TW201437293A - Coloring composition, coloring cured film and display element - Google Patents

Abstract

The purpose of this invention is to provide a coloring composition which is suitable for forming a coloring cured film with both the thermal resistance and solvent resistance and the inhibited migration property and contains the dye. The solution of this invention is a coloring composition which comprises (A) the coloring agent and (C) the polymerizable compound, wherein the coloring agent contains a polymer with structural units represented by formula (1) below, wherein R0 represents the hydrogen atom or methyl, X represents the halogen group, the halogenated hydrocarbyl, or a group having a bonding group containing atoms other than the carbon atom, hydrogen atom or halogen atom between the C-C bond of the halogenated hydrocarbyl, Y represents the single bond or bivalent organic group, Z+ represents at least one cationic chromophore with a specific structure selected from a triarylmethane-based cationic chromophore, a methylene-based cationic chromophore, azo-based cationic chromophore, a diarylmethane-based cationic chromophore, a quinone-imine-based cationic chromophore, an anthraquinone-based cationic chromophore, a phthalocyanine-based cationic chromophore, and a xanthene-based cationic chromophore.

Description

Coloring composition, coloring cured film, and display element

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

When a color filter is produced using a coloring sensitizing radiation composition, it is known that 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 A method of performing development to obtain pixels of respective colors (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is known (for example, see Patent Document 3). Further, a method of obtaining pixels of respective colors by an inkjet method using a pigment-dispersed colored resin composition is known (for example, see Patent Document 4).

In recent years, there has been a demand for high contrast of liquid crystal display elements and high definition of solid-state imaging elements. In order to achieve these, techniques using dyes as colorants have been studied. However, in general, heat resistance, solvent resistance, and the like are often problematic in the case of using a dye as compared with the case of using a pigment as a colorant.

In the above-mentioned background, as a dye-containing coloring composition which can form a pixel excellent in heat resistance, for example, Patent Document 5 proposes the use of a triarylmethane dye having an alkylsulfonimide anion.

Prior 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. 2012-83652

However, in the dye proposed in Patent Document 5, it is clearly known that the balance between heat resistance and solvent resistance of the pixel is poor. In addition, the inventors of the present invention have found that a dye which is transferred to a pixel of a colored pattern to a neighboring pixel of another color or a cured film containing no coloring agent such as a protective film (hereinafter also referred to as "transfer property") is This also causes a problem that the display characteristics of the display element are lowered, but this problem is not considered at all in Patent Document 5.

Therefore, an object of the present invention is to provide a colored composition suitable for forming a colored cured film which can achieve both heat resistance and solvent resistance and which has improved transfer resistance. Further, an object of the present invention is to provide a colored cured film formed using the colored composition and a display element including the same.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a coloring agent having a specific structure.

In other words, the present invention provides a coloring composition comprising (A) a coloring agent containing a polymer having a structural unit represented by the following formula (1), and (C) a coloring composition of the polymerizable compound ( Hereinafter also referred to as "this coloring agent").

[In the formula (1), R ⁰ represents a hydrogen atom or a methyl group, and X represents a halogen group, a halogenated hydrocarbon group, or a link having an atom other than a carbon atom, a hydrogen atom or a halogen atom between CC bonds of a halogenated hydrocarbon group. The group of the group, Y represents a single bond or a divalent organic group, and Z ⁺ represents a cationic chromophore selected from the triarylmethane group represented by the following formula (2-1), and the following formula (2-2) a triarylmethane-based cationic chromophore, a methine-based cationic chromophore, an azo-based cationic chromophore, a diarylmethane-based cationic chromophore, and a quinone Cationic chromophore, lanthanide cationic chromophore, cation chromophore of phthalocyanine At least one cationic chromophore of the cationic chromophore. ]

[In the formula (2-1), R ¹ to R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted ring having 3 to 8 carbon atoms; An alkyl group, or a substituted or unsubstituted aryl group, R ⁷ to R ⁹ independently of each other represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and l and m each independently represent an integer of 0 to 4, and n represents 0. An integer of ~6.

Where l, m and n are not 0 at the same time. ]

[In the formula (2-2), R ¹¹ to R ¹⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted ring having 3 to 8 carbon atoms; The alkyl group or the substituted or unsubstituted aryl group, R ¹⁷ to R ¹⁹ independently of each other represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and s, t and u each independently represent an integer of 0 to 4. ]

Further, the present invention provides a colored cured film formed using the above colored composition and a display element comprising the colored cured film. Here, the "coloring cured film" means a pixel for each color of a display element or a solid-state image sensor, a black matrix, a black spacer, or the like.

When the colored composition of the present invention is used, it is possible to form a colored cured film which has high heat resistance and solvent resistance at a high level and which has suppressed transfer property.

Therefore, the coloring composition of the present invention is extremely suitable for producing a solid-state imaging element such as a color liquid crystal display element, an organic EL display element, a display element such as an electronic paper, or a CMOS image sensor.

Form of implementing the invention

Hereinafter, the present invention will be described in detail.

[Coloring composition]

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

- (A) colorant -

The colored composition of the present invention contains a polymer having a structural unit represented by the following formula (1) as a colorant.

[In the formula (1), R ⁰ represents a hydrogen atom or a methyl group, and X represents a halogen group, a halogenated hydrocarbon group, or a link having an atom other than a carbon atom, a hydrogen atom or a halogen atom between CC bonds of a halogenated hydrocarbon group. The group of the group, Y represents a single bond or a divalent organic group, and Z ⁺ represents a cationic chromophore selected from the triarylmethane group represented by the following formula (2-1), and the following formula (2-2) a triarylmethane-based cationic chromophore, a methine-based cationic chromophore, an azo-based cationic chromophore, a diarylmethane-based cationic chromophore, and a quinone Cationic chromophore, lanthanide cationic chromophore, cation chromophore of phthalocyanine At least one cationic chromophore of the cationic chromophore. ]

R ⁰ is preferably a methyl group in a hydrogen atom or a methyl group.

Examples of the halogen group in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the hydrocarbon group which forms the skeleton of the halogenated hydrocarbon group in X include (1) an aliphatic hydrocarbon group, (2) an alicyclic hydrocarbon group, and (3) an aliphatic hydrocarbon group having an alicyclic hydrocarbon group as a substituent (hereinafter referred to as An "alicyclic hydrocarbon-substituted aliphatic hydrocarbon group"), (4) an aromatic hydrocarbon group, and (5) an aromatic hydrocarbon group having an aliphatic hydrocarbon group as a substituent (hereinafter referred to as "aliphatic hydrocarbon-substituted aromatic hydrocarbon group") (6) An aliphatic hydrocarbon group having an aromatic hydrocarbon group as a substituent (hereinafter referred to as "aromatic hydrocarbon-substituted aliphatic hydrocarbon group"). The hydrocarbon group which forms the skeleton of the halogenated hydrocarbon group is preferably the following characteristic group from the viewpoint of solubility in an organic solvent.

That is, as the above (1) aliphatic hydrocarbon group, an alkyl group is preferable, and the alkyl group may be a straight chain or a branched chain. The alkyl group preferably has 1 to 20 carbon atoms, particularly preferably 1 to 8. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, secondary butyl group, tert-butyl group, n-pentyl group, second pentyl group, and new Amyl, n-hexyl, n-heptyl, n-octyl and the like.

