JP2012107192A - Coloring composition, color filter, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition containing a xanthene-based colorant excellent in heat resistance.SOLUTION: The coloring composition contains a colorant (A), a binder resin (B) and a cross-linking agent (C), and is characterized by containing as the colorant (A), a colorant represented by formula (1): XZ(wherein Xis a xanthene chromophore; and Zis a conjugate base of an acid having a halogenated hydrocarbon group).

Description

  The present invention relates to a coloring composition, a color filter, and a display element, and more specifically, a coloring composition containing a specific coloring agent, a color filter including a coloring layer containing the coloring agent, and the color filter. The present invention relates to a display element.

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

  By the way, it is known that it is effective to use a dye as a colorant in order to realize high luminance and high color purity of a display element or high definition of a solid-state imaging element. For example, Patent Document 5 proposes the use of a xanthene dye having a specific structure.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2010-32999 A

However, the xanthene dyes proposed in Patent Document 5 have insufficient heat resistance, and after passing through a heating (post-baking) step after exposure / development exceeding 200 ° C., the chromaticity characteristics of the pigment The advantage is lost. In view of the above background, development of a dye excellent in heat resistance is strongly demanded.
Therefore, the subject of this invention is providing the coloring composition containing the xanthene-type colorant excellent in heat resistance. Furthermore, the subject of this invention is providing the display element which comprises the color filter provided with the colored layer containing the said coloring agent, and the said color filter.

  As a result of intensive studies, the present inventors have found that a xanthene dye having an organic acid conjugate base having a strong acidity as an anion part can solve the above-mentioned problems.

  That is, the present invention is a coloring composition containing (A) a coloring agent, (B) a binder resin, and (C) a crosslinking agent, and (A) a coloring agent represented by the following formula (1) as a coloring agent. (Hereinafter also referred to as “the present colorant”).

X ⁺ Z ^- (1)

[In the formula (1), X ⁺ represents a xanthene chromophore, and Z ⁻ represents a conjugate base of an organic acid having a halogenated hydrocarbon group. ]

In the present invention, Z ⁻ is preferably an anion represented by the following formula (1a) or an anion represented by the following formula (1b).

[In Formula (1a), R ¹ represents a halogenated hydrocarbon group which may have a linking group. ]

[In Formula (1b), R ² independently represents a halogenated hydrocarbon group which may have a linking group, and R ² may be bonded to each other to form a ring. ]

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

  Furthermore, this invention provides the coloring agent represented by following formula (3).

_{^{X + (R 1 SO 3 -}} ) (3)

[In Formula (3), X ^<+> and R ^{< 1 >} are synonymous with the above. ]

This colorant is extremely excellent in heat resistance. If the coloring composition of this invention containing this coloring agent is used, even if it passes through a high temperature heating process, the colored layer which hold | maintains the outstanding chromaticity characteristic can be formed.
Therefore, this colorant is extremely useful for the production of various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be preferably used.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described in detail components of the colored composition of the present invention.
-(A) Colorant-
The colored composition of the present invention is characterized by containing the present colorant, that is, the colorant represented by the above formula (1) as (A) the colorant.

First, Z ⁻ in the formula (1) will be described.
Z ⁻ is not particularly limited as long as it is a conjugate base of an organic acid having a halogenated hydrocarbon group. Examples of the organic acid having a halogenated hydrocarbon group include sulfone having a halogenated hydrocarbon group. acid (-SO ₃ H), sulfonimide acid (-SO ₂ NHSO ₂ -) and the like. In the xanthene-based basic colorant, the present inventors consider that by introducing a conjugated base of an organic acid having a higher acidity as the anion part, the ionic bond strength is increased and the heat resistance of the colorant is increased. This colorant was completed.
Specific examples of Z ⁻ include an anion represented by the following formula (1a), an anion represented by the following formula (1b), and the like.

Among these colorants having anions, the colorant represented by the following formula (3) is a novel colorant.
_{^{X + (R 1 SO 3 -}} ) (3)

Next, definitions of symbols in the formulas (1a), (1b) and (3) will be described.
R ¹ and R ² represent a halogenated hydrocarbon group which may have a linking group. Examples of the hydrocarbon group constituting the skeleton include (1) an aliphatic hydrocarbon group and (2) an aliphatic group. A cyclic hydrocarbon group, (3) an aliphatic hydrocarbon group having an alicyclic hydrocarbon group as a substituent (hereinafter referred to as "alicyclic hydrocarbon-substituted aliphatic hydrocarbon group"), (4) aromatic A hydrocarbon group, (5) an aromatic hydrocarbon group having an aliphatic hydrocarbon group as a substituent (hereinafter referred to as an “aliphatic hydrocarbon-substituted aromatic hydrocarbon group”), and (6) an aromatic carbon group as a substituent. And an aliphatic hydrocarbon group having a hydrogen group (hereinafter referred to as “aromatic hydrocarbon-substituted aliphatic hydrocarbon group”). The hydrocarbon group constituting the skeleton of R ¹ and R ² is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.

  That is, the (1) aliphatic hydrocarbon group is preferably an alkyl group, and the number of carbon atoms thereof is preferably 1-20, and particularly preferably 1-8. Moreover, as said (2) alicyclic hydrocarbon group, an alicyclic saturated hydrocarbon group is preferable, As that carbon number, it is preferable that it is 3-20, and it is especially preferable that it is 3-12. The (3) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the total carbon number is preferably 4 to 20, particularly 6 It is preferably ~ 14. Moreover, as said (4) aromatic hydrocarbon group, C6-C14 (more preferably C6-C10) is preferable, and especially a phenyl group is preferable. The (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the total number of carbon atoms is preferably 7 to 30, particularly 7 to 20. preferable. Moreover, as said (6) aromatic-hydrocarbon substituted aliphatic hydrocarbon group, an aralkyl group is preferable, As the total carbon number, it is preferable that it is 7-30, and it is especially preferable that it is 7-20. In addition, the alkyl group in this paragraph may be linear or branched.

