents an integer from 1 to 6, and b represents an integer from 0 to 5. However, when Z and R ⁰ respectively exist, they may be the same or different. In the present invention, b = 0, that is, a is preferably 2, 4 or 6.

In the present invention, preferred examples of the (Z _a R ⁰ _b M) ^- are an anion represented by the following formula (1a), an anion represented by the following formula (1b), an anion represented by the following formula (1c), and the like.

[(R ¹ ) _c P Hal _6-c ] ^- (1a)

In the formula (1a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, and Hal represents a halogen group. When a plurality of R ¹ and Hal are present, they may be the same or different. c represents an integer from 0 to 6. ]

[(R ² ) _d B Hal _4-d ] ^- (1b)

[In the formula (1b), R ^{2 is} independent of each other, and represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a cyano group, B represents a boron atom, Hal represents a halogen group, and when R ² and Hal are respectively present, respectively , can be the same or different. d represents an integer from 0 to 4. ]

[(EA) ₂ N] ^- (1c)

In the formula (1c), EA independently of each other represents a cyano group, an FSO ₂ group or a fluorinated alkanesulfonyl group. However, at least one of the two EAs represents a cyano group or an FSO ₂ group. ]

The definitions of the symbols in the formula (1a), the formula (1b), and the formula (1c) will be described below.

R ¹ represents a halogenated hydrocarbon group, and examples of the halogenated hydrocarbon group include the halogenated hydrocarbon group exemplified in the above description of Z. In the present invention, R ^{1 is} preferably a fluorinated alkyl group, and more specifically, preferably a fluorinated alkyl group as exemplified in the above description of Z.

R ² independently of each other represents a halogenated hydrocarbon group, a cyano group or a phenyl group substituted with a nitro group or a cyano group, and examples of the halogenated hydrocarbon group include a halogenated hydrocarbon group as exemplified in the above description of Z. In the present invention, R ^{2 is} preferably a fluorinated alkyl group, a fluorinated aryl group, a cyano group or a phenyl group substituted with a trifluoromethyl group or a fluorine atom, and more specifically, preferably exemplified in the above description of Z The basis.

Further, in the formulae (1a) and (1b), as the Hal, a fluorine group is preferred from the viewpoint of heat resistance of the colorant.

On the other hand, in the formula (1c), EA represents a cyano group, an FSO ₂ group or a fluorinated alkanesulfonyl group. The fluorinated alkanesulfonyl group is preferably a fluorinated alkanesulfonyl group exemplified in the above description of Z. Further, in the formula (1c), as the EA, it is preferred that both of them are a cyano group or an FSO ₂ group, or one of them is an FSO ₂ group, and the other is a fluorinated alkanesulfonyl group.

Representative examples of the anion represented by the above formula (1a) include PF ₆ ^- , (CF ₃ ) ₃ PF ₃ ^- , (C ₂ F ₅ ) ₂ PF ₄ ^- , and (C ₂ F ₅ ) ₃ PF _{3 .} ^- , [(CF ₃ ) ₂ CF] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CF] ₃ PF ₃ , (nC ₃ F ₇ ) ₂ PF ₄ ^- , (nC ₃ F ₇ ) ₃ PF ₃ ^- , ( nC 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 ^- , (nC ₄ F ₉ ) ₂ PF ₄ ^- , (nC 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 ^-, and the like. Among them, preferred are PF ₆ ^- , (C ₂ F ₅ ) ₂ PF ₄ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , (nC ₃ F ₇ ) ₃ PF ₃ ^- , (nC ₄ F ₉ ) ₃ PF ₃ ^- , [(CF ₃ ) ₂ CF] ₃ PF ₃ ^- , [(CF ₃ ) ₂ CF] ₂ PF ₄ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₃ PF ₃ ^- , [(CF ₃ ) ₂ CFCF ₂ ] ₂ PF ₄ ^- .

Representative examples of the anion represented by the above formula (1b) include, for example, BF ₄ ^- , (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) ^- , 肆 (pentafluorophenyl) boric acid Root anion, etc. Wherein BF ₄ ^- , B(CN) ₃ F ^- , (CF ₃ ) ₄ B ^- , (C ₆ F ₅ ) ₄ B ^- , [(CF ₃ ) ₂ C ₆ H ₃ ] ₄ B ^- , 肆 (five A fluorophenyl) borate anion is preferred.

Among the anions represented by the above formula (1c), preferred anions include, for example, [(CN) ₂ N] ^- , [(FSO ₂ ) ₂ N] ^- , [(FSO ₂ ) N (CF ₃ SO _{2 ^{)] -, [(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 }] ^- , [ (FSO ₂ ) N{CF ₃ CF ₂ (CF ₃ )CFSO ₂ }] ^- , [(FSO ₂ )N{(CF ₃ ) ₃ CSO ₂ }] ^- and the like. Among them, the special one is [(CN) ₂ N] ^- .

Next, the X ⁺ in the formula (1) will be described.

X ⁺ is not particularly limited as long as it is a cationic chromophoric group, that is, a cation which forms a basic coloring agent as X ⁺ (Z _a R ⁰ _b M) ^- , and examples thereof include: Methane-based chromophoric group, methine-based chromophoric group, azo-based chromophoric group, diarylmethane-based chromophoric group, quinoneimine-based chromophore group, fluorene-colored group , indigo chromophores, A chromophore group or the like.

The triarylmethane-based chromophoric group is preferably represented by the following formula (2). Further, the cation represented by the following formula (2) has various resonance structures, but in the present specification, the resonance structure is the same as the cation represented by the following formula. The cations represented by the respective formulas are also the same below.

In the formula (2), Ar represents an aromatic hydrocarbon group, and R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ⁵ and R ⁶ independently represent a hydrogen atom and have a carbon number of 1 to 2; 8 alkyl or phenyl, R ⁷ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, -COOR'(R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) or a chlorine atom, R ⁸ and R ¹¹ independently of each other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or R ⁸ and R ^{11 are} integrated to each other to represent a sulfur atom, and R ⁹ and R ¹⁰ independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms. Or a chlorine atom, and Y represents a hydrogen atom or a group represented by the following formula (3). ]

In the formula (3), R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

As the aromatic hydrocarbon group in Ar, an aromatic hydrocarbon group having 6 to 20 carbon atoms (more preferably 6 to 10 carbon atoms) is preferable, and specific examples thereof include a benzene ring, a naphthalene ring, a biphenyl ring, and an anthracene ring. A group in which an arene ring removes 2 to 4 hydrogen atoms.

Examples of the alkyl group having R ³ to R ^{11 in the} above formula (2) (including R' in -COOR') and the alkyl group having 1 to 8 carbon atoms in R ¹² and R ¹³ in the above formula (3) include The same group as the alkyl group of Z.

In the present invention, among the cations represented by the above formula (2), a cation represented by the following formula (4) is particularly preferable from the viewpoint of improving the luminance and the color purity.

[In the formula ^{(4), R 3, R} 4, R 5, R 6, R 12 and R ^13, the above formula (2) and in the ^{(3) R 3, R 4} , R 5, R 6, R ¹² and R ¹³ are synonymous. ]

In the above formula (4), R ³ , R ⁴ , R ¹² and R ^{13 are} preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), and further preferably R ⁵ . It is an alkyl group or a phenyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms), and further preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6 carbon atoms) as R ⁶ . Or a hydrogen atom.