The above (2) alicyclic hydrocarbon group may be a 2 to 4 ring crosslinked alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and more preferably an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms. Specific examples thereof include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group; a decyl group, a decyl group, and an adamantane; Base, bicyclooctyl and the like.

The (3) alicyclic hydrocarbon-substituted aliphatic hydrocarbon group is preferably an alicyclic saturated hydrocarbon-substituted alkyl group, and the number of carbon atoms thereof is preferably 4 to 20, particularly preferably 6 to 14. Specific examples thereof include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclohexylmethyl group, a cyclohexylpropyl group, an adamantylmethyl group, a 1-(1-adamantyl)ethyl group, and a cyclopentyl group B. Base.

The (4) aromatic hydrocarbon group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, a fluorenyl group and the like. Among them, a phenyl group is preferred.

The (5) aliphatic hydrocarbon-substituted aromatic hydrocarbon group is preferably an alkyl-substituted phenyl group, and the number of carbon atoms thereof is preferably 7 to 30, particularly preferably 7 to 20. Specific examples thereof include a tolyl group and a xylyl group. Base.

The aliphatic hydrocarbon group substituted with the above (6) aromatic hydrocarbon is preferably an aralkyl group, and the number of carbon atoms thereof is preferably 7 to 30, particularly preferably 7 to 20. Specifically, a benzyl group, a phenethyl group, etc. are mentioned, for example.

Further, the alkyl group in the present specification may be linear or branched.

Among them, as the hydrocarbon group forming the skeleton of the halogenated hydrocarbon group, (1) an aliphatic hydrocarbon group, (3) an alicyclic hydrocarbon-substituted aliphatic hydrocarbon group, (4) an aromatic hydrocarbon group, (5) an aliphatic hydrocarbon-substituted aromatic hydrocarbon group or (6) an aromatic hydrocarbon-substituted aliphatic hydrocarbon group, more preferably an alkyl group, an alicyclic saturated hydrocarbon-substituted alkyl group, a phenyl group, or An alkyl-substituted phenyl group or an aralkyl group is particularly preferably an alkyl group.

Further, in X, the halogen atom in the halogenated hydrocarbon group is preferably a fluorine atom from the viewpoint of heat resistance of the colorant, and the fluorine atom may be substituted for a part or all of the hydrogen atom of the hydrocarbon group. It is considered that by selecting a fluorine atom as a substituent, a salt having a stronger ion binding force can be formed to improve heat resistance.

X may be a group having a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between CC bonds of a halogenated hydrocarbon group, and may be a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom. Examples include -O-, -S-, -CO-, -COO-, -CONH-, -SO ₂ -, and the like. Further, the number of carbon atoms referred to in the fifth to sixth rows on page 6 means the total number of carbon atoms in a portion other than the carbon atoms constituting the linking group.

In the present invention, from the viewpoint of heat resistance of the coloring agent, X is preferably a halogenated hydrocarbon group or a group having a linking group containing an atom other than a carbon atom, a hydrogen atom or a halogen atom between CC bonds of a halogenated hydrocarbon group. The group represented by the following formula (3) or (4) is more preferably a group represented by the following formula (3) which forms a conjugated fluorene of an organic acid having a higher acidity.

[In the formula (3), R ²⁰ represents a hydrogen atom, a fluorine atom, an alkyl group, a fluoroalkyl group, an alicyclic hydrocarbon group, an alkoxy group, a fluoroalkoxy group, R ²¹ COOR ²² - or R ²³ COOR ²⁴ CFH-, R ²¹ and R ²³ independently of each other represent an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group, and R ²² and R ²⁴ independently of each other represent an alkanediyl group, and q represents 1 or more. An integer, "*" indicates a binding site. ]

[In the formula (4), R ²⁵ to R ²⁹ each independently represent a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a fluoroalkyl group or an alkoxy group, and "*" represents a binding site.

Wherein at least one of R ²⁵ to R ²⁹ is a fluorine atom or a fluoroalkyl group. ]

In the formula (3), the alkyl group in R ²⁰ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably a carbon number. It is an alkyl group of 1 to 4. Further, the alkyl group may be straight or branched. Specific examples thereof include the same alkyl groups as described above.

Further, the fluoroalkyl group in R ²⁰ is preferably a fluoroalkyl group having 1 to 20 carbon atoms, more preferably a fluoroalkyl group having 1 to 8 carbon atoms, still more preferably 1 carbon atom. ~4 fluoroalkyl. Further, the fluoroalkyl group may be straight or branched. Specific examples thereof include a fluoroalkyl group in which a part or the whole of a hydrogen atom of the above alkyl group is substituted with a fluorine atom, and a perfluoroalkyl group is particularly preferable.

The alicyclic hydrocarbon group in R ²⁰ may be a 2 to 4 ring crosslinked alicyclic hydrocarbon group. The alicyclic hydrocarbon group is preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, more preferably an alicyclic saturated hydrocarbon group having 3 to 12 carbon atoms. Specific examples thereof include the same alicyclic saturated hydrocarbon group as described above.

The alkoxy group in R ²⁰ is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms, still more preferably 1 to 4 carbon atoms. Alkoxy group. Further, the alkoxy group may be a straight chain or a branched chain. Specific examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a tertiary butoxy group, a secondary butoxy group, a n-pentyloxy group, and an isopentyloxy group. Base, n-hexyloxy, methoxymethoxy, ethoxyethoxy, 3-(isopropoxy)propoxy and the like.

Further, the fluoroalkoxy group in R ²⁰ is preferably a fluoroalkoxy group having 1 to 10 carbon atoms, more preferably a fluoroalkoxy group having 1 to 6 carbon atoms, and further preferably It is a fluoroalkoxy group having 1 to 4 carbon atoms. Further, the fluoroalkoxy group may be straight or branched. Specific examples thereof include a fluoroalkoxy group in which a part or the whole of a hydrogen atom of the above alkoxy group is substituted with a fluorine atom, and a perfluoroalkoxy group is particularly preferable.

In R ²¹ COOR ²² -, R ²³ COOR ²⁴ CFH- in R ²⁰ , R ²¹ and R ²³ independently of each other represent an alkyl group, an alicyclic hydrocarbon group, a heteroaryl group or a substituted or unsubstituted aryl group, an alkyl group It may be linear or branched, and the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms. Specific examples thereof include the same alkyl groups as described above. Further, the alicyclic hydrocarbon group may be a 2 to 4 ring crosslinked alicyclic hydrocarbon group, preferably an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, more preferably an alicyclic ring having 3 to 12 carbon atoms. Saturated hydrocarbon group. The heteroaryl group is preferably a group composed of a 5- to 10-membered aromatic heterocyclic ring containing one or more hetero atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples thereof include a furyl group, a thienyl group, and a pyrrolyl group. Azolyl, pyridyl, quinolyl, oxazolyl and the like. The aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and particularly preferably a phenyl group. In addition, examples of the substituent of the aryl group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a trifluoromethyl group, and the position and number of the substituents are arbitrary. When there are two or more substituents, the substituents may be the same or different.

Further, R ²² and R ²⁴ each independently represent an alkanediyl group, and preferably have a linear or branched alkanediyl group having 1 to 10 carbon atoms. Specific examples thereof include a methylene group, an ethylidene group, an ethane-1,1-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, and a propane-1,3-two group. Base, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,4-diyl Pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, octane-1,8-diyl, decane-1,10-diyl Wait. Among them, an alkanediyl group having 2 to 6 carbon atoms is preferred, and an alkanediyl group having 2 to 4 carbon atoms is more preferred. Among them, from the viewpoint of easiness of production, an ethyl group is preferably stretched.