Among these, as the hydrocarbon group constituting the skeleton of R ¹ and R ² , (1) an aliphatic hydrocarbon group, (3) an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, (4) an aromatic hydrocarbon A group (5) an aliphatic hydrocarbon-substituted aromatic hydrocarbon group or (6) an aromatic hydrocarbon-substituted aliphatic hydrocarbon group, preferably an alkyl group, an alicyclic saturated hydrocarbon-substituted alkyl group, a phenyl group, an alkyl-substituted phenyl Group and an aralkyl group are more preferable, and an alkyl group is particularly preferable. In formula (1b), R ² may be bonded to each other to form a divalent hydrocarbon group.

In R ¹ and R ² , the halogen in the halogenated hydrocarbon group is preferably a fluorine atom from the viewpoint of heat resistance of the colorant. By selecting a fluorine atom as a substituent, the anion portion of the colorant becomes a conjugate base of an organic acid having a higher acidity, so that a salt with a stronger ionic bond is formed and heat resistance is increased. Conceivable.

In R ¹ and R ² , examples of the linking group include —O—, —S—, —CO—, —COO—, —CONH—, —SO ₂ — and the like. And the number of carbons referred to in paragraph [0025] of the present specification means the total number of carbons excluding the carbon atoms constituting the linking group.

In the present invention, from the viewpoint of the heat resistance of the colorant, R ¹ and R ² are preferably groups represented by the following formula (1-1) or (1-2), and particularly an organic acid having a higher acidity. A group represented by the following formula (1-1) which forms a conjugate base of an acid is preferable.

[In the formula (1-1), R ¹⁹ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluorinated alkoxy group, R ²⁰ COOR ²¹ — or R ²⁰ COOR. ²¹ CFH— (R ²⁰ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group, R ²¹ represents a methylene group or an alkylene group), and n is 1 or more And “*” indicates a bond. ]

[In the formula (1-2), R ^{14 to} R ¹⁸ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluorinated alkyl group or an alkoxy group, and “*” is a bond. It shows that. However, at least one of R ^{14 to} R ¹⁸ is a fluorine atom or a fluorinated alkyl group. ]

In the formula (1-1), R ¹⁹ is preferably a fluorine atom, a fluorinated alkyl group, an alicyclic hydrocarbon group, a fluorinated alkoxy group, R ²⁰ COOR ²¹ — or R ²⁰ COOR ²¹ CFH—, particularly fluorine. atoms, alicyclic hydrocarbon group, perfluoroalkoxy group, R ²⁰ COOCH ₂ CH ₂ - or R ²⁰ COOCH ₂ CH ₂ CFH- are preferred.
R ²⁰ represents an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group, and the alkyl group may be linear or branched, and the alkyl group has 1 to 12 carbon atoms. (More preferably, 1 to 8). The alicyclic hydrocarbon group may be a 2-4 ring bridged alicyclic hydrocarbon group, and the alicyclic hydrocarbon group preferably has 3-20 carbon atoms (more preferably 3-12). The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocycle containing one or more heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. As the aryl group, an aryl group having 6 to 14 carbon atoms (more preferably 6 to 10 carbon atoms) is preferable, and a phenyl group is particularly preferable. In addition, as a substituent, a C1-C6 alkyl group, a C1-C6 alkoxy group, a halogen atom, or a trifluoromethyl group is mentioned, for example, The position and number of a substituent are arbitrary, Substitution In the case of having two or more groups, the substituents may be the same or different.
R ²¹ represents a methylene group or an alkylene group, and a methylene group or an alkylene group having 2 to 6 carbon atoms is preferred, and an ethylene group is particularly preferred from the viewpoint of ease of production.
In addition, 10 is preferable and the upper limit of n is more preferable.
In formula (1-2), it is preferable that at least three of R ^{14 to} R ¹⁸ are a fluorine atom or a fluorinated alkyl group. In the formula (1b), it is also preferable that R ² are bonded to each other to form a fluorinated alkylene group, particularly a perfluoroalkylene group.

  Representative examples of the anion represented by the above formula (1-1) or (1-2) include anions shown in the following compound group a and compound group b.

Next, X ⁺ in the formulas (1) and (3) will be described.
X ⁺ is not particularly limited as long as it is a xanthene chromophore, that is, a cation having a xanthene structure, but is preferably represented by the following formula (2). In addition, although various resonance structures exist in the cation represented by the following formula (2), in this specification, when the resonance structure exists in the cation represented by each formula, the cation represented by the formula Equivalent.

[In Formula (2),
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, —R ¹⁰ or an aromatic hydrocarbon group having 6 to ¹⁰ carbon atoms. However, the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, —R ¹⁰ , —OH, —OR ¹⁰ , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ¹⁰ , It may be substituted with —SO ₃ R ¹⁰ , —SO ₂ NHR ¹¹ or —SO ₂ NR ¹¹ R ¹² .
R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁹ represents —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ¹⁰ , —SO ₃ R ¹⁰ , —SO ₂ NHR ¹¹ or —SO ₂ NR ¹¹ R ¹² .
m shows the integer of 0-5. When m is an integer of 2 or more, the plurality of R ⁹ may be the same or different.
R ¹⁰ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom, a carbonyl group or —NR ¹⁰ —. May be.
R ¹¹ and R ¹² each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q, or R ¹¹ and R ¹² are mutually A C1-C10 heterocyclic group formed by bonding is shown. However, the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ¹⁰ , and the alkyl group and cycloalkyl The methylene group contained in the group may be substituted with an oxygen atom, a carbonyl group or —NR ¹⁰ —, and the hydrogen atom contained in the heterocyclic group is substituted with —R ¹⁰ , —OH or —Q. May be.
M represents a sodium atom or a potassium atom.
Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. However, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is —OH, R ¹⁰ , —OR ¹⁰ , —NO ₂ , —CH═CH ₂ , —CH═CHR ¹⁰ or a halogen atom. May be substituted. ]