The representative example of the cation represented by the above formula (2) is, for example, the cation represented by the following compound group c and the compound group d, and among them, the compound c2, the compound c3, and the compound c4 are preferable.

As the methine-based chromophoric group, those represented by the following formulae (5-1) to (5-3) are preferred.

[In the formulae (5-1) to (5-3), R ³¹ represents a hydrogen atom or a halogen group, and R ³² , R ³³ , R ³⁴ and R ³⁵ independently of each other represent an alkyl group having 1 to 6 carbon atoms, R ³⁶ A substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and G represents -CH=CH-, -CH=CH-NR ³⁷ - (R ³⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -CH =N-NR ³⁷ - (R ³⁷ is synonymous with the foregoing) or -N=N-NR ³⁷ - (R ³⁷ is synonymous with the foregoing), and R ^a represents a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted Heterocyclic group. ]

R ^{a is} preferably a group represented by the following formulas (5a) to (5g).

[In the formulae (5a) to (5g), R ³⁸ and R ⁴⁵ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ³⁹ represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, R ⁴⁰ and R; ⁴² , R ⁴³ and R ⁴⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴¹ and R ⁴⁶ each independently represent a hydrogen atom, a halogen group, an alkoxy group having 1 to 6 carbon atoms, a substitution or An unsubstituted alkyl group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group. ]

The substituent of the above alkyl group is, for example, a halogen group, a cyano group, a hydroxyl group or the like.

Representative examples of the cation represented by the above formulas (5-1) to (5-3) include cations represented by the following compound group e.

The azo-based chromophoric group is preferably represented by the following formulas (6-1) to (6-6).

[In the formulae (6-1) to (6-6), R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁷ each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R ⁵⁶ and R ⁶⁰ each independently represent a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group, and R ⁵⁸ represents a carbon number of 1 to 6 The alkyl group, R ⁵⁹ represents a group forming a 4-stage ammonium group, and R ^b represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. ]

R ^{59 is} preferably -NR ⁶¹ C _ma H _2ma N ⁺ R ⁶² R ⁶³ R ⁶⁴ (ma is an integer of 1 to 5, and R ⁶¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁶² , R ⁶³ and R ⁶⁴ independently of each other represent an alkyl group having 1 to 6 carbon atoms), -COC _ma H _2ma N ⁺ R ⁶² R ⁶³ R ⁶⁴ (ma, R ⁶² , R ⁶³ and R ⁶⁴ are synonymous with the foregoing), - C _ma H _2ma N ⁺ (NH ₂ )R ⁷⁴ R ⁷⁵ (ma is synonymous with the above, R ⁷⁴ and R ⁷⁵ independently of each other represent an alkyl group having 1 to 6 carbon atoms), or the following formula (6-i) or ( 6-ii) The basis of the representation.

[In the formulae (6-i) and (6-ii), R ⁶¹ and ma are synonymous with the above. ]

The above R ^{b is} preferably a group represented by the following formulas (6a) to (6e), a substituted or unsubstituted phenyl group.

[In the formulae (6a) to (6d), R ⁶⁵ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, and R ⁶⁶ represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; R ⁶⁷ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁶⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁷⁰ to R ⁷³ independently of each other represent a hydrogen atom, a halogen group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group. ]

Examples of the substituent of the alkyl group include a halogen group, a hydroxyl group, a cyano group, and a —CONH ₂ group. Examples of the substituent of the phenyl group include a halogen group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, and a nitro group.

Representative examples of the cation represented by the above formulas (6-1) to (6-6) include cations represented by the following compound group f or compound group g.

The diarylmethane-based chromophore is preferably represented by the following formula (7-1) or (7-2).

In the formulae (7-1) and (7-2), R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ and R ⁸⁹ each independently represent an alkyl group having 1 to 6 carbon atoms. R ⁸⁵ , R ⁹⁰ and R ⁹¹ are each independently and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

Representative examples of the cation represented by the above formulas (7-1) to (7-2) include cations represented by the following compound group h.

The quinone imine chromophore is preferably represented by the following formulas (8-1) to (8-3).

[In the formulae (8-1) to (8-3), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹⁰ , R ¹¹¹ , R ¹¹⁴ , R ¹¹⁵ R ¹¹⁶ , R ¹¹⁷ and R ¹¹⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a benzyl group, R ¹⁰⁷ and R ¹¹³ independently of each other represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R ¹¹² represents -NR ¹¹⁹ R ¹²⁰ (R ¹¹⁹ and R ¹²⁰ independently of each other represent a substituted or unsubstituted carbon number 1~ 6 alkyl), hydroxy, nitro or cyano, and Q represents an oxygen atom or a sulfur atom. ]

The substituent of the above alkyl group may, for example, be a halogen group, a hydroxyl group or a cyano group.

Representative examples of the cation represented by the above formulas (8-1) to (8-3) include cations represented by the following compound group i.

The above-mentioned fluorene color group is preferably represented by the following formula (9-1) or (9-2).

[In the formulae (9-1) and (9-2), R ¹³¹ , R ¹³⁵ and R ¹³⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted one. Phenyl, R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁸ , R ¹³⁹ and R ¹⁴⁰ each independently represent an alkyl group having 1 to 6 carbon atoms, and R ¹³⁷ represents a methylene group or a substituted or unsubstituted alkylene group. ]

The substituent of the alkyl group or the phenyl group may, for example, be an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group or a cyano group. Further, examples of the alkylene group include an alkylene group having 2 to 4 carbon atoms such as an ethyl group, a trimethylene group, a propyl group and a tetramethylene group, and a substituent of the alkylene group may, for example, be a hydroxyl group. , cyano or nitro, etc.

A representative example of the cation represented by the above formula (9-1) or (9-2) is, for example, a cation represented by the following compound group j.

The indigo chromophore group is preferably represented by the following formula (10).

CuPC-T (10)

In the formula (10), CuPc represents a copper indigo residue, and T represents a group represented by the following formula (10a) or (10b). ]

[In the formulae (10a) and (10b), R ¹⁵¹ , R ¹⁵² , R ¹⁵³ , R ¹⁵⁴ , R ¹⁵⁵ , R ¹⁵⁶ , R ¹⁵⁷ and R ¹⁵⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or Phenyl, p independently of each other represents an integer from 2 to 8, and mb represents an integer from 1 to 5. ]

Representative examples of the cation represented by the above formula (10) include cations represented by the following compound group k.

As above The chromophore group is preferably represented by the following formula (11).

In the formula (11), R ¹⁶¹ to R ¹⁶⁴ each independently represent a hydrogen atom or a phenyl group, and the phenyl group may be a halogen group, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms; -SO ₃ ^- , -SO ₃ H, -SO ₃ R ¹⁶⁶ or -SO ₂ N(R ¹⁶⁷ )R ^{168 is} substituted. R ¹⁶⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ R ¹⁶⁶ or -SO ₂ N(R ¹⁶⁷ )R ¹⁶⁸ , and may be the same or different when a plurality of R ¹⁶⁵ are present. R ¹⁶⁶ represents an alkyl group having 1 to 8 carbon atoms, and R ¹⁶⁷ and R ¹⁶⁸ each independently represent a hydrogen atom and an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be substituted by a halogen group or an alkoxy group having 1 to 6 carbon atoms. . Mc represents an integer from 0 to 5. ]

Among the cations represented by the above formula (11), a cation represented by the following formula (11a) is particularly preferred.