Further, the upper limit of q is preferably 10, more preferably 8.

R ^{20 is} preferably a fluorine atom, a fluoroalkyl group, an alicyclic hydrocarbon group, a fluoroalkoxy group, R ²¹ COOR ²² - or R ²³ COOR ²⁴ CFH-, particularly preferably a fluorine atom or an alicyclic hydrocarbon group. , perfluoroalkoxy, R ²¹ COOCH ₂ CH ₂ - or R ²³ COOCH ₂ CH ₂ CFH-.

Further, in the formula (4), as the alkyl group, the fluoroalkyl group and the alkoxy group in R ²⁵ to R ²⁹ , an alkyl group having a R ²⁰ group of the above formula (3), a fluoroalkyl group and The alkoxy group has the same composition. Here, at least one of R ²⁵ to R ²⁹ is a fluorine atom or a fluoroalkyl group, and preferably at least three of R ²⁵ to R ²⁹ are a fluorine atom or a fluoroalkyl group.

Examples of the divalent organic group in Y include a divalent hydrocarbon group, a group in which a divalent hydrocarbon group and a linking group containing an atom other than a carbon atom and a hydrogen atom, or hydrogen of these groups are mentioned. A group in which a part of an atom is substituted by a halogen atom. Examples of such an organic group include an alkanediyl group having 1 to 10 carbon atoms, an extended aryl group having 6 to 20 carbon atoms, an extended arylalkyldiyl group having 7 to 20 carbon atoms, or a combination thereof. At least one selected from the group consisting of an alkanediyl group having 1 to 10 carbon atoms and an extended aryl group having 6 to 20 carbon atoms is selected from the group consisting of -O-, -S-, -COO-, -CONR'-(R' A group represented by at least one of a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and -SO ₂ -.

Specific examples of the alkanediyl group include the same alkanediyl groups as described above. Among them, an alkanediyl group having 2 to 8 carbon atoms is preferred, and an alkanediyl group having 2 to 6 carbon atoms is more preferred.

Examples of the extended aryl group include a stretching phenyl group, a naphthylene group, a biphenylylene group, a fluorenyl group and the like. Among them, a aryl group having 6 to 10 carbon atoms is preferred, and a phenyl group is particularly preferred.

The arylalkylene group refers to a divalent group in which an aryl group and an alkanediyl group are combined. The arylalkylene group is preferably an arylalkylene group having 7 to 15 carbon atoms, more preferably an aryl group having 7 to 13 carbon atoms, from the viewpoint of easiness of obtaining and producing a raw material. Alkanediyl. Specific examples thereof include a stretch phenylmethylene group, a phenylene dimethylene group, a phenyltrimethylene group, a phenylene tetramethylene group, a phenylphenylpentamethylene group, and a phenylene group. Methylene is an extended phenyl C _1-6 alkanediyl group. Further, an ortho, a meta and a para-position are present in the arylalkylene group, and from the viewpoint of less steric hindrance, a counterpart is preferred.

Further, at least one selected from the group consisting of an alkanediyl group having 1 to 10 carbon atoms and an exoaryl group having 6 to 20 carbon atoms is selected from -O-, -S-, -COO-, -CONR' a group in which (R' represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) and at least one of -SO ₂ -, preferably a combination of an alkanediyl group selected from the group consisting of 1 to 10 carbon atoms. And a group of at least one selected from the group consisting of at least one of -O-, -COO-, and -SO ₂ -, more preferably a combination selected from carbon atoms. At least one of an alkyldiyl group having 1 to 10 and an extended aryl group having 6 to 20 carbon atoms and at least one selected from the group consisting of -O- and -SO ₂ -.

Next, the Z ^{+ will} be explained.

Z ⁺ represents a triarylmethane-based cationic chromophore represented by the following formula (2-1), a triarylmethane-based cationic chromophore represented by the following formula (2-2), and a methine group. Cationic chromophore, azo-based cationic chromophore, diarylmethane-based cationic chromophore, quinone-based cationic chromophore, lanthanide cationic chromophore a cationic chromophore of the phthalocyanine At least one cationic chromophore of the cationic chromophore.

Further, the triarylmethane-based cationic chromophore represented by the formula (2-1) and the triarylmethane-based cationic chromophore represented by the formula (2-2) have various resonance structures, and in the present specification, When a resonance structure exists in the chromophore represented by each formula, it is the same as the chromophore represented by the formulas (2-1) and (2-2).

[In the formulae (2-1) and (2-2), R ¹ to R ⁶ and R ¹¹ to R ¹⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and a substitution. Or an unsubstituted cycloalkyl group having 3 to 8 carbon atoms or a substituted or unsubstituted aryl group, and R ⁷ to R ⁹ and R ¹⁷ to R ¹⁹ independently of each other represent an alkyl group having 1 to 8 carbon atoms or chlorine. The atoms, l, m, s, t, and u each independently represent an integer of 0 to 4, and n represents an integer of 0 to 6.

Where l, m and n are not 0 at the same time. ]

Specific examples of the alkyl group having 1 to 8 carbon atoms in R ¹ to R ⁹ and R ¹¹ to R ¹⁹ include the same alkyl groups as described above. Among them, an alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group or an ethyl group is particularly preferred.

Specific examples of the cycloalkyl group having 3 to 8 carbon atoms in R ¹ to R ⁶ and R ¹¹ to R ¹⁶ include the same cycloalkyl groups as described above. Among them, a cycloalkyl group having 4 to 6 carbon atoms is preferred, and a cyclohexyl group is particularly preferred.

The aryl group in R ¹ to R ⁶ and R ¹¹ to R ¹⁶ is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include the same aryl groups as described above, and among them, a phenyl group is preferred.

Examples of the substituent of the alkyl group, the cycloalkyl group and the aryl group in R ¹ to R ⁶ and R ¹¹ to R ¹⁶ include an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a trifluoromethyl group, and cyanogen. The group, the cycloalkyl group and the aryl group may be substituted by an alkyl group having 1 to 6 carbon atoms. Specific examples of the substituents include the same substituents as described above. Further, when the position and the number of the substituent are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

R ⁷ to R ⁹ and R ¹⁷ to R ^{19 are} preferably an alkyl group having 1 to 4 carbon atoms or a chlorine atom, more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group or an ethyl group. .

In the formula (2-1), l and m are preferably integers of 0 to 2, and n is preferably 0 or 1. However, l, m, and n are not 0 at the same time. Wherein, as a combination of l, m, and n, a combination of l=1, m=0, n=0, a combination of l=0, m=0, n=1, l=2, m=0, a combination of n=0, a combination of l=1, m=1, n=0, a combination of l=1, m=1, n=1, more preferably a combination of l=1, m=0, n=0 a combination of l=0, m=0, n=1, l=1, m=1, n=0.

In the formula (2-2), s is preferably an integer of 0 to 2, and t and u are preferably 0 or 1, and more preferably one or more of s, t, and u are 1~. An integer of 4. Wherein, as a combination of s, t, and u, it is preferably s Combination of =0, t=0, u=0, combination of s=1, t=0, u=0, combination of s=2, t=0, u=0, s=1, t=1, u a combination of =0, a combination of s=1, t=1, and u=1, particularly preferably a combination of s=0, t=0, u=0, a combination of s=1, t=0, u=0, A combination of s=1, t=1, u=0.