The saturated hydrocarbon group for R ¹⁰ may be linear, branched, or cyclic as long as it has 1 to 10 carbon atoms, and may have a bridged structure. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decanyl Examples thereof include an alkyl group such as a group, a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and a bridged alicyclic hydrocarbon group such as a tricyclodecanyl group. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. The methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom, a carbonyl group or —NR ¹⁰ —. For example, examples of the group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom include a methoxypropyl group, an ethoxypropyl group, a hexyloxypropyl group, a methoxyhexyl group, and an ethoxypropyl group.

The aromatic hydrocarbon group for R ³ , R ⁴ , R ⁵ , R ⁶ and Q is not particularly limited as long as it has 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. Moreover, as a halogen atom mentioned as a substituent of this aromatic hydrocarbon group, a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned.
Examples of —SO ₃ R ¹⁰ in R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁹ include a methanesulfonyl group, an ethanesulfonyl group, a hexanesulfonyl group, and a decanesulfonyl group.
As —CO ₂ R ¹⁰ in R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁹ , methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, isobutyloxy Carbonyl group, pentyloxycarbonyl group, isopentyloxycarbonyl group, neopentyloxycarbonyl group, cyclopentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, cycloheptyloxycarbonyl group, octyloxycarbonyl group 2-ethylhexyloxycarbonyl group, cyclooctyloxycarbonyl group, nonyloxycarbonyl group, decanyloxycarbonyl group, tricyclodecanyloxycarbonyl group Methoxypropyloxycarbonyl group, ethoxypropyloxycarbonyl group, hexyloxypropyloxycarbonyl group, 2-ethylhexyloxypropyloxycarbonyl group, methoxyhexyloxycarbonyl group and the like.

As —SO ₂ NHR ¹¹ in R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁹ , sulfamoyl group, methanesulfamoyl group, ethanesulfamoyl group, propanesulfamoyl group, isopropanesulfamoyl group, Butane sulfamoyl group, isobutane sulfamoyl group, pentanes sulfamoyl group, isopentane sulfamoyl group, neopentane sulfamoyl group, cyclopentane sulfamoyl group, hexane sulfamoyl group, cyclohexane sulfamoyl group, Heptanesulfamoyl group, cycloheptanesulfamoyl group, octanessulfamoyl group, 2-ethylhexanesulfamoyl group, 1,5-dimethylhexanesulfamoyl group, cyclooctanesulfamoyl group, nonanesulfamoyl group Group, decansulfamoyl group, tricyclode Cansulfamoyl group, methoxypropanesulfamoyl group, ethoxypropanesulfamoyl group, propoxypropanesulfamoyl group, isopropoxypropanesulfamoyl group, hexyloxypropanesulfamoyl group, 2-ethylhexyloxypropane sulfa A moyl group, a methoxyhexanesulfamoyl group, a 3-phenyl-1-methylpropanesulfamoyl group and the like can be mentioned.

Examples of —SO ₂ NHR ¹¹ and —SO ₂ NR ¹¹ R ^{12 in} R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁹ further include groups represented by the following substituent group a to substituent group u. be able to.

In the above substituent group d, X ¹ represents a halogen atom. Examples of the halogen atom for X ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

In the substituent group h, X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. Good.
Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the alkyl group having 1 to 3 carbon atoms substituted with a halogen atom include a perfluoromethyl group and the like. Can be mentioned.
Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.

In the above substituent group l, X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and the alkoxy group is a halogen atom. May be substituted.
Examples of the halogen atom include the same as those described above for X ^1, and an alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom, and 1 to 3 carbon atoms which may be substituted with a halogen atom. As the alkoxy group, the same groups as those described above for X ³ can be mentioned.

In the substituent group q, X ² has the same meaning as described above.

In the substituent group u, X ³ has the same meaning as described above.

The -SO ₂ NHR ^11, as the R ^11, R ¹² in -SO ₂ NR ¹¹ R ^12, branched alkyl groups having 6 to 8 carbon atoms, alicyclic hydrocarbon group having 5 to 7 carbon atoms, an allyl group , An aralkyl group having 8 to 10 carbon atoms, a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms, an alkoxy group-containing alkyl group having 2 to 8 carbon atoms, and an aryl group are preferable, and a branched alkyl group having 6 to 8 carbon atoms is preferable. More preferred is a 2-ethylhexyl group.

Examples of the substituent for the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ³ , R ⁴ , R ⁵ and R ⁶ include an alkyl group having 1 to 4 carbon atoms, an aryl group, an alkyl-substituted phenyl group, —SO ₃ R ¹⁰ or —SO ₂ NHR ¹¹ is preferable, and ethyl group, propyl group, dimethylphenyl group, —SO ₃ R ¹⁰ or —SO ₂ NHR ¹¹ is more preferable.

Specific examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent in R ³ , R ⁴ , R ⁵ and R ⁶ include methylphenyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, hexyl. Phenyl group, decanylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, hydroxyphenyl group, methoxyphenyl group, dimethoxyphenyl group, ethoxyphenyl group, hexyloxyphenyl group, decanyloxyphenyl group, trifluoromethylphenyl Groups and the like.