[In the formula (11a), R ¹⁶⁹ independently represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₃ R ¹⁶⁶ or -SO ₂ NHR ¹⁶⁷ , and R ¹⁶⁵ , R ¹⁶⁶ and R ^{167 have the} same meanings as defined above. ]

The representative example of the cation represented by the above formula (11a) includes, for example, a cation represented by the following compound group m.

Examples of the other cationic chromophore group represented by X ⁺ include a cation represented by the following compound group n.

The specific coloring compound can be produced by a known method, for example, as disclosed in JP-A-2007-503477, and can be produced by a salt exchange reaction. In this case, _a salt of an anion represented by (Z _a R ⁰ _b M) ^- is required, and a commercially available product can be used as the salt, and a well-known method can also be used, for example, refer to Japanese Patent Publication No. 2004-533473, Japanese Special Table Synthesized by the publication of the publication No. 2006-517546.

A specific coloring compound, for example, when X ⁺ is a triarylmethane-based chromophoric group, it is blue to red due to being dissolved in an organic solvent, so that it can be suitably used by using the compound alone or in combination with other coloring agents. A colored composition of, for example, blue pixels, red pixels, and a black colored layer is formed.

As other coloring agents, colors or materials may be appropriately selected depending on the application. Specifically, any of a pigment, a dye, and a natural coloring matter can be used, but a pigment and/or a dye is used from the viewpoint of requiring high color purity, brightness, contrast, light blocking property, and the like for the color layer constituting the color filter. good.

The pigment may be any of an organic pigment and an inorganic pigment, and examples of the organic pigment include a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists). Specifically, a name named as the following color index (C.I.) can be cited.

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14 , CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138 , CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 180, CI Pigment Yellow 211; CI Pigment Orange 5 , CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49 , CI Pigment Orange 61, CI Pigment Orange 64, CI Pigment Orange 68, CI Pigment Orange 70, CI Pigment Orange 71, CI Pigment Orange 72, CI Pigment Orange 73, CI Pigment Orange 74; CI Pigment Red 1, CI Pigment Red 2 , CI Pigment Red 5, CI Pigment Red 17, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 41, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 149, CI Pigment Red 166 , CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 175, CI Yan Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Red 214, CI Pigment Red 220, CI Pigment Red 221, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 262, CI Pigment Red 264, CI Pigment Red 272; CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23 , CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38; CI Pigment Blue 1, CI Pigment Blue 15, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15: 6. CI Pigment Blue 60, CI Pigment Blue 80; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, CI Pigment Black 7.

Moreover, examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, and indigo. Chromium oxide green, cobalt green, alumina, titanium black, synthetic iron black, carbon black, and the like.

In the present invention, the pigment may be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or the like. Further, the pigment can be modified and used as a resin surface as desired. The resin which modifies the surface of the pigment particle is, for example, a vehicle resin described in JP-A-2001-108817 or a commercially available resin for pigment dispersion. For the resin coating method of the surface of the carbon black, for example, a method described in, for example, JP-A-H09-71733, JP-A-H09-95625, JP-A-9-124969, and the like can be employed. Further, the organic pigment is preferably used by refining the primary particles by a so-called salt milling. For the method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

Further, the dye can be appropriately selected from various oil-soluble dyes, direct dyes, acid dyes, metal-coordinate dyes, and the like. For example, it can be named as the following color index (C.I.) name.

CI Solvent Yellow 4, CI Solvent Yellow 14, CI Solvent Yellow 15, CI Solvent Yellow 24, CI Solvent Yellow 82, CI Solvent Yellow 88, CI Solvent Yellow 94, CI Solvent Yellow 98, CI Solvent Yellow 162, CI Solvent Yellow 179; CI Solvent Red 45, CI Solvent Red 49; CI Solvent Orange 2, CI Solvent Orange 7, CI Solvent Orange 11, CI Solvent Orange 15, CI Solvent Orange 26, CI Solvent Orange 56; CI Solvent Blue 35, CI Solvent Blue 37, CI Solvent Blue 59, CI Solvent Blue 67; CI Acid Yellow 17, CI Acid Yellow 29, CI Acid Yellow 40, CI Acid Yellow 76; CI Acid Red 91, CI Acid Red 92, CI Acid Red 97, CI Acid Red 114, CI Acid Red 138, CI Acid Red 151; CI Acid Orange 51, CI Acid Orange 63; CI Acid Blue 80, CI Acid Blue 83, CI Acid Blue 90; CI Acid Green 9, CI Acid Green 16, CI Acid Green 25, CI acid green 27.

The other coloring agents in the present invention may be used singly or in combination of two or more.

The total content of the specific coloring compound and the other coloring agents used as the case may be, in view of the formation of a pixel having a high luminance and excellent color purity, or a black matrix having excellent light shielding properties, usually 5 to 5 in the solid content of the coloring composition. 70% by mass, preferably 5 to 60% by mass. The solid component referred to herein means a component other than the solvent described later.

When a pigment is used as another coloring agent in the present invention, the pigment It can be used together with dispersing agents and dispersing aids as the case may be. As the dispersing agent, for example, a suitable dispersing agent such as a cationic system, an anionic surfactant or a nonionic surfactant can be used, but a polymer dispersant is preferred. Specific examples thereof include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polyethylene glycol diester system. A dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, or the like.

Such a dispersing agent is commercially available. For example, as an acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK chemie (BYK)), as Examples of the urethane-based dispersing agent include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK chemie (BYK)), and Solsperse 76500 (Lubrizol ( (available as a polyethyleneimine-based dispersing agent): Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and polyester dispersant: Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (above It is manufactured by Finetech Co., Ltd.).

In addition, examples of the dispersing aid include a pigment derivative, and specific examples thereof include a copper phthalocyanine, a diketopyrrolopyrrole, and a sulfonic acid derivative of quinophthalone. Further, the content of the dispersing agent and the dispersing aid can be appropriately determined within the range not impairing the object of the present invention.

- (B) Adhesive Resin -

The binder resin in the present invention is not particularly limited, and is preferably a member. A resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl group-containing polymer") is preferably an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer (b1)" )") a copolymer with another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2-(methyl) propylene oxyethyl ester], and ω-carboxyl polymerization. Caprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

Further, examples of the unsaturated monomer (b2) include an N-position substituted maleimide such as N-phenylmaleimide or N-cyclohexylmaleimide; and benzene; An aromatic vinyl compound such as ethylene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl epoxidized propyl ether or vinyl naphthalene; (methyl) Methyl acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, (meth)acrylic acid Benzyl ester, polyethylene glycol (n=2~10) methyl ether (meth) acrylate, polypropylene glycol (n=2~10) methyl ether (meth) acrylate, polyethylene glycol (n=2~ 10) Mono (meth) acrylate, polypropylene glycol (n = 2 ~ 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate Tricyclo[5.2.1.0 ^2,6 ]癸-8-ester, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl (meth)acrylate, p-isopropyl Oxyethylene modified methacrylate, (meth) acrylate (meth) acrylate, (methyl) 3,4-epoxycyclohexylmethyl olefin, 3-[(meth)acrylomethoxymethyl]oxetane, 3-[(methyl)acryloxymethyl]-3-ethyl (meth) acrylate such as oxetane; cyclohexyl vinyl ether, isodecyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] fluoren-8-yl vinyl ether, pentacyclopentadecyl vinyl a vinyl ether such as ether or 3-(vinyloxymethyl)-3-ethyloxetane; polystyrene, poly(methyl) methacrylate, poly(meth)acrylic acid-n-butyl ester, A macromonomer having a mono(meth)acrylonitrile group at the end of a polymer molecular chain, such as a polyoxyalkylene.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

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 from 5 to 50% by mass, and more preferably 10%. ~40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a coloring 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-10-10 Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Copolymer.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei 5-19467, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain is used as a binder resin, as disclosed in JP-A-2008-181095.