The chromophore represented by the formula (2-1) or the chromophore represented by the formula (2-2) may, for example, be a chromophore represented by the following compound group a and compound group b, wherein Preferred are chromophores a1, a2, a3, a4, a5, a6, b1, b2, b3, b4, b6, more preferably a2, a3, a4, a5, a6, b3, b4.

[Compound group a]

[Compound group b]

In addition, as the cationic chromophore of the triarylmethane type represented by the formula (2-1), for example, the chromophore described in JP-A-2012-17425 can be mentioned.

The methacrylic chromophore is preferably a chromophore represented by the following formulas (5-1) to (5-3), more preferably a chromophore represented by the following formula (5-1).

[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 represents a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and G represents -CH=CH-, -CH=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 above) or -N=N-NR ³⁷ - (R ³⁷ is synonymous with the above), and R ^a represents a substitution or an unsubstituted An aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. ]

R ^{a is} preferably a group represented by the following formula (5a) to (5h), and more preferably a group represented by the following formula (5b) or (5h).

[In the formulae (5a) to (5h), 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 , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁷ , R ⁴⁸ and R ⁴⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴¹ , R ⁴⁶ and R ⁵⁰ independently represent a hydrogen atom. a halogen group, an alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a nitro group, a hydroxyl group or a cyano group. ]

The alkyl group in R ³² to R ⁵⁰ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. Further, examples of the substituent of the alkyl group include a halogen group, a cyano group, and a hydroxyl group. Further, the halogen group in R ³¹ , R ⁴¹ , R ⁴⁶ and R ⁵⁰ , as the alkoxy group in R ⁴¹ , R ⁴⁶ and R ⁵⁰ , is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably It is a methoxy group or an ethoxy group.

Representative examples of the chromophore represented by the above formulas (5-1) to (5-3) include, for example, chromophores represented by the following compound group c.

[Compound group c]

Examples of the azo-based chromophore include chromophores represented by the following formulae (6-1) to (6-6), and preferably represented by the following formulae (6-1) to (6-5). The chromophore is more preferably a chromophore represented by the following formula (6-1).

[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 alkane 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 An alkyl group having 1 to 6 carbon atoms, R ⁵⁹ represents a group forming a quaternary 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 each independently 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 above), - 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 The group represented by (6-ii).

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

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

[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 carbon atom number 1~ An alkyl group of 6, 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 a carbon atom number of 1. The alkyl group of ~6, R ⁷⁰ to R ⁷³ 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. . ]

The alkyl group in R ⁵¹ to R ⁵⁸ and R ⁶⁰ to R ⁷⁵ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. Further, examples of the substituent of the alkyl group include a halogen group, a hydroxyl group, a cyano group, and a —CONH ₂ group.

Representative examples of the chromophore represented by the above formulas (6-1) to (6-6) include, for example, the following chromophores of the compound group d or the compound group e.

[Compound group d]

[Compound group e]

The diaryl chromophore is preferably a chromophore represented by the following formula (7-1) or (7-2), more preferably a chromophore represented by the following formula (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 independently of each other represent a carbon number of 1 to 6; The alkyl group, R ⁸⁵ , R ⁹⁰ and R ⁹¹ independently of each other represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

The alkyl group in R ⁸¹ to R ⁹¹ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group.

Representative examples of the chromophore represented by the above formulas (7-1) to (7-2) include, for example, chromophores represented by the following compound group f.

[Compound group f]

The quinone imine chromophore is preferably a chromophore represented by the following formulas (8-1) to (8-3), more preferably the following formula (8-1) or (8-3). The chromophore represented.

[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 represent 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 substitution or an unsubstituted An alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a nitro group or a cyano group, and Q represents an oxygen atom or a sulfur atom. ]

The alkyl group in R ¹⁰¹ to R ¹¹¹ and R ¹¹³ to R ¹²⁰ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. Further, examples of the substituent of the alkyl group include a halogen group, a hydroxyl group, and a cyano group. The aryl group having 6 to 20 carbon atoms in R ¹⁰⁷ and R ¹¹³ is preferably a phenyl group.

Representative examples of the chromophore represented by the above formulas (8-1) to (8-3) include, for example, chromophores represented by the following compound group g.

[Compound group g]

The chromophore represented by the following formula (9-1) or (9-2) is more preferably a chromophore represented by the following formula (9-1).

[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 substitution or a non- a substituted phenyl group, 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 extension. alkyl. ]

The alkyl group in R ¹³¹ to R ¹³⁶ and R ¹³⁸ to R ¹⁴⁰ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group. In addition, examples of the substituent of the alkyl group include a halogen group, a hydroxyl group, and a cyano group. Examples of the substituent of the phenyl group include an alkyl group having 1 to 6 carbon atoms, a halogen group, a hydroxyl group, and a cyanogen group. Base.

Further, as the alkylene group, an alkylene group having 2 to 4 carbon atoms such as an ethyl group, a trimethylene group, a propyl group or a tetramethylene group is preferable, and as the substituent of the alkylene group, a substituent may be mentioned. Hydroxyl, cyano or nitro groups.

Representative examples of the chromophore represented by the above formula (9-1) or (9-2) include, for example, chromophores represented by the following compound group h.

[Compound group h]

The phthalocyanine chromophore is preferably a chromophore represented by the following formula (10).

CuPC-T (10)

[In the formula (10), CuPc represents a copper phthalocyanine 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 or an alkane having 1 to 6 carbon atoms. The base or the phenyl group, p ¹ independently represents an integer of 2 to 8, and mb independently represents an integer of 1 to 5. ]

Representative examples of the chromophore represented by the above formula (10) include, for example, chromophores represented by the following compound group k.

[Compound group k]

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

[In the formula (11), R ¹⁷¹ , R ¹⁷² , R ¹⁷³ and R ¹⁷⁴ each independently represent a hydrogen atom, -R ¹⁷⁸ or an aromatic hydrocarbon group having 6 to 10 carbon atoms (wherein the aromatic hydrocarbon group is contained) The hydrogen atom may be a halogen atom, -R ¹⁷⁸ , -OH, -OR ¹⁷⁸ , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ¹⁷⁸ , -SO ₃ R ¹⁷⁸ , -SO ₂ NHR ¹⁷⁹ Or -SO ₂ NR ¹⁷⁹ R ¹⁸⁰ substituted); R ¹⁷⁵ and R ¹⁷⁶ independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R ¹⁷⁷ represents -SO ₃ H, -SO ₃ M, -CO ₂ H , -CO ₂ R ¹⁷⁸ , -SO ₃ R ¹⁷⁸ , -SO ₂ NHR ¹⁷⁹ or -SO ₂ NR ¹⁷⁹ R ¹⁸⁰ ; k represents an integer of 0 to 5, and when k is an integer of 2 or more, a plurality of R ¹⁷⁷ may be the same or R ¹⁷⁸ represents a saturated hydrocarbon group having 1 to 10 carbon atoms (wherein the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and the methylene group contained in the saturated hydrocarbon group may be an oxygen atom, a carbonyl group or -NR ¹⁷⁸⁾ -substituted); R ¹⁷⁹ and R ¹⁸⁰ independently of each other represent a chain alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms or -Z, or R ¹⁷⁹ and R ¹⁸⁰ are bonded to each other. a substituted or unsubstituted heteroatom having 1 to 10 carbon atoms Groups. Wherein the hydrogen atom contained in the alkyl group and the cycloalkyl group may be substituted by a hydroxyl group, a halogen atom, -Z, -CH=CH ₂ or -CH=CHR ¹⁷⁸ , and the methylene group contained in the alkyl group and the cycloalkyl group The group may be substituted by an oxygen atom, a carbonyl group or -NR ¹⁷⁸ -, the hydrogen atom contained in the heterocyclic group may be substituted by -R ¹⁷⁸ , -OH or -Z; M represents a sodium atom or a potassium atom; Z represents a carbon atom number of 6 An aromatic hydrocarbon group of ~10 or an aromatic heterocyclic group having 5 to 10 carbon atoms. Here, the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted by -OH, R ¹⁷⁸ , -OR ¹⁷⁸ , -NO ₂ , -CH=CH ₂ , -CH=CHR ¹⁷⁸ or a halogen atom. ]