At least one of R ³ and R ⁴ or at least one of R ⁵ and R ⁶ is an alkyl group having 1 to 4 carbon atoms or an optionally substituted aromatic carbon atom having 6 to 10 carbon atoms. A hydrogen group is preferred.
More preferably, at least one of R ³ and R ⁴ and at least one of R ⁵ and R ⁶ is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ⁹ represents a carboxyl group, an ethyloxycarbonyl group, a sulfoxyl group, a 2-ethylhexyloxypropane sulfamoyl group, a 1,5-dimethylhexanesulfamoyl group, a 3-phenyl-1-methylpropanesulfamoyl group, or It is preferably an isopropoxypropane sulfamoyl group.

  The cation represented by the above formula (2) is preferably a cation represented by the following formula (1-1), (1-2), (1-3) or (1-4).

[In the formula (1-1), R ^3a , R ^4a , R ^5a and R ^6a each independently represent a hydrogen atom, —R ¹⁰ or an aromatic hydrocarbon group having 6 to ¹⁰ carbon atoms; hydrogen atoms contained in the group hydrocarbon group, a halogen ^{atom, -R 10, -OH, -OR 10} , -SO 3 H, -SO 3 Na, -CO 2 H, -CO 2 R 10, -SO 3 R ¹⁰ , may be substituted with —SO ₂ NHR ¹¹ or —SO ₂ NR ¹¹ R ¹² .
R ^9a represents —SO ₃ H, —SO ₂ NHR ¹¹ or —SO ₂ NR ¹¹ R ¹² .
R ^9b represents a hydrogen atom, —SO ₃ H, —SO ₂ NHR ¹¹ or —SO ₂ NR ¹¹ R ¹² .
R ¹⁰ , R ¹¹ and R ¹² are as defined above. ]

[In Formula (1-2), R ^3b , R ^4b , R ^5b, and R ^6b each independently represent a hydrogen atom, —R ^10b, or an aromatic hydrocarbon group having 6 to 10 carbon atoms; The hydrogen atom contained in the group hydrocarbon group is a halogen atom, —R ^10b , —OH, —OR ^10b , —SO ₃ ⁻ , —SO ₃ Na, —CO ₂ H, —CO ₂ R ^10b , —SO ₃ H , —SO ₃ R ^10b or —SO ₂ NHR ²² may be substituted.
R ^7b and R ^8b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ^9c represents —SO ₃ Na, —CO ₂ H, —CO ₂ R ^10b , —SO ₃ H or SO ₂ NHR ²² .
R ^10b represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OR ^10b or a halogen atom.
R ²² represents a hydrogen atom, —R ^10b , —CO ₂ R ^10b or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is —R ^10b or —OR ^It may be substituted with ^10b .
m is as defined above. ]

[In Formula (1-3), R ^3c and R ^5c each independently represent a phenyl group, and the hydrogen atom contained in the phenyl group is a halogen atom, —R ^10b , —OR ^10b , —CO ₂ R ^10b , —SO ₃ R ^10b or —SO ₂ NHR ²² may be substituted.
R ^9d represents —SO ₂ NHR ²² .
R ^9e represents a hydrogen atom or —SO ₂ NHR ²² .
R ^10b and R ²² are as defined above. ]

[In Formula (1-4), R ^3d and R ^5d each independently represent a phenyl group, and a hydrogen atom contained in the phenyl group is substituted with —R ^10b or —SO ₂ NHR ^22. May be.
R ^9f represents —SO ₂ NHR ²² .
R ^10b and R ²² are as defined above. ]

Specific examples of X ⁺ in the formula (1) include cations shown in the following compound group c and compound group d.

This colorant can be produced by a known method, and can be produced, for example, by the same method as in the examples of JP-T-2007-503477. When the present colorant is produced by a salt exchange reaction as in the examples of JP-T-2007-503477, an anion represented by the above formula (1a) or an anion salt represented by the above formula (1b) is required. However, as the salt, a commercially available product may be used, and a known method, for example, one synthesized by the method described in paragraphs [0149] to [0153] of JP-A-2008-7410 is used. Also good.
In the present invention, the colorant can be used alone or in admixture of two or more.

  The coloring composition of this invention can contain the other coloring agent different from this coloring agent further as (A) coloring agent. Other colorants are not particularly limited, but the colorant and other red colorant are used in combination to form a color composition for forming a red pixel, or the present colorant and other blue colorant. It is preferable to use a coloring agent in combination to form a coloring composition for forming a blue pixel. Also, as other colorants, any of pigments, dyes and natural pigments can be used. However, the color layer constituting the color filter is required to have high color purity, brightness, contrast, light shielding properties, etc. It is preferred to use pigments and / or dyes.

The red colorant as the other colorant is preferably a red organic pigment, and examples thereof include those having the following color index (CI) names.
C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment Red 272.

  Of these, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. At least one selected from the group consisting of CI Pigment Red 254 is preferred. I. Pigment red 177 and C.I. I. At least one selected from the group consisting of CI Pigment Red 254 is preferred.

  When using this coloring agent and the other coloring agent of red as a coloring composition for red pixel formation, the content rate of this coloring agent is preferably 1-30 mass% in all coloring agents, More preferably 3 to 15% by mass. In this case, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Yellow or orange colorants such as CI Pigment Orange 38 can also be used.

The blue colorant as the other colorant is preferably a blue organic pigment and / or an organic dye. Examples of the blue organic pigment include the following color index (CI) names: What is attached can be mentioned.
C. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 17: 1, C.I. I. Pigment blue 24, C.I. I. Pigment blue 24: 1, C.I. I. Pigment blue 56, C.I. I. Pigment blue 60, C.I. I. Pigment blue 61, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 80.