The binder resin in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC (solution solvent: tetrahydrofuran), and is usually 1,000 to 100,000, preferably 3,000 to 50,000. When the Mw is too small, the residual film ratio of the obtained coating film or the like may be lowered or impaired in the shape of the pattern, heat resistance, etc., and the electrical characteristics may deteriorate. On the other hand, if the film size is too large, the resolution may be lowered or the pattern shape may be impaired. When it is applied by a slit nozzle method, there is a tendency that dry foreign matter is likely to occur.

In the present invention, the weight average molecular weight of the binder resin and the ratio (Mw/Mn) of the number average molecular weight (Mn) in terms of polystyrene measured by GPC (solution solvent: tetrahydrofuran) are preferably 1.0 to 5.0. More preferably 1.0~3.0.

In the present invention, the binder resin can be produced by a known method, or can be controlled according to the method disclosed in, for example, Japanese Laid-Open Patent Publication No. 2003-222717, Japanese Patent Laid-Open Publication No. Hei. No. 2006-259680, and International Publication No. 07/029871. Its structure or Mw, Mw / Mn.

In the present invention, the binder resin may be used singly or in combination of two or more.

In the present invention, the content of the binder resin is relative to a specific The total amount of the coloring compound and other coloring agents used as the case may be, usually, 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass. If the content of the binder resin is too small, for example, the alkali developability may be lowered or the storage stability of the obtained colored composition may be lowered. On the other hand, if the amount of the colorant is excessively lowered, it may be difficult to achieve the result. The color density of the purpose of the film.

-(C) Crosslinker -

In the present invention, the (C) crosslinking agent means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxirane group, an oxypropylene group, and an N-alkoxymethylamino group. In the present invention, as the (C) crosslinking agent, a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups is preferable, and particularly preferably used in combination. A compound having two or more (meth) acrylonitrile groups and a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylonitrile groups include, for example, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. A caprolactone-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, and a hydroxyl group-containing (meth) acrylate reacted with a polyfunctional isocyanate The obtained polyfunctional urethane (meth) acrylate, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a hydroxyl group-containing (meth) acrylate with an acid anhydride, and the like.

Here, examples of the aliphatic polyhydroxy compound include ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol. A trivalent or higher aliphatic polyhydroxy compound such as an aliphatic polyhydroxy compound, glycerin, trimethylolpropane, pentaerythritol or dipentaerythritol. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and Pentaerythritol penta (meth) acrylate, glyceryl dimethacrylate, and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dianhydride such as hexahydrophthalic anhydride, pyromellitic anhydride, and biphenyl tetra A tetrabasic acid dianhydride such as carboxylic acid dianhydride or diphenyl ketone tetracarboxylic dianhydride.

In addition, as the above-mentioned caprolactone-modified polyfunctional (meth) acrylate, a compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified. Examples of the polyoxyalkyl (meth)acrylate modified with the oxidized olefin include oxyethylene and/or oxypropylene modified di(meth)acrylate of bisphenol A, and oxyethylene of iso-cyanuric acid and/or Or oxypropylene modified tri(meth)acrylate, trimethylolpropane oxyethylene and/or oxypropylene modified tri(meth)acrylate, pentaerythritol oxyethylene and/or oxypropylene modified tris(A) Ethylene acrylate, pentaerythritol oxyethylene and/or oxypropylene modified tetra(meth) acrylate, dipentaerythritol oxyethylene and/or oxypropylene modified penta (meth) acrylate, dipentaerythritol oxyethylene and / or oxypropylene modified hexa (meth) acrylate and the like.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Moreover, the structure of melamine and the structure of benzoguanamine means that one or more of them are contained. Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton also includes the concept of melamine, benzoguanamine or the like. 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'-tetrakis (alkoxymethyl) benzoguanamine, N, N, N', N'-tetrakis (alkoxymethyl) glycoluril, and the like.

Among these polyfunctional monomers, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, and a polycaprolactone-modified polyfunctional (A) Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzamide are preferred. Among the polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound having a valence of three or more with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate And dipentaerythritol hexaacrylate, and a compound obtained by reacting pentaerythritol triacrylate with succinic anhydride in a polyfunctional (meth) acrylate having a carboxyl group, and reacting dipentaerythritol pentaacrylate with succinic anhydride The compound is excellent in the viewpoint that the strength of the colored layer is high and the surface smoothness of the colored layer is excellent, and the underlying layer and the light-shielding layer are less likely to cause underlying contamination and film retention.

In the present invention, the (C) crosslinking agent may be used singly or in combination of two or more.

In the present invention, the content of the (C) crosslinking agent is relative to the (B) viscosity. The amount of the binder resin is preferably from 10 to 1,000 parts by mass, particularly preferably from 20 to 500 parts by mass, based on 100 parts by mass of the resin. Here, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, when the content of the crosslinking agent is too large, when the alkali developability is imparted to the coloring composition of the invention, the alkali developability is likely to be lowered, and the underlying layer or the light-shielding layer on the unexposed portion is subjected to underlying contamination and film residue. The tendency to wait.

-(D) Photopolymerization initiator -

The coloring composition of the present invention may contain (D) a photopolymerization initiator. Thereby, the coloring composition can be imparted with radiation linearity. The (D) photopolymerization initiator used in the present invention is an active material capable of starting polymerization of the above (C) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, or X-ray. Compound.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, diphenyl ketone compound, α-diketone compound, polynuclear oxime compound, diazo compound, sulfimine sulfonate An acid ester compound or the like.

In the present invention, the photopolymerization initiator may be used singly or in combination of two or more. The photopolymerization initiator is preferably a thioxanthone compound, an acetophenone compound, a biimidazole compound, or the like. At least one selected from the group consisting of a compound and an O-mercapto lanthanide compound.

Among the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone-based compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropyl group. Thiophenone, 4-isopropylthioxanthone, 2,4- Dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Phenylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenanylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole-based 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.

Further, when a biimidazole-based compound is used as a photopolymerization initiator, a hydrogen donor is used in combination, and it is preferable from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound which can supply a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine-based hydrogen donor such as a thiol-based hydrogen donor such as azole or 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino)diphenyl ketone. In the present invention, the hydrogen donor may be used singly or in combination of two or more kinds, but one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors may be used, and it is preferable from the viewpoint of further improving the sensitivity. .

Again, as the above three Specific examples of the compound include, for example, 2,4,6-paran (trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halogenated methyl groups a compound.

Further, specific examples of the O-fluorenyl fluorene-based compound include, for example, 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzamide). Ketone, ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-ethylindenyl), Ethylketone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-, 1-(O-acetamidine) Ketone, ethyl ketone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzidine }}-9H-carbazol-3-yl]-, 1-(O-ethylindenyl) and the like.

In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone-based compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4′-bis(dimethylamino)diphenyl ketone, 4,4′-bis(diethylamino)diphenyl ketone, and 4-diethylamine. Acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethyl) Aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone, and the like.