The saturated hydrocarbon group in R ¹⁷⁸ may be a saturated hydrocarbon group having 1 to 10 carbon atoms, and may be any of a linear chain, a branched chain, and a cyclic chain, and may have a crosslinked structure. Specifically, in addition to the alkyl group similar to R ⁴ in the above formula (2), an anthracenyl group, a fluorenyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclic fluorene may be mentioned. base. The group in which the methylene group contained in the saturated hydrocarbon group is substituted with an oxygen atom may, for example, be a methoxypropyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group or a methoxyhexyl group.

^Examples of the substituted or unsubstituted heterocyclic group having 1 to 10 carbon atoms which are formed by bonding R ¹⁷⁹ and R ^{180 to} each other include pyrrole, pyridine, fluorene, isoindole, quinoline, isoquinoline and anthracene. Oxazole, phenanthridine, acridine, furan, pyran, isobenzofuran, iso Terpene, Thiophene, thiophene, phenanthrene Thiophene Wait. The substituent in the above heterocyclic group may, for example, be a halogen group, a hydroxyl group, an alkoxy group, an amine group or an alkyl group. Further, examples of the aromatic heterocyclic group having 5 to 10 carbon atoms in Z include a furyl group, a thienyl group, a pyridyl group, and a pyrrolyl group. Azolyl, different Azolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, pyrimidinyl and the like.

Examples of the aromatic hydrocarbon group in R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ and Z include a phenyl group and a naphthyl group.

^Examples of the -SO ₃ R ^{178 in} R ¹⁷¹ , R ¹⁷² , R ¹⁷³ , R ¹⁷⁴ and R ¹⁷⁷ include a methylsulfonyl group, an ethylsulfonyl group, a hexylsulfonyl group, and a sulfonyl group. Further, examples of the -CO ₂ R ¹⁷⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a cyclohexyloxycarbonyl group, and a methoxypropoxycarbonyl group. ^Further , R ¹⁷⁹ and R ^{180 in} -SO ₂ NHR ¹⁷⁹ and -SO ₂ NR ¹⁷⁹ R ¹⁸⁰ are preferably a branched alkyl group having 6 to 8 carbon atoms or an alicyclic ring having 5 to 7 carbon atoms. a hydrocarbon group, 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.

R ¹⁷¹ , R ¹⁷² , R ¹⁷³ and R ^{174 are} preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group. .

R ¹⁷⁵ and R ^{176 are} preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group has more preferably 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group.

R ^{177 is} preferably -SO ₃ H, -SO ₃ M, -CO ₂ H, or -CO ₂ R ¹⁷⁸ , more preferably -CO ₂ H or -CO ₂ R ¹⁷⁸ . -CO ₂ R ¹⁷⁸ is R ¹⁷⁸ is preferably an alkyl group having a carbon number of 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4, further more preferably methyl or ethyl.

k is preferably 1 or 2, more preferably 1.

A representative example of the cation represented by the above formula (11) is, for example, a cation represented by the following formula.

Cationic triarylmethane system wherein, from the viewpoint of heat resistance as Z ^+, a cationic chromophore triarylmethane system is preferably represented by the formula (2-1), (2-2) a chromophore, a methine-based cationic chromophore, an azo-based cationic chromophore, a diarylmethane-based cationic chromophore, a quinone-based cationic chromophore, The cationic chromophore of the system is more preferably a triarylmethane-based cationic chromophore represented by the formula (2-1) or a triarylmethane-based cationic chromophore represented by the formula (2-2). a methyl-based cationic chromophore, a cationic chromophore.

The reason for the difference in heat resistance due to the type and structure of the chromophore has not been determined. The inventors of the present invention thought that the chromophore having a resonance structure interacts with the structural unit represented by the formula (1), so that it is easily stabilized and the heat resistance is improved.

The coloring agent may have a structural unit other than the structural unit represented by the formula (1) (hereinafter also referred to as "another structural unit"), and examples of such a structural unit include, for example, one or more carboxyl groups. a structural unit of an ethylenically unsaturated monomer, a structural unit derived from an N-membered substituted maleimide, a structural unit derived from an aromatic vinyl compound, a structural unit derived from a (meth) acrylate, and a vinyl group A structural unit of an ether, a structural unit derived from a macromonomer having a mono(meth)acrylinyl group at the terminal of the polymer molecular chain, and the like.

The structural unit derived from the ethylenically unsaturated monomer having one or more carboxyl groups may be obtained from an ethylenically unsaturated monomer having a carboxyl group, for example, (meth)acrylic acid, maleic acid, maleic anhydride, Succinic acid mono [2-(methyl) propylene methoxyethyl] ester, ω-carboxy polycaprolactone mono (meth) acrylate, p-vinyl benzoic acid.

Further, the structural unit derived from the N-position substituted maleimine may be obtained by substituting a maleimine at the N-position, for example, N-phenylmaleimide, N-cyclohexylmalanium Imine.

Further, the structural unit derived from the aromatic vinyl compound can be obtained from an aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, or the like. P-vinylbenzyl glycidyl ether, vinyl naphthalene.

Further, the structural unit derived from (meth) acrylate may be obtained from (meth) acrylate such as methyl (meth) acrylate, n-butyl (meth) acrylate or (meth) acrylate 2 -ethylhexyl ester, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate, polyethylene glycol (degree of polymerization 2 to 10) methyl ether (methyl Acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) Mono(meth)acrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]non-8-yl ester, (a) Dicyclopentenyl acrylate, glycerol mono(meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-anisyl, (methyl) Glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acrylomethoxymethyl]oxetane, 3-[(meth) propylene oxime Oxymethyl]-3-ethyloxetane.

Further, the structural unit derived from a vinyl ether can be obtained from a vinyl ether such as cyclohexyl vinyl ether, isodecyl vinyl ether or tricyclo [5.2.1.02, 6] fluoren-8-yl vinyl. Ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane.

Further, the structural unit derived from a macromonomer having a mono(meth)acryl fluorenyl group at the end of the polymer molecular chain may have a large mono(meth)acryl fluorenyl group at the end of the polymer molecular chain as follows Molecular monomer For example, polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, polyoxyalkylene.

Among them, from the viewpoint of dispersibility, the coloring agent preferably has a structural unit derived from a (meth) acrylate as another structural unit, and more preferably has a structural unit derived from an alkyl (meth) acrylate.