  In addition, as a blue organic dye as another colorant, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 37, C.I. I. Solvent Blue 59, C.I. I. Solvent Blue 67, C.I. I. Acid Blue 80, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Basic Blue 3, C.I. I. Basic Blue 7, C.I. I. Basic Blue 9, C.I. I. Examples include Basic Blue 11.

  Of these, C.I. I. Pigment blue 1, C.I. I. Pigment blue 2, C.I. I. Pigment blue 3, C.I. I. Pigment blue 9, C.I. I. Pigment blue 10, C.I. I. Pigment blue 14, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 62, C.I. I. Basic Blue 7, C.I. I. At least one selected from the group consisting of Basic Blue 11 is preferred. I. Pigment Blue 15: 6 is preferable.

  When the colorant and other blue colorant are used in combination to form a colored composition for forming a blue pixel, the content of the colorant is preferably from 3 to 70% by mass, more preferably from all colorants. 3 to 50% by mass. In this case, C.I. I. A purple colorant such as CI Pigment Violet 23 can also be used.

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

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

  In the present invention, when a pigment is used as a colorant, it can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, urethane dispersant, polyethyleneimine dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene alkylphenyl ether dispersant, polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester Examples thereof include an acrylic dispersant and an acrylic dispersant.

Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) And Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol Co., Ltd.) ), Polyethylene imine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), polyester-based dispersant, Azisper PB821, Jisupa PB822, Adisper PB880, mention may be made of Ajisper PB881 (Ajinomoto Fine-Techno Co., Ltd.), and the like.
Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The contents of the dispersant and the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

-(B) Binder resin-
Although it does not specifically limit as binder resin in this invention, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (B1) ") and other copolymerizable ethylenically unsaturated monomers (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- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

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

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

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

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

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

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

  The ratio (Mw / Mn) of the weight average molecular weight of the binder resin in the present invention to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5. 0, more preferably 1.0 to 3.0.

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

  In this invention, binder resin can be used individually or in mixture of 2 or more types.

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

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

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

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

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

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

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

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

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

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

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

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

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

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

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

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

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

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-(E) Solvent-
The colored composition of the present invention contains the above components (A) to (C) and other components that are optionally added, but is usually prepared as a liquid composition by blending a solvent.
As said solvent, (A)-(C) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has appropriate volatility. You can choose to use.

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

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

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

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

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

  Although content of a solvent is not specifically limited, From viewpoints of the applicability | paintability of a coloring composition obtained, stability, etc., the total density | concentration of each component remove | excluding the solvent from the said coloring composition is 5-50. An amount of mass% is preferred, and an amount of 10 to 40 mass% is particularly preferred.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And a siloxane oligomer having a reactive functional group disclosed in Japanese Patent Application Laid-Open No. 2008-2242078 and the like.

  The coloring composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in JP 2008-58642 A, JP 2010-132874 A, and the like. be able to. When both the present colorant and the pigment are used as the colorant, as disclosed in JP 2010-132874 A, after passing the dye solution containing the present colorant through the first filter, A method is preferred in which the dye solution that has passed through the filter is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter. In addition, the dye containing the present colorant, the components (B) to (C), and the component (D) and the additive component, if necessary, are dissolved in the solvent (E). Also preferred is a method of preparing a solution obtained by passing the first filter after passing through the first filter and mixing with a separately prepared pigment dispersion and passing the resulting colored composition through the second filter. Moreover, after passing the dye solution containing this coloring agent through a 1st filter, the dye solution which passed the 1st filter, said (B)-(C) component, and said (D)-as needed (E) Component and additive component were mixed and dissolved, and the resulting solution was passed through a second filter, and the solution that passed through the second filter was further mixed with a separately prepared pigment dispersion. A method of preparing the colored composition by passing it through a third filter is also preferred.

Color filter and production method thereof The color filter of the present invention comprises a colored layer containing the present colorant.

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

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

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel. The colored composition of the present invention can also be suitably used for forming such black tricks.

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

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

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

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

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

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

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

The post-baking conditions are usually 120 to 280 ° C. for about 10 to 60 minutes, but from the viewpoint of heat resistance of the present colorant, the post-baking temperature is preferably 240 ° C. or less, particularly preferably 230 ° C. or less. is there.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

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

  Subsequently, using each coloring composition of green or red, a green pixel pattern and a red pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

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

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

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

  The color liquid crystal display device including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light using a red LED, a green LED, and a blue LED having independent spectra, a white LED that obtains white light by mixing colors by combining the red LED, the green LED, and the blue LED, White LED that obtains white light by color mixing by combining blue LED, red LED and green phosphor, White LED that obtains white light by color mixing by combining blue LED, red light emitting phosphor and green light emitting phosphor, Blue LED and YAG system White LED that obtains white light by mixing phosphors, white LED that obtains white light by mixing blue LED, orange light emitting phosphor and green light emitting phosphor, UV LED, red light emitting phosphor, green light emitting phosphor and blue A white LED that obtains white light by mixing colors by combining light emitting phosphors can be exemplified.

  The color liquid crystal display device having the color filter of the present invention includes a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical alignment) type, and an OCB (Optic Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.

  Moreover, the organic EL display element provided with the color filter of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

  In addition, the electronic paper including the color filter of the present invention can adopt an appropriate structure, and examples thereof include a structure disclosed in Japanese Patent Application Laid-Open No. 2007-41169.