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, per 100 parts by mass of the (C) crosslinking agent. Here, if the content of the photopolymerization initiator is too small, it will be advantageous. If the curing by the exposure is insufficient, on the other hand, if the amount is too large, the colored layer formed tends to fall off from the substrate during development.

- (E) Solvent -

The coloring composition of the present invention contains the above components (A) to (C) and any other components added arbitrarily, but is usually prepared by mixing a solvent to prepare a liquid composition.

The solvent is appropriately selected as long as it can disperse or dissolve the components (A) to (C) constituting the coloring composition or other components, and does not react with the components and has moderate volatility.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and 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 , (poly) olefin based propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Alkenyl ethers: alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, (cyclo)alkanols such as 2-ethylhexanol and cyclohexanol; keto alcohols such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethyl Glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol single (poly)alkylene glycol monoalkyl ether acetate such as methyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc. Ketones; diacetates such as propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate; methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropane Alkoxycarboxylates such as acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate Ester, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate, ethyl acetate Other esters such as ethyl ester and ethyl 2-oxobutanoate; aromatics such as toluene and xylene Hydrocarbons; N, N- dimethylformamide, N, N- dimethylacetamide, N- methylpyrrolidone or the like Amides Amides like.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol are preferred from the viewpoints of solubility, pigment dispersibility, and coating properties. Monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3 - Butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, isobutyl acetate , n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate and the like.

In the present invention, the solvent may be used singly or in combination of two or more.

The content of the solvent is not particularly limited, and the total concentration of each component other than the solvent to be removed from the coloring composition is preferably from 5 to 50% by mass, particularly preferably from the viewpoints of coating properties and stability of the obtained coloring composition. In order to become 10 to 40% by mass.

-additive-

The colored composition of the present invention may contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); and an interfacial activity such as a fluorine-based surfactant or a lanthanoid surfactant; Agent; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Dimethoxyoxane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyl Trimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethyl Adhesion promoter of oxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, etc.; 2,2-sulfur An antioxidant such as bis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol; 2-(3-tert-butyl-5-methyl-2-hydroxyl Ultraviolet absorbers such as phenyl)-5-chlorobenzotriazole and alkoxydiphenyl ketone; anti-agglomerating agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, and citrine Acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amine Residue improver of 1,3-1,3-propanediol, 4-amino-1,2-butanediol, etc.; succinic acid mono[2-(methyl)propenyloxyethyl], phthalic acid mono[ a developer improving agent such as 2-(meth)acryloxyethyloxyethyl ester] or ω-carboxypolycaprolactone mono(meth)acrylate; and a reactive functional group disclosed in JP-A-2008-242078 a base oxane oligomer or the like.

The colored composition of the present invention can be produced according to an appropriate method, and examples of the preparation method thereof include those disclosed in JP-A-2008-58642 and JP-A-2010-132874. When a specific coloring compound is used together with a pigment as another coloring agent, as disclosed in Japanese Laid-Open Patent Publication No. 2010-132874, the first filter is passed through the first filter after passing the dye solution containing the specific coloring compound. A method in which the dye solution is mixed with a separately prepared pigment dispersion or the like, and the obtained colored composition is passed through a second filter is preferred. Further, by dissolving the dye containing the specific coloring compound, the above components (B) to (C), and optionally the component (D) and the additive component in the solvent (E), the obtained solution is passed through the first filter. Preferably, a method in which the solution having passed through the first filter is mixed with the separately prepared pigment dispersion and the obtained colored composition is passed through the second filter is also preferred. Further, by passing the dye solution containing the specific coloring compound through the first filter, the dye solution having passed through the first filter and the above components (B) to (C), and optionally (D) to (E) Mixing and dissolving the ingredients and additive components, and passing the obtained solution It is also preferred to pass the second filter, and to mix the solution which has passed through the second filter with the separately prepared pigment dispersion, and to obtain the colored composition obtained by passing through the third filter.

Color filter and manufacturing method thereof

The color filter of the present invention is provided with a coloring layer containing a specific coloring compound.

As a method of manufacturing a color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate as needed, such as to form a portion of the pixel. Next, a liquid composition containing, for example, a blue radiation-sensitive composition of a specific coloring compound is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, after the coating film was exposed through a photomask, development was carried out using an alkali developing solution, and the unexposed portion of the coating film was dissolved and removed. Thereafter, by post-baking, a pixel array in which the blue pixel patterns are arranged in a predetermined arrangement is formed.

Next, using a coloring composition of green or red coloring, the coating, prebaking, exposure, development, and post-baking of each coloring radiation composition are performed in the same manner as described above, and green paintings are sequentially formed on the same substrate. Prime array and red pixel array. Thereby, a color filter in which a pixel array of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above.

Further, the black matrix may be formed by a photolithography method using a metal film such as a chromium film formed by sputtering or vapor deposition, but a color ray emission in which a black colorant is dispersed may be used. The composition is formed in the same manner as in the case of forming the above-described pixels. The colored composition of the present invention can also be suitably used to form the black matrix.

Examples of the substrate used in forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, as necessary, appropriate pre-treatments such as drug treatment, plasma treatment, ion implantation, sputtering, gas phase reaction, vacuum vapor deposition, and the like using a decane coupling agent or the like may be performed on the substrates.

When the colored radiation-sensitive composition is applied to a substrate, an appropriate coating method such as a spray coating 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, and it is particularly preferable to use a spinning method. Coating method, slot die coating method.

The pre-baking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. Further, the conditions of heat drying are usually carried out at 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness is usually from 0.6 to 8.0 μm, preferably from 1.2 to 5.0 μm, as the film thickness after drying.

Examples of the light source used for forming the pixels and/or the black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, or the like. A laser source such as an argon ion laser, a YAG laser, a XeCl excimer laser, or a nitrogen laser is preferably a radiation having a wavelength in the range of 190 to 450 nm.

The amount of exposure of the radiation is generally preferably from 10 to 10,000 J/m ² .

Further, as the alkali developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4.0]-7- is preferable. An aqueous solution of undecene, 1,5-diazabicyclo-[4.3.0]-5-decene or the like.

In the above alkali developing solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after alkali development, water washing is usually performed.

As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be used. The developing conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually carried out at 120 to 280 ° C for about 10 to 60 minutes. From the viewpoint of the heat resistance of the coloring agent, the post-baking temperature is preferably 240 ° C or less, and particularly preferably 230 ° C or less.

The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

Moreover, as a second method of producing a color filter, a method of obtaining each color pixel by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a partition wall having a shading function is formed on the surface of the substrate. Next, for example, a liquid composition in which a blue colored composition containing a specific coloring compound is dispersed is discharged from an ink jet apparatus into a partition wall formed, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then hardened by post-baking to form a blue pixel pattern.

Next, using a green or red colored composition, a green pixel pattern is sequentially formed on the same substrate as described above. Red pixel pattern. Thereby, a color filter in which a pixel pattern of three primary colors of red, green, and blue is disposed on the substrate is obtained. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above.

Further, the partition wall not only has a light-shielding function, but also realizes a function of preventing color mixing of the coloring compositions discharged into the compartments, so that the film thickness is thicker than the black matrix used in the first method. Therefore, the partition walls are usually formed using a black sensitizing radioactive composition.

The substrate or the source of radiation used in forming the color filter, and the method or condition of prebaking or post-baking are the same as the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is the same as the height of the partition wall.