When the coloring agent has other structural units, the copolymerization ratio of the other structural units is preferably the following from the viewpoint of dispersibility.

That is, the ratio r of the structural unit represented by the formula (1) in the structural unit of the present colorant to the other structural unit is in terms of a molar ratio, preferably p/r = 1/0.5 to 1/19. More preferably, it is p/r=1/1.5~1/9, and further preferably p/r=1/2~1/7.

The polystyrene-equivalent weight average molecular weight (Mw) of the coloring agent measured by a gel permeation chromatography (hereinafter referred to as GPC) (elution solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. . In this manner, heat resistance, film properties, electrical properties, pattern shape, and resolution can be improved.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the present colorant in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, Mn is a polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

The coloring agent can be produced by a known method, and can be produced, for example, by the same method as the example of JP-A-2012-194466. The colorant thus obtained is soluble in propylene glycol monomethyl Various organic solvents represented by ether acetate and the like have excellent solvent resistance.

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

The coloring composition of the present invention may further contain other coloring agents as the (A) coloring agent. In this case, the content ratio of the coloring agent is preferably from 0.1 to 99% by mass, more preferably from 1 to 80% by mass, still more preferably from 10 to 70% by mass, particularly preferably from 20 to 60% by mass of the total coloring agent. %.

Other coloring agents are not particularly limited, and colors and materials may be appropriately selected depending on the application, and pigments, dyes, and natural colors other than the coloring agent may be used, and it is preferable to obtain pixels having high luminance and color purity. It is an organic pigment, an organic dye, and more preferably an organic pigment.

As the above-mentioned organic pigment, for example, a compound classified as a pigment in a color index (CI; The Society of Dyers and Colourists Co., Ltd.) may be mentioned, and it is preferable to use it in addition to Japanese Patent Laid-Open Publication No. 2001-081348, Japanese Laid-Open Patent Publication No. 2010- 219334, Japanese Laid-Open Patent Publication No. 2010-237304, Japanese Laid-Open Patent Publication No. 2010-237384, Japanese Laid-Open Patent Publication No. 2010-237569, No. JP-A-2011-006602, No. 2011-145346 The lake pigment, CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI described in the Gazette, etc. Pigment Blue 15:6, CI Pigment Blue 80, CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Orange 38, CI Pigment Violet 23 Organic pigments other than lake pigments. Further, among the lake pigments, a triarylmethane-based lake pigment is preferred, a lake pigment, an azo lake pigment, more preferably a triaryl methane lake pigment and It is a lake pigment.

In the present invention, when another coloring agent is used as the pigment, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Further, the surface of the pigment particles may be modified with a resin as needed. The resin which is modified by the surface of the pigment particle, for example, a vehicle resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments. For the resin coating method of the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like can be used. Further, the organic pigment can be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

In the present invention, when a pigment is used as the other coloring agent, a known dispersing agent and a dispersing aid may be further contained. Examples of the known dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene alkyl phenyl ether dispersant, and a polydispersant. A glycol diester dispersing agent, a sorbitan fatty acid ester dispersing agent, a polyester dispersing agent, an acrylic dispersing agent, etc., and a dispersing auxiliary agent, a pigment derivative etc. are mentioned.

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 a urethane-based dispersing agent, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182, Disperbyk-2164 (above BYK-Chemie) As a polyethyleneimine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and a polyester-based dispersant, Adisper PB821, Adisper PB822, Adisper PB880, and Adisper PB881 (above, Ajinomoto Fine-Techno Co., Ltd.) and the like.

In addition, specific examples of the pigment derivative include sulfonium cyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

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

From the viewpoint of forming a black matrix or a black spacer having excellent heat resistance and solvent resistance, and suppressing the transfer property, and having high luminance and high color purity, or a black matrix having excellent light blocking properties, (A) the content ratio of the coloring agent is in the coloring composition. The solid content is usually 5 to 70% by mass, preferably 5 to 60% by mass. Here, the solid content means a component other than the solvent described later.

- (B) Adhesive Resin -

In the colored composition of the present invention, a binder resin (but a polymer having a structural unit represented by the above formula (1)) may be contained. Thereby, the solubility of the coloring composition, the adhesion to the substrate, the storage stability, and the like can be improved. The binder resin is not particularly limited as long as it does not contain the structural unit represented by the above formula (1), and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. In particular, a polymer having a carboxyl group (hereinafter referred to as a "carboxyl group-containing polymer") is preferable, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "unsaturated monomer". (b1)") a copolymer of another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)").

The unsaturated monomer (b1) is the same as the above-mentioned ethylenically unsaturated monomer which has a carboxyl group. Further, the unsaturated monomer (b1) may be used singly or in combination of two or more.

Further, examples of the unsaturated monomer (b2) include an N-position substituted maleimide, an aromatic vinyl compound, a (meth) acrylate, a vinyl ether, and an end of a polymer molecular chain. A macromonomer having a mono(meth)acryl fluorenyl group or the like can be exemplified as the specific examples thereof. Further, the unsaturated monomer (b2) may be used singly or in combination 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 from 5 to 50% by mass, further preferably from 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- 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. The copolymer disclosed in the above.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acrylonyl group in a side chain as disclosed in JP-A-H08-140095, and the like, is disclosed as a binder resin.

The weight average molecular weight (Mw) in terms of polystyrene measured by a gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) in the present invention is usually from 1,000 to 100,000, preferably from 1,000 to 100,000. It is 3000~50000. In this manner, heat resistance, film properties, electrical properties, pattern shape, and resolution can be improved.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. Further, Mn referred to herein is a polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

The binder resin in the present invention can be produced by a known method. For example, the method disclosed in JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 07/029871 can be used. , control its structure, 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 usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, more preferably 50 to 350 parts by mass, even more preferably 100 parts by mass of the (A) coloring agent, further preferably 100 to 250 parts by mass. In this manner, heat resistance, solvent resistance, alkali developability, storage stability of the colored composition, and chromaticity characteristics can be improved. In addition, the transfer property can be suppressed.

- (C) Polymeric Compound -

In the present invention, the polymerizable compound means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an epoxy group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, a compound having two or more (meth)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups is preferred as the polymerizable compound.

Specific examples of the compound having two or more (meth) acryloyl fluorenyl groups include polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid, and a lactone-modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a polyfunctional isocyanate Urethane (meth) propylene An acid ester, a polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a (meth) acrylate having a hydroxyl group and an acid anhydride, or the like.

Here, examples of the aliphatic polyhydroxy compound include a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol; for example, glycerin or trimethylolpropane. A ternary or higher aliphatic polyhydroxy compound such as pentaerythritol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(methyl). Acrylate, dipentaerythritol penta (meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, such as pyromelli-4. A tetrabasic acid dianhydride such as formic acid dianhydride, biphenyltetracarboxylic dianhydride, or benzophenone tetracarboxylic dianhydride.

In addition, examples of the polyfunctional (meth) acrylate modified by the caprolactone include the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. The polyfunctional (meth) acrylate modified with the alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. And at least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, modified by at least one selected from the group consisting of ethylene oxide and propylene oxide Trimethylolpropane tris(meth)propene An acid ester, at least one modified pentaerythritol tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, and at least one selected from the group consisting of ethylene oxide and propylene oxide Modified pentaerythritol tetra(meth)acrylate, at least one modified dipentaerythritol penta (meth) acrylate selected from the group consisting of ethylene oxide and propylene oxide, selected from At least one modified dipentaerythritol hexa(meth)acrylate or the like of ethylene oxide and propylene oxide.