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

<Synthesis and Evaluation of the Colorant>
1. Synthesis synthesis example 1 of this colorant

Into the screw tube into which the stirrer is charged, C.I. I. 1.3 g (2.71 mmol) of Basic Red 1, 0.766 g (4.07 mmol) of potassium trifluoromethanesulfonate (manufactured by Wako Pure Chemical Industries), 20 mL of chloroform and 10 mL of water were added and stirred at room temperature for 7 hours. After separating and removing the aqueous layer, the organic layer was washed twice with water, concentrated under reduced pressure, and the obtained solid was dried under reduced pressure to obtain 1.61 g of a dark blue solid (yield 72%). This is designated Compound A. The ¹ H-NMR (solvent: deuterated chloroform) spectrum of Compound A was as follows and was confirmed to be the target compound.

¹ H-NMR: 8.25 (dd, 1H), 7.87 (m, 2H), 7.70 (t, 2H), 7.47 (dd, 1H), 6.94 (d, 3H), 6.81 (s, 2H), 3.95 (q , 2H), 3.50 (quintet, 4H), 2.10 (s, 6H), 1.27 (t, 6H), 0.85 (t, 3H,)

Synthesis example 2
A coloring agent was synthesized in the same manner as in Synthesis Example 1 except that potassium nonafluorobutanesulfonate (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of potassium trifluoromethanesulfonate in Synthesis Example 1, and ¹ H-NMR (solvent : Deuterated chloroform) was confirmed to be the target compound. This is designated Compound B. The ¹ H-NMR spectrum of Compound B is as follows.

¹ H-NMR: 8.32 (d, 1H), 7.78 (m, 2H), 7.28 (dd, 1H), 6.81 (d, 2H), 6.76 (s, 2H), 6.68 (s, 2H), 4.04 (q , 2H), 3.51 (quintet, 4H), 2.18 (s, 6H), 1.38 (t, 6H), 1.00 (t, 3H,)

Synthesis example 3
A colorant was synthesized in the same manner as in Synthesis Example 1 except that bis (trifluoromethanesulfonyl) imide potassium was used in place of potassium trifluoromethanesulfonate in Synthesis Example 1, and ¹ H-NMR (solvent: deuterated chloroform). ) Measurement confirmed that the compound was the target compound. This is designated Compound C. The ¹ H-NMR spectrum of Compound C is as follows.

¹ H-NMR: 8.33 (d, 1H), 7.79 (m, 2H), 7.28 (dd, 1H), 6.81 (d, 2H), 6.76 (d, 2H), 5.94 (d, 2H), 4.04 (q , 2H), 3.50 (quintet, 4H), 2.15 (s, 6H), 1.39 (t, 6H), 1.01 (t, 3H,)

Synthesis example 4
In Synthesis Example 3, C.I. I. Instead of Basic Red 1, C.I. I. A colorant was synthesized in the same manner as in Synthesis Example 3 except that Basic Red 1: 1 was used, and confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement. This is designated Compound D. The ¹ H-NMR spectrum of Compound D is as follows.

¹ H-NMR: 8.33 (d, 1H), 7.80 (m 2H), 7.28 (d, 1H), 6.77 (d, 4H), 5.95 (t, 2H), 3.66 (s 3H), 3.49 (quintet, 4H ), 2.13 (s, 6H), 1.38 (t, 6H)

Synthesis example 5
In Synthesis Example 3, C.I. I. In place of Basic Red 1, C.I. represented by the following formula (4): I. A colorant was synthesized in the same manner as in Synthesis Example 3 except that Basic Violet 10 was used, and the compound was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement. This is designated Compound E. The ¹ H-NMR spectrum of Compound E is as follows.

¹ H-NMR: 8.28 (d, 1H), 7.77 (t, 1H), 7.69 (t, 1H), 7.26 (dd, 2H), 7.02 (d, 2H), 6.76-6.83 (m 4H), 5.95 ( t, 2H), 3.58 (q, 8H), 1.30 (t, 12H)

Synthesis Example 6
In Synthesis Example 3, C.I. I. In place of Basic Red 1, C.I. represented by the following formula (5): I. A colorant was synthesized in the same manner as in Synthesis Example 3 except that Basic Violet 11: 1 was used, and the compound was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement. This is designated Compound F. The ¹ H-NMR spectrum of Compound F is as follows.

¹ H-NMR: 8.31 (d, 1H), 7.77 (dt, 2H), 7.30 (m, 1H), 7.06 (m 2H), 6.83 (d, 4H), 3.68 (s 3H), 3.60 (q, 8H ), 1.32 (t, 12H)

Synthesis example 7
In Synthesis Example 3, C.I. I. In place of Basic Red 1, C.I. I. A colorant was synthesized in the same manner as in Synthesis Example 3 except that Basic Red 3 was used, and the compound was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

Synthesis Example 8
In Synthesis Example 3, C.I. I. In place of Basic Red 1, C.I. represented by the following formula (7): I. A colorant was synthesized in the same manner as in Synthesis Example 3 except that Basic Red 4 was used, and the compound was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

Synthesis Example 9
In Synthesis Example 3, C.I. I. In place of Basic Red 1, C.I. I. A colorant was synthesized in the same manner as in Synthesis Example 3 except that Basic Violet 11 was used, and the compound was confirmed to be the target compound by ¹ H-NMR (solvent: deuterated chloroform) measurement.

2. Evaluation of Colorant Compound A obtained in Synthesis Example 1 was dissolved in cyclohexanone by 10% by mass or more, and the solution was red. All the colorants obtained in Synthesis Examples 2 to 9 were dissolved in cyclohexanone by 10% by mass or more.
Moreover, all the 5% mass reduction | decrease temperatures based on the thermogravimetric-differential-thermal simultaneous measurement analysis of the coloring agent obtained by the synthesis examples 1-9 were 250 degreeC or more. On the other hand, C.I. I. Basic Red 1, C.I. I. Basic Red 1: 1, C.I. I. Basic Red 3, C.I. I. Basic Red 4, C.I. I. Basic Violet 10, C.I. I. Basic Violet 11, C.I. I. The 5% mass loss temperature of Basic Violet 11: 1 based on the thermogravimetric-differential thermal simultaneous measurement analysis was less than 200 ° C.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by mass of Pigment Red 177, 12.5 parts by mass of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (A-1) was prepared by using a bead mill.