On the pixel pattern obtained in this manner, a transparent conductive film is formed by sputtering after forming a protective film as needed. It is also possible to form a transparent conductive film and then form a spacer as a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). At this time, a color-sensing radiation composition in which a black colorant is dispersed may be used, but the coloring composition of the present invention may also be suitably used for the formation of a black spacer.

The color filter of the present invention obtained in this manner is extremely useful for color liquid crystal display elements, color image sensor elements, color sensors, organic EL display elements, electronic paper, and the like because of extremely high luminance and color purity.

Display component

The display element of the present invention is provided with the color filter of the present invention. As the display element, for example, a color liquid crystal display element, EL display elements, electronic paper, and the like.

The color liquid crystal display element having the color filter of the present invention can have an appropriate structure. For example, the color filter may be formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed may be opposed to each other by the liquid crystal layer. Further, a substrate on which a color filter is formed and a substrate on which an ITO (indium oxide-doped indium oxide) electrode is formed may be formed on the surface of the driving substrate on which the thin film transistor (TFT) is disposed. The structure is opposed to the liquid crystal layer. The structure of the latter can make the aperture ratio exceptionally high, and has the advantage of being able to obtain a bright and high-definition liquid crystal display element.

The color liquid crystal display element including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a CCFL (Cold Cathode Fluorescent Lamp). As the white LED, for example, a white LED which obtains white light by combining a mixed color red LED and a green LED and a blue LED, and white light by obtaining a mixed color blue LED and a red LED and a green phosphor are mentioned. LED, a white LED that obtains white light by combining a mixed color blue LED with a red illuminating phosphor and a green illuminating phosphor, and a white LED that obtains white light by mixing a blue LED and a YAG-based phosphor. A white LED that obtains white light by combining a mixed color blue LED with an orange luminescent phosphor and a green luminescent phosphor, by combining a mixed color ultraviolet LED with a red luminescent phosphor and a green luminescent phosphor and blue luminescent fluorescent A white LED or the like of white light is obtained.

A color liquid crystal display element having the color filter of the present invention can be suitably used for a TN (Twisted Nematic) type. , STN (Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Alignment) type, OCB (Optically Compensated Birefringence) )) The appropriate liquid crystal mode.

In addition, the organic EL display element having the color filter of the present invention may have a suitable structure, and a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242, for example.

Further, the electronic paper having the color filter of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169.

[Examples]

The embodiments of the present invention will be more specifically described below by way of examples. However, the invention is not limited to the embodiments described below.

<Synthesis and evaluation of specific coloring compounds>

1. Synthesis of specific coloring compounds

Synthesis Example 1

To the spiral tube to which the stirrer was placed, 1.4 g (2.72 mmol) of CI basic blue 7 (Cl ^- salt of the compound c2 of the above compound group c) and 0.768 g of potassium tetrafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.) were added ( 4.08 mmol), 20 mL of chloroform and 10 mL of water were stirred at room temperature for 7 hours. After the aqueous layer was separated and evaporated, the organic layer was washed twice, and concentrated under reduced pressure, and the obtained solid was dried under reduced pressure to yield 1.70 g (yield 80.2%) of a blue-black solid. This was designated as Compound A. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of the compound A was confirmed to be the objective compound.

¹ H-NMR: δ 7.95 (d, 1H), 7.06-7.60 (m, 8H), 6.75 (brs, 3H), 6.68 (d, 2H), 6.05 (brs, 1H), 3.58 (q, 10H) , 1.58(s,1H), 1.49(t,3H),1.31(t,12H)

Synthesis Example 2

The specific coloring compound was synthesized in the same manner as in Synthesis Example 1 except that the potassium hexafluoroborate in the synthesis example 1 was changed to the use of lithium hexafluoroborate (manufactured by Wako Pure Chemical Industries, Ltd.), and ¹ H-NMR (solvent: deuteration) was measured. Chloroform) was confirmed as the target compound. This was designated as Compound B. The ¹ H-NMR spectrum of Compound B was as follows.

¹ H-NMR: δ 8.08 (d, 1H), 7.05-7.62 (m, 8H), 6.75 (brs, 3H), 6.68 (d, 2H), 6.38 (brs, 1H), 3.55 (q, 10H) , 1.63 (s, 1H), 1.49 (t, 3H), 1.31 (t, 12H)

Synthesis Example 3

The specific coloring compound was synthesized in the same manner as in Synthesis Example 1 except that potassium tetrafluoroborate in Synthesis Example 1 was changed to use yttrium (pentafluorobenzene) borate (manufactured by Wako Pure Chemical Industries, Ltd.), and ¹ H was measured by measurement. - NMR (solvent: deuterated chloroform), which was confirmed to be the objective compound. This was designated as Compound C. The ¹ H-NMR spectrum of Compound C was as follows.

¹ H-NMR: δ 7.95 (d, 1H), 7.06-7.60 (m, 8H), 6.75 (brs, 3H), 6.68 (d, 2H), 6.05 (brs, 1H), 3.58 (q, 10H) , 1.58(s,1H), 1.49(t,3H),1.31(t,12H)

Synthesis Example 4

The specific coloring compound was synthesized in the same manner as in Synthesis Example 1 except that the potassium tetrafluoroborate in the synthesis example 1 was changed to K [BF(CN) ₃ ], and ¹ H-NMR (solvent: deuteration) was measured. Chloroform) was confirmed as the target compound. This was designated as Compound D. The ¹ H-NMR spectrum of Compound D was as follows.

¹ H-NMR: δ 7.95 (d, 1H), 7.06-7.60 (m, 8H), 6.75 (brs, 3H), 6.68 (d, 2H), 6.13 (brs, 1H), 3.58 (q, 10H) , 1.58(s,1H), 1.49(t,3H),1.31(t,12H)

Synthesis Example 5

In the same manner as in Synthesis Example 1, except that CI basic blue 7 in Synthesis Example 1 was changed to CI basic blue 11 (Cl ^- salt of compound c4 of the above compound group c), a specific coloring compound was synthesized by The title compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform).

Synthesis Example 6

A specific coloring compound was synthesized in the same manner as in Synthesis Example 1 except that CI basic blue 7 in Synthesis Example 1 was changed to use CI basic violet 16 (Cl ^- salt of compound e2 of the above compound group e). The title compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform).

Synthesis Example 7

A specific coloring compound was synthesized by the same procedure as in Synthesis Example 1 except that CI basic blue 7 in Synthesis Example 1 was changed to use CI basic blue 41 (methane sulfate of compound f13 of the above compound group f). The title compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform).

Synthesis Example 8

A specific coloring compound was synthesized in the same manner as in Synthesis Example 1 except that CI basic blue 7 in Synthesis Example 1 was changed to use CI basic blue 3 (Cl ^- salt of compound i4 of the above compound group i). The title compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform).

Synthesis Example 9

The specific coloring compound was synthesized by the same procedure as in Synthesis Example 1 except that CI basic blue 7 in Synthesis Example 1 was changed to use CI basic blue 22 (Cl ^- salt of compound j1 of the above compound group j). The title compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform).

Example 1

In the same manner as in Synthesis Example 1, except that the potassium tetrafluoroborate in the synthesis example 1 was changed to the use of sodium dicyanamide (manufactured by Wako Pure Chemical Industries, Ltd.), a specific coloring compound was synthesized by performing ¹ H-NMR (solvent: The measurement was confirmed to be the objective compound by deuterated chloroform. This was designated as Compound E. The ¹ H-NMR spectrum of Compound E was as follows.