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. In addition, the melamine structure and the benzoguanamine structure mean that there are one or more three Ring or phenyl substituted three The chemical structure of the ring as a basic skeleton is also 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, and N. , N, N', N'-tetrakis(alkoxymethyl)benzoguanamine, N, N, N', N'-tetrakis(alkoxymethyl) glycoluril, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid or a polyfunctional group modified by caprolactone is preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa Oxymethyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. The strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and the unexposed portion is less likely to cause scumming or film residue on the substrate and the light shielding layer, and the trihydric or higher aliphatic polyhydroxy compound is (methyl) Among the polyfunctional (meth) acrylates obtained by the reaction of acrylic acid, trimethylolpropane triacrylate, neopentyl alcohol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. The ester is particularly preferably 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. compound of.

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

The content of the (C) polymerizable compound in the present invention is preferably 10 to 1000 parts by mass, more preferably 20 to 700 parts by mass, still more preferably 100 to 500 parts by mass, per 100 parts by mass of the (A) coloring agent. Very good for 200 to 400 parts by mass. In this manner, heat resistance, solvent resistance, curability, and alkali developability are improved. In addition, it is also possible to suppress the transfer property.

-Photopolymerization initiator -

The coloring composition of the present invention may contain a photopolymerization initiator. Thereby, the radiation-sensitive linearity can be imparted to the colored composition. The photopolymerization initiator used in the present invention is a compound which generates an active species which can initiate polymerization of a polymerizable polymer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

As such a photopolymerization initiator, for example, oxygen sulfur can be mentioned Compound, acetophenone compound, biimidazole compound, three Compound, O-antimony compound, phosphonium salt compound, benzoin compound, benzophenone compound, α-diketone compound, polycyclic anthraquinone compound, diazole 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. As the photopolymerization initiator, it is preferably selected from the group consisting of oxygen and sulfur Compound, acetophenone compound, biimidazole compound, three At least one of a compound and an O-lanthanide compound.

In the preferred photopolymerization initiator of the present invention, as oxygen sulphur Specific examples of the compound, oxygen sulphur 2-chlorooxosulfur 2-methyloxosulfur 2-isopropyloxysulfur 4-isopropyloxysulfur 2,4-dichlorooxosulfur 2,4-dimethyloxosulfur 2,4-diethyloxysulfide 2,4-diisopropyloxysulfide Wait.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Tropicpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)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, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of supplying a hydrogen atom to a radical generated by a biimidazole-based compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. a thiol-based hydrogen donor such as azole; an amine-based hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone . In the present invention, the hydrogen donor may be used alone or in combination of two or more. However, from the viewpoint of further improving the sensitivity, it is preferred to combine one or more kinds of thiol-based hydrogen donors and one or more kinds of amine-based hydrogens. Use it for the body.

In addition, as the above three Specific examples of the compound include 2,4,6-tris(trichloromethyl)-all. 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Three with a halogenated methyl group a compound.

Further, specific examples of the O-lanthanoid compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), 1 -[9-ethyl-6-(2-methylbenzylidenyl)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl- 6-(2-methyl-4-tetrahydrofurylmethoxybenzylidene)-9H-indazol-3-yl]-ethanone 1-(O-acetamidine), 1-[9-ethyl -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzylidene}-9H-indazol-3-yl]-B Ketone 1-(O-acetamidine) and the like. As a commercial item of the O-oxime compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), etc. can also be used.

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. As such a sensitizer, for example, 4,4'-bis(dimethyl) can be mentioned. Aminopheny)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4- Ethyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-di Ethylamino-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) polymerizable compound. In this manner, heat resistance, solvent resistance, curability, and film properties can be improved. In addition, it is also possible to suppress the transfer property.

- solvent -

The colored composition of the present invention contains the above components (A) to (C) and optionally added other components, and is usually prepared as a liquid composition in combination with a solvent.

As the solvent, if the components (A) to (C) constituting the colored composition and other components are dispersed or dissolved, and do not react with these components, they have appropriate volatility, and can be appropriately selected and used.

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 diethyl ether. 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 single positive Propylene ether, 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, etc. Glycol monoalkyl ethers; Methyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol Ketone alcohols such as (cyclo)alkyl alcohols; diacetone alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Alcohol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy acetate (poly)alkylene glycol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, Ketones such as cyclohexanone, 2-heptanone, and 3-heptanone; diacetate such as propylene glycol diacetate, 1,3-butanediol diacetate, and 1,6-hexanediol diacetate Class; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, C Alkoxycarboxylates such as acid-3-methyl-3-methoxybutyl ester; ethyl acetate, B N-propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate Ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl ethyl acetate, ethyl acetate, ethyl 2-oxobutyrate and other esters; toluene An aromatic hydrocarbon such as xylene; a decylamine such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone; or an indoleamine.

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 preferable from the viewpoints of solubility, pigment dispersibility, coating properties and the like. Monoethyl ether acetate, acetic acid-3-methoxybutyl ester, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butyl Glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl ester, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, butyl Isopropyl acrylate, 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 of the coloring composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. By adopting such a method, it is possible to obtain a colorant dispersion having good dispersibility and stability, and a coloring composition having good coatability and stability.

-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); a surfactant such as a fluorine surfactant or a lanthanoid surfactant; Vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris (2-A Oxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Trimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2- (3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyl An adhesion promoter such as trimethoxydecane or 3-mercaptopropyltrimethoxydecane; 2,2-thiobis(4-methyl-6-tertiarybutylphenol), 2,6-di-tertiary Antioxidant such as phenol; ultraviolet absorber such as 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone; Anti-flocculant such as sodium acrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amine Residue improver such as keto-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono[ 2-(methyl)propenyloxyethyl]ester, Acid mono- [2- (meth) Bing Xixi oxyethyl] ester, ω- carboxy-polycaprolactone mono (meth) acrylate developability improving agent.

[Coloring cured film and method of forming the same]

The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically refers to a pixel for each color of a display element or a solid-state image sensor, a black matrix, a black spacer, and the like.

Hereinafter, a colored cured film used in a color filter constituting a display element or a solid-state image sensor, and a method of forming the same will be described.

As a method of manufacturing a color filter, the first method is as follows. First, on the surface of the substrate, as needed, to form a partition A light shielding layer (black matrix) is formed in a manner of a portion of the pixel. Next, a liquid composition of, for example, a blue radiation sensitive composition of the present invention is applied onto the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkaline developing solution to dissolve and remove the unexposed portion of the coating film. Thereafter, by post-baking, a pixel array in which blue pixel patterns are arranged in a predetermined array is formed.

Next, using each of the green or red radiation-sensitive coloring compositions, the coating, prebaking, exposure, development, and post-baking of the respective radiation-sensitive coloring compositions are performed in the same manner as described above, and green color is sequentially formed on the same substrate. Pixel 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 order.

The black matrix may be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, or a radiation-sensitive coloring composition in which a black colorant is dispersed may be used and formed. The above-described pixels are formed in the same manner.

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

Further, as appropriate, these substrates may be subjected to an appropriate pretreatment such as chemical treatment, plasma treatment, ion plating, sputtering, gas phase reaction, or vacuum vapor deposition using a decane coupling agent or the like.