Preparation Example 2
As a coloring agent, C.I. I. Pigment Red 177 instead of C.I. I. A pigment dispersion (A-2) was prepared in the same manner as in Preparation Example 1, except that CI Pigment Red 254 was used.

<Preparation of dye solution>
Preparation Example 3
20 parts by mass of Compound A as a colorant and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare Dye Solution A.

Preparation Example 4
20 parts by mass of Compound B as a colorant and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare Dye Solution B.

Preparation Example 5
20 parts by mass of Compound C as a colorant and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare Dye Solution C.

Adjustment example 6
20 parts by mass of Compound D as a colorant and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare Dye Solution D.

Preparation Example 7
20 parts by mass of Compound E as a colorant and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare Dye Solution E.

Preparation Example 8
20 parts by mass of Compound F as a colorant and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare Dye Solution F.

Preparation Example 9
As a coloring agent, C.I. I. 20 parts by mass of Basic Red 1 and 80 parts by mass of propylene glycol monomethyl ether as a solvent were mixed to prepare a dye solution G.

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

<Preparation and evaluation of coloring composition>
Example 1
25.6 parts by mass of the pigment dispersion (A-1), 2.6 parts by mass of the pigment dispersion (A-2), 2.2 parts by mass of the dye solution A, and 16.1 of the binder resin (B1) solution as a binder resin M-402 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a mass part and a crosslinking agent, and 2-benzyl-2-dimethylamino-1 as a photopolymerization initiator -(4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2.2 parts by mass, and Megafac F-554 manufactured by DIC Corporation as a fluorosurfactant is 0. .2 parts by mass and cyclohexanone as a solvent were mixed to prepare a colored composition (CR1) having a solid content concentration of 20% by mass.

The coloring composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film for evaluation.

  Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. From the measurement results, the chromaticity coordinate value y, the stimulus value (Y), and the film thickness at the chromaticity coordinate value x = 0.655 were obtained. The evaluation results are shown in Table 1. The larger the stimulus value (Y), the higher the light transmittance (brightness), and the thinner the film thickness, the higher the coloring power.

  A substrate on which a cured film is formed is sandwiched between two deflecting plates, and the front deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and a luminance meter LS-100 (Minolta Co., Ltd.) is rotated. The maximum value and the minimum value of the light intensity transmitted through (made by)) were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value x = 0.655 was obtained. The evaluation results are shown in Table 1.

Example 2
23.6 parts by mass of the pigment dispersion (A-1), 2.6 parts by mass of the pigment dispersion (A-2), 3.2 parts by mass of the dye solution B, and 16.1 of the binder resin (B1) solution as a binder resin M-402 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a mass part and a crosslinking agent, and 2-benzyl-2-dimethylamino-1 as a photopolymerization initiator -(4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2.2 parts by mass, and Megafac F-554 manufactured by DIC Corporation as a fluorosurfactant is 0. .2 parts by mass and cyclohexanone as a solvent were mixed to prepare a colored composition (CR2) having a solid content concentration of 20% by mass.
Evaluation was performed in the same manner as in Example 1 except that the colored composition (CR2) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Example 3
22.3 parts by mass of the pigment dispersion (A-1), 1.6 parts by mass of the pigment dispersion (A-2), 1.2 parts by mass of the dye solution C, and 16.1 of the binder resin (B1) solution as a binder resin M-402 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a mass part and a crosslinking agent, and 2-benzyl-2-dimethylamino-1 as a photopolymerization initiator -(4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2.2 parts by mass, and Megafac F-554 manufactured by DIC Corporation as a fluorosurfactant is 0. .2 parts by mass and cyclohexanone as a solvent were mixed to prepare a colored composition (CR3) having a solid content concentration of 20% by mass.
Evaluation was performed in the same manner as in Example 1 except that the colored composition (CR3) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Example 4
24.3 parts by mass of the pigment dispersion (A-1), 2.6 parts by mass of the pigment dispersion (A-2), 1.3 parts by mass of the dye solution D, and 16.1 of the binder resin (B1) solution as a binder resin M-402 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a mass part and a crosslinking agent, and 2-benzyl-2-dimethylamino-1 as a photopolymerization initiator -(4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2.2 parts by mass, and Megafac F-554 manufactured by DIC Corporation as a fluorosurfactant is 0. .2 parts by mass and cyclohexanone as a solvent were mixed to prepare a colored composition (CR4) having a solid content concentration of 20% by mass.
Evaluation was performed in the same manner as in Example 1 except that the colored composition (CR4) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Example 5
22.6 parts by mass of the pigment dispersion (A-1), 5.6 parts by mass of the pigment dispersion (A-2), 3.2 parts by mass of the dye solution E, and 16.1 of the binder resin (B1) solution as a binder resin M-402 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a mass part and a crosslinking agent, and 2-benzyl-2-dimethylamino-1 as a photopolymerization initiator -(4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2.2 parts by mass, and Megafac F-554 manufactured by DIC Corporation as 0 .2 parts by mass and cyclohexanone as a solvent were mixed to prepare a colored composition (CR5) having a solid content concentration of 20% by mass.
Evaluation was performed in the same manner as in Example 1 except that the colored composition (CR5) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Example 6
24.2 parts by mass of the pigment dispersion (A-1), 4.6 parts by mass of the pigment dispersion (A-2), 2.2 parts by mass of the dye solution F, and 16.1 of the binder resin (B1) solution as a binder resin M-402 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as a mass part and a crosslinking agent, and 2-benzyl-2-dimethylamino-1 as a photopolymerization initiator -(4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), 2.2 parts by mass, and Megafac F-554 manufactured by DIC Corporation as 0 .2 parts by mass and cyclohexanone as a solvent were mixed to prepare a colored composition (CR6) having a solid concentration of 20% by mass.
Evaluation was performed in the same manner as in Example 1 except that the colored composition (CR6) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Comparative Example 1
22.1 parts by mass of the 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 Toagosei Co., Ltd. as the crosslinking agent 5.5 parts by mass of M-402 and 2.4 parts by mass of MW-30 manufactured by Sanwa Chemical Co., Ltd., 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) as a photopolymerization initiator Butan-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals, Inc.) 2.2 parts by weight, DIC Corporation Megafac F-554 as a fluorine-based surfactant, 0.2 parts by weight, and solvent Propylene glycol monomethyl ether acetate was mixed to prepare a colored composition (CR7) having a solid content concentration of 20% by mass.
Evaluation was performed in the same manner as in Example 1 except that the colored composition (CR7) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