¹ H-NMR: δ 7.95 (d, 1H), 6.98-7.65 (m, 7H), 6.76 (brs, 4H), 6.69 (d, 1H), 5.96 (brs, 1H), 3.56 (q, 10H) , 1.50 (t, 3H), 1.30 (t, 12H)

Example 2

The specific coloring compound was synthesized by the same procedure as in Synthesis Example 1, except that CI basic blue 7 in Synthesis Example 1 was changed to use CI basic blue 3 and potassium tetrafluoroborate instead of sodium dicyanamide. The title compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform).

Example 3

The specific coloring compound was synthesized by the same procedure as in Synthesis Example 1 except that CI basic blue 7 in Synthesis Example 1 was changed to use CI basic blue 22 and potassium tetrafluoroborate instead of sodium dicyanamide. The title compound was confirmed by ¹ H-NMR (solvent: deuterated chloroform).

2. Evaluation of specific coloring compounds

The compound A obtained in Synthesis Example 1 was dissolved in 10% by mass or more in cyclohexanone, and the solution was blue. All of the specific coloring compounds obtained in Synthesis Examples 2 to 9 and Examples 1 to 3 were dissolved in cyclohexanone in an amount of 10% by mass or more.

Further, the specific coloring compounds obtained in Synthesis Examples 1 to 9 and Examples 1 to 3 were all subjected to a thermogravimetric-differential heat simultaneous measurement and analyzed to have a 5% mass reduction temperature of 250 ° C or higher. On the other hand, simultaneous determination of CI basic blue 7, CI basic blue 11, CI alkaline violet 16, CI basic blue 41, CI basic blue 3 and CI basic blue 22 by thermogravimetry-differential heat The 5% mass reduction temperature is below 200 °C.

<Preparation of Pigment Dispersion>

Preparation Example 1

Using 15 parts by mass of CI Pigment Blue 15:6 as a coloring agent, BYK-LPN21116 (manufactured by BYK Chemie (BYK) Co., Ltd.), 12.5 parts by mass (solid content concentration = 40% by mass) as a dispersing agent, propylene glycol monomethyl ether acetate 72.5 parts by mass as a solvent, a pigment dispersion (A-1) was prepared by a bead mill.

Preparation Example 2

A pigment dispersion liquid (A-2) was prepared in the same manner as in Production Example 1 except that C.I. Pigment Blue 15:6 was used instead of C.I. Pigment Violet 23 as a colorant.

<Preparation of dye solution>

Preparation Example 3

Dye solution A was prepared by mixing 5 parts by mass of the compound A as a coloring agent and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 4

Dye solution B was prepared by mixing 5 parts by mass of Compound B as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 5

Dye solution C was prepared by mixing 5 parts by mass of the compound C as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 6

Dye solution D was prepared by mixing 5 parts by mass of the compound D as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 7

Dye solution E was prepared by mixing 5 parts by mass of compound E as a colorant and 95 parts by mass of propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 8

Dye solution F was prepared by mixing 7 parts by mass of C.I. Basic Blue as a coloring agent and 95 parts by mass of propylene glycol monomethyl ether as a solvent.

<Synthesis of binder resin>

To a flask equipped with a cooling tube and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was added and nitrogen substitution was carried out. The mixture was heated to 80 ° C, and 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, and methacrylic acid were added dropwise at the same temperature for 1 hour. 2-hydroxyethyl ester 15 parts by mass, methacryl 23 parts by mass of 2-ethylhexyl acid, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid mono(2-propenyloxyethyl), and 2,2'-azobis ( 2,4-dimethylvaleronitrile) 6 parts by mass of a mixed solution, and maintained at this temperature for 2 hours of polymerization. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was further carried out for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin: Mw = 12,200, Mn = 6,500. This binder resin is referred to as "adhesive resin (B1)".

<Preparation and evaluation of coloring composition>

Example 4

13.6 parts by mass of the mixed pigment dispersion (A-1), 27.2 parts by mass of the dye solution A, 18.1 parts by mass of a binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass with MW-30 manufactured by Sanwa Chemical Co., Ltd. (with N, N, N', N', N", N"-six (a Oxymethyl group) melamine as a main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator 2.2 parts by mass of phenyl phenyl)butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGACURE 369), 0.2 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol as a solvent Monomethyl ether acetate was used to prepare a coloring composition (CR1) having a solid concentration of 20% by mass.

The colored composition (CR1) was applied onto a glass substrate using a spin coater, and then prebaked on a hot plate at 80 ° C for 10 minutes to form a coating film. The same operation was carried out by changing the number of revolutions of the spin coater to form three coating films having different film thicknesses.

Next, after cooling the substrate to room temperature, the high-pressure mercury lamp was exposed to light at a wavelength of 2,000 J/m ² for each coating film at a wavelength of 365 nm, 405 nm, and 436 nm without using a photomask. Thereafter, a 0.04 mass% potassium hydroxide aqueous solution containing 23 ° C was spray-developed for 90 seconds by a developing solution discharged onto the substrate at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm). Thereafter, the substrate was washed with ultrapure water and air-dried, and then baked in a clean oven at 230 ° C for 30 minutes to form a cured film for evaluation.

For the obtained three cured films, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and the stimulus value at the C light source, the 2 degree field of view, and the CIE color system. (Y). Further, the film thickness of the obtained cured film was measured using Alpha-Step IQ manufactured by KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulation value (Y), and the film thickness at the chromaticity coordinate value y=0.080 were obtained. The evaluation results are shown in Table 1. The larger the stimulation value (Y), the higher the light transmittance (luminance), and the thinner the film thickness, the higher the coloring power.

The substrate on which the cured film is formed is sandwiched between two deflecting plates, and is irradiated with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and at the same time, the deflecting plate of the front side is rotated by a luminance meter LS-100 (Minolta ( The system determines the maximum and minimum values of the transmitted light intensity. Further, for each of the cured films, the value obtained by dividing the maximum value by the minimum value is taken as the contrast ratio. From the measurement results, the contrast ratio at the chromaticity coordinate value y = 0.080 was obtained. The evaluation results are shown in Table 1.

Example 5

15.5 parts by mass of the mixed pigment dispersion (A-1), 22.3 parts by mass of the dye solution B, 16.1 parts by mass of a binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass with MW-30 manufactured by Sanwa Chemical Co., Ltd. (with N, N, N', N', N", N"-six (a Oxymethyl group) melamine as a main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator 2.2 parts by mass of phenyl phenyl)butan-1-one (manufactured by Ciba speciality chemicals, trade name IRGACURE 369), 0.2 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol as a solvent Methyl ether acetate, a coloring composition (CR2) having a solid concentration of 20% by mass was prepared.

Evaluation was carried out in the same manner as in Example 4 except that the coloring composition (CR2) was used instead of the coloring composition (CR1). The evaluation results are shown in Table 1.

Example 6

16.2 parts by mass of the mixed pigment dispersion (A-1), 21.3 parts by mass of the dye solution C, 16.1 parts by mass of a binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass with MW-30 manufactured by Sanwa Chemical Co., Ltd. (with N, N, N', N', N", N"-six (a Oxymethyl group) melamine as a main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator 2.2 parts by mass of phenyl phenyl)butan-1-one (manufactured by Ciba speciality chemicals, trade name IRGACURE 369), 0.2 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol as a solvent Methyl ether acetate was used to prepare a coloring composition (CR3) having a solid concentration of 20% by mass.