When a radiation-sensitive coloring composition is applied onto a substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method, a slit die coating method (slit coating method), or a bar coating method may be employed. Jiawei uses spin coating and slot die coating.

The prebaking is usually carried out by combining drying under reduced pressure and drying by heating. Drying under reduced pressure usually proceeds until it reaches 50 to 200 Pa. In addition, the conditions of heat drying are usually about 1 to 10 minutes at 70 to 110 °C.

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

Examples of the light source for forming radiation used in at least one selected from the group consisting of a pixel and a 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, and a medium voltage. Light source such as mercury lamp, low-pressure mercury lamp or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the exposure light source, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10000 J/m ² .

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4 is preferred. .0] An aqueous solution of 7-undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene or the like.

A water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like may be added to the alkaline developing solution in an appropriate amount. Further, after alkaline development, water washing is usually carried out.

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 development conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually about 10 to 60 minutes at 180 to 280 °C.

The film thickness thus formed is usually 0.5 to 5 μm , preferably 1.0 to 3 μm .

In addition, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. 2000-310706, and the like. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, a liquid composition of, for example, a blue thermosetting coloring composition is ejected into the formed partition walls by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then cured by post-baking to form a blue pixel pattern.

Next, using a green or red thermosetting coloring composition, 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 three primary colors of red, green, and blue are arranged 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 order.

Further, the partition wall not only functions as a light-shielding function but also functions to prevent color mixing of the coloring compositions discharged into the cells, 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 used for forming the color filter, the light source of the radiation, and the methods and conditions for prebaking and postbaking are the same as those of the first method described above. The film thickness of the pixel formed by the inkjet method is equivalent to the height of the partition wall.

After the protective film is formed on the pixel pattern thus obtained as needed, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, and may be formed into a light-shielding spacer (black spacer). At this time, a radiation-sensitive coloring composition in which a black colorant is dispersed is used, but the coloring composition of the present invention is also suitable for forming the above black spacer.

The radiation sensitive coloring composition of the present invention is also suitable for forming a colored cured film of any of the color pixels, the black matrix, the black spacer, and the like used in the above color filter.

The color filter including the colored cured film of the present invention thus formed is extremely useful in color brightness and color purity, and thus is useful for a color liquid crystal display element, a color image pickup device element, a color sensor, an organic EL display element, an electronic paper, or the like. . Further, the display element to be described later may have at least one or more colored cured films formed using the radiation sensitive coloring composition of the present invention.

[display component]

The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a 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 with the liquid crystal layer interposed therebetween. Further, a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode or IZO (indium oxide and zinc oxide) may be used. The mixture of the electrodes is separated from the substrate by a structure in which the liquid crystal layers are opposed to each other. The structure of the latter can significantly increase the aperture ratio, and has the advantage of being able to obtain a bright and high-definition liquid crystal display element. Further, in the latter configuration, the black matrix and the black spacer may be formed on one of the substrate side on which the color filter is formed and the substrate side on which the ITO electrode or the IZO electrode is formed.

The color liquid crystal display device including the colored cured film of the present invention includes a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp) and a backlight unit using a white LED as a light source. As the white LED, for example, a white LED in which white light is obtained by combining a red LED, a green LED, and a blue LED by color mixing, and a white LED in which a combination of a blue LED, a red LED, and a green phosphor is mixed to obtain white light can be cited. A white LED that combines a blue LED, a red illuminating phosphor, and a green illuminating phosphor to obtain a white light by color mixing, and obtains a white LED of white light by a color mixture of a blue LED and a YAG-based phosphor, and combines blue. The LED, the orange illuminating phosphor, and the green illuminating phosphor obtain white light white LED by color mixing, and the combined ultraviolet LED, red luminescent phosphor, green luminescent phosphor, and blue luminescent phosphor are white by color mixing. Light white LEDs, etc.

In the color liquid crystal display device including the colored cured film of the present invention, TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and IPS (In-Planes Switching) can be used. A suitable liquid crystal mode such as a VA (Vertical Alignment) type or an OCB (Optically Compensated Birefringence) type.

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

In addition, the electronic paper provided with the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be cited.

Example

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following examples.

<Synthesis of Colorants> Synthesis Example 1 (Synthesis of Polymer (1))

5.46 g of p-(vinylphenyl)trifluoromethanesulfinamide triethylamine salt, 4.51 g of methyl methacrylate, and 0.130 g of α-thioglycerol were added to the reaction vessel equipped with the condenser tube, and They are soluble in 20 g of cyclohexanone. The solution was heated to 100 ° C while stirring under a nitrogen stream. A solution obtained by dissolving 98.0 mg of α,α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise thereto under stirring at the same temperature for 30 minutes, and further stirred at the same temperature for 3 hours while the dropwise addition was completed. Thereafter, after cooling the reaction solution to room temperature, 60 g of acetone was added to prepare a homogeneous solution, which was added dropwise to 1.1 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C to obtain 8.14 g of a polymer represented by the following structural formula. The obtained polymer had a Mw of 7800 and an Mn of 3600. It was confirmed by ¹ H-NMR analysis that the ratio of p to r was 1/2.2 in terms of a molar ratio (p/r). This was taken as the polymer (1).

(Synthesis of Polymer A)

2.0 g of the above polymer (1) was dissolved in 40 mL of acetone. Next, as shown in the following flow chart, the molar ratio of the structural unit derived from the (triphenylphenyl)trifluoromethanesulfonate triethylamine salt was calculated from the copolymerization ratio of the polymer (1). The molar amount of the compound (1) was added to the molar amount of the compound (1), and the mixture was stirred at room temperature for 1 hour. Thereafter, the resulting residue was concentrated by adding 200 mL of ion-exchanged water to the residue obtained by concentrating the reaction solution under reduced pressure, and the resulting precipitate was washed with water. The obtained solid was dried under reduced pressure at 50 ° C to obtain 2.54 g of the polymer A represented by the following structural formula. Polymer A corresponds to the present colorant.

Synthesis Example 2 (Synthesis of polymer (2))

In the synthesis of the polymer (1), a p-styrenesulfonic acid tetraethylammonium salt is used in place of the p-(vinylphenyl)trifluoromethanesulfonimide triethylamine salt, in addition to the synthesis example. 1 In the same manner, 8.29 g of the polymer (2) represented by the following structural formula was obtained. The obtained polymer (2) had an Mw of 8,800 and an Mn of 4,300. It was confirmed by ¹ H-NMR analysis that the ratio of p to r was 1/2.8 in terms of a molar ratio (p/r).

(Synthesis of Polymer B)

In the synthesis of the polymer A, 2.50 g of the polymerization represented by the following structural formula was obtained in the same manner as in the synthesis example 1 except that the polymer (2) was used instead of the polymer (1). Matter B. Polymer B is not the present colorant.

Synthesis Example 3 (Synthesis of Polymer (3))

To a reaction vessel equipped with a condenser, 4.55 g of p-(vinylphenyl) n-nonafluorobutanesulfatide triethylamine salt, 5.41 g of methyl methacrylate, 0.130 g of α-thioglycerol, and They were dissolved in 20 g of cyclohexanone. The solution was heated to 100 ° C while stirring under a nitrogen stream. A solution obtained by dissolving 98.0 mg of α,α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise thereto under stirring