Comparative Example 2
24.1 parts by mass of the pigment dispersion (A-1), 4.6 parts by mass of the pigment dispersion (A-2), 2.2 parts by mass of the dye solution G, and 16.1 of the binder resin (B1) solution as a binder resin 5.5 parts by mass of M-402 manufactured by Toagosei Co., Ltd. and 2.4 parts by mass of MW-30 manufactured by Sanwa Chemical Co., Ltd. as a crosslinking agent, and 2-benzyl-2-dimethylamino as a photopolymerization initiator -2- (4-morpholinophenyl) butan-1-one (trade name IRGACURE 369, manufactured by Ciba Specialty Chemicals) 2.2 parts by mass, Megafac F-554 manufactured by DIC Corporation as a fluorosurfactant 0.2 parts by mass and cyclohexanone as a solvent were mixed to prepare a colored composition (CR8) having a solid content concentration of 20% by mass.
Evaluation was performed in the same manner as in Example 1 except that the colored composition (CR8) was used instead of the colored composition (CR1). The evaluation results are shown in Table 1.

  In Table 1, “R254” means C.I. I. Pigment Bread 254, “R177” is C.I. I. Pigment Red 177, “BR1” is C.I. I. Each means Basic Red 1.

Claims (7)

A coloring composition containing (A) a coloring agent, (B) a binder resin and (C) a crosslinking agent,
(A) A coloring composition comprising a coloring agent represented by the following formula (1) as a coloring agent.
X ⁺ Z ^- (1)
[In the formula (1), X ⁺ represents a xanthene chromophore and Z ⁻ represents a conjugate base of an acid having a halogenated hydrocarbon group. ] The colored composition according to claim 1, wherein Z ^- is an anion represented by the following formula (1a) or an anion represented by the following formula (1b).

[In Formula (1a), R ¹ represents a halogenated hydrocarbon group which may have a linking group. ]

[In Formula (1b), R ² independently represents a halogenated hydrocarbon group which may have a linking group, and R ² may be bonded to each other to form a ring. ] The coloring composition according to claim 1 or 2, wherein the X ⁺ is represented by the following formula (2).

[In Formula (2),
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, —R ¹⁰ or an aromatic hydrocarbon group having 6 to ¹⁰ carbon atoms. However, the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, —R ¹⁰ , —OH, —OR ¹⁰ , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ¹⁰ , It may be substituted with —SO ₃ R ¹⁰ , —SO ₂ NHR ¹¹ or —SO ₂ NR ¹¹ R ¹² .
R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ⁹ represents —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ¹⁰ , —SO ₃ R ¹⁰ , —SO ₂ NHR ¹¹ or —SO ₂ NR ¹¹ R ¹² .
m shows the integer of 0-5. When m is an integer of 2 or more, the plurality of R ⁹ may be the same or different.
R ¹⁰ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. However, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom, a carbonyl group or —NR ¹⁰ —. May be.
R ¹¹ and R ¹² each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q, or R ¹¹ and R ¹² are mutually A C1-C10 heterocyclic group formed by bonding is shown. However, the hydrogen atom contained in the alkyl group and cycloalkyl group may be substituted with a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ¹⁰ , and the alkyl group and cycloalkyl group The methylene group contained in may be substituted with an oxygen atom, a carbonyl group or —NR ¹⁰ —, and the hydrogen atom contained in the heterocyclic group is substituted with —R ¹⁰ , —OH or —Q. Also good.
M represents a sodium atom or a potassium atom.
Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms. However, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is —OH, R ¹⁰ , —OR ¹⁰ , —NO ₂ , —CH═CH ₂ , —CH═CHR ¹⁰ or a halogen atom. May be substituted. ]   (A) The coloring composition of any one of Claims 1-3 which contains the red or blue coloring agent different from the coloring agent represented by said Formula (1) as a coloring agent further. A color filter comprising a colored layer containing a colorant represented by the following formula (1).
X ⁺ Z ^- (1)
[In the formula (1), X ⁺ represents a xanthene chromophore and Z ⁻ represents a conjugate base of an acid having a halogenated hydrocarbon group. ]   A display device comprising the color filter according to claim 5. A colorant represented by the following formula (3).
_{^{X + (R 1 SO 3 -}} ) (3)
[In Formula (3), X ⁺ represents a xanthene chromophore, and R ¹ represents a halogenated hydrocarbon group which may have a linking group. ]