Evaluation was carried out in the same manner as in Example 4 except that the coloring composition (CR3) was used instead of the coloring composition (CR1). The evaluation results are shown in Table 1.

Example 7

15.5 parts by mass of the mixed pigment dispersion (A-1), 23.2 parts by mass of the dye solution D, 16.1 parts by mass of a binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass with MW-30 manufactured by Sanwa Chemical Co., Ltd. (with N, N, N', N', N", N"-six (a Oxymethyl group) melamine as a main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator 2.2 parts by mass of phenyl phenyl)butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGACURE 369), 0.2 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol as a solvent Monomethyl ether acetate was used to prepare a coloring composition (CR4) having a solid concentration of 20% by mass.

Evaluation was carried out in the same manner as in Example 4 except that the coloring composition (CR4) was used instead of the coloring composition (CR1). The evaluation results are shown in Table 1.

Example 8

13.6 parts by mass of the mixed pigment dispersion (A-1), 25.2 parts by mass of the dye solution E, 18.1 parts by mass of a binder resin (B1) solution as a binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 5.5 parts by mass with MW-30 manufactured by Sanwa Chemical Co., Ltd. (with N, N, N', N', N", N"-six (a Oxymethyl group) melamine as a main component, weight average degree of polymerization 1.3) 2.4 parts by mass, 2-benzyl-2-dimethylamino-1-(4-) as a photopolymerization initiator 2.2 parts by mass of phenyl phenyl)butan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: IRGACURE 369), 0.2 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol as a solvent Monomethyl ether acetate was used to prepare a coloring composition (CR5) having a solid concentration of 20% by mass.

Evaluation was carried out in the same manner as in Example 4 except that the coloring composition (CR5) was used instead of the coloring composition (CR1). The evaluation results are shown in Table 1.

Comparative example 1

18.1 parts by mass of the mixed pigment dispersion (A-1), 4.5 parts by mass of the pigment dispersion (A-2), 16.1 parts by mass of the binder resin (B1) solution as the binder resin, and the East Asia Synthetic Co., Ltd. as a crosslinking agent The company made 5.5 parts by mass of M-402 and 2.4 parts by mass of MW-30 manufactured by Sanhe Chemical Co., Ltd., and 2-benzyl-2-dimethylamino-1-(4- as a photopolymerization initiator. 2.2 parts by mass of phenyl phenyl)butan-1-one (manufactured by Ciba speciality chemicals, trade name IRGACURE 369), 0.2 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol as a solvent Methyl ether acetate was used to prepare a coloring composition (CR6) having a solid concentration of 20% by mass.

Evaluation was carried out in the same manner as in Example 4 except that the coloring composition (CR6) was used instead of the coloring composition (CR1). The evaluation results are shown in Table 1.

Comparative example 2

18.1 parts by mass of the mixed pigment dispersion (A-1), 24.2 parts by mass of the dye solution F, 16.1 parts by mass of a binder resin (B1) solution as a binder resin, and 5.5 parts by mass of East Asia Synthetic Co., Ltd. as a crosslinking agent M-402 and Sanwa Chemical Co., Ltd. made 2.4 parts by mass of MW-30, and 2-benzyl-2-dimethylamino-1-(4- as a photopolymerization initiator 2.2 parts by mass of phenyl phenyl)butan-1-one (manufactured by Ciba speciality chemicals, trade name IRGACURE 369), 0.2 parts by mass of Megafac F-554 manufactured by DIC Co., Ltd. as a fluorine-based surfactant, and propylene glycol as a solvent Methyl ether acetate was used to prepare a coloring composition (CR7) having a solid concentration of 20% by mass.

Evaluation was carried out in the same manner as in Example 4 except that the coloring composition (CR7) was used instead of the coloring composition (CR1). The evaluation results are shown in Table 1.

In Table 1, "B15:6" means C.I. Pigment Blue 15:6, "V23" means C.I. Pigment Violet 23, and "BB-7" means C.I. Basic Blue 7.

Claims (8)

A colored composition comprising: (A) a compound represented by the following formula (1), (B) a binder resin, and (C) a crosslinking agent; X ⁺ (Z _a R ⁰ _b M) ^- (1) [ In the formula (1), X ⁺ represents a cationic chromophore group, Z represents an electron withdrawing group, R ⁰ represents an alkyl group, an aryl group, a cycloalkyl group or an alkylaryl group, and M represents a phosphorus atom or a boron atom, Z, R ^When there are multiple existences of ⁰ , they may be the same or different; a represents an integer from 1 to 6, b represents an integer from 0 to 5, and a+b is 4 or 6; however, when M is a phosphorus atom, the (Z _a R ⁰ _b M) ^- is an anion represented by the following formula (1a), and when M is a boron atom, the (Z _a R ⁰ _b M) ^- is an anion represented by the following formula (1b); [(R ¹ ) _c P Hal _6-c ] ^- (1a) [In the formula (1a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, and Hal represents a halogen group. When a plurality of R ¹ and Hal are present, they may be the same or different; Indicates 0, 5 or 6][(R ² ) _d B Hal _4-d ] ^- (1b) [In the formula (1b), R ² represents a cyano group, B represents a boron atom, Hal represents a halogen group, R ² , Hal When there are multiple existences, they may be the same or different; d means 2 or 3]. The coloring composition of claim 1, wherein in the formula (1a), the R ¹ is a fluorinated alkyl group and the Hal is a fluorine group. The coloring composition of claim 1, wherein in the formula (1b), the Hal is a fluorine group. The colored composition of claim 1 or 3, wherein the anion represented by the formula (1b) is selected from B(CN) ₂ F ₂ ^- or B(CN) ₃ F ^- . The colored composition of claim 1, wherein the (C) crosslinking agent is a compound having two or more polymerizable groups. The coloring composition of claim 1, wherein the X ⁺ is a triarylmethane chromophore group, a methine chromophore group, an azo chromophore group, a diarylmethane chromophore group, a quinone imine group, a lanthanide chromophore or A chromophore group. A color filter comprising a coloring layer containing a compound represented by the following formula (1); X ⁺ (Z _a R ⁰ _b M) ^- (1) [in the formula (1), X ⁺ represents a cationic property a chromophoric group, Z represents an electron withdrawing group, R ⁰ represents an alkyl group, an aryl group, a cycloalkyl group or an alkylaryl group, and M represents a phosphorus atom or a boron atom, and when Z and R ⁰ respectively exist, they may be the same It may be different; a represents an integer from 1 to 6, b represents an integer from 0 to 5, and a+b is 4 or 6; however, when M is a phosphorus atom, the (Z _a R ⁰ _b M) ^- is the following formula (1a) ) an anion, when M is a boron atom, the (Z _a R ⁰ _b M) ^- is an anion represented by the following formula (1b)]; [(R ¹ ) _c P Hal _6-c ] ^- (1a) In (1a), R ¹ represents a halogenated hydrocarbon group, P represents a phosphorus atom, Hal represents a halogen group, and when R ¹ and Hal are respectively present, respectively, they may be the same or different; c represents 0, 5 or 6] [(R ² _d B Hal _4-d ] ^- (1b) [In the formula (1b), R ² represents a cyano group, B represents a boron atom, and Hal represents a halogen group. When a plurality of R ² and Hal are present, the same may be used. Different; d means 2 or 3]. A display element comprising the color filter of claim 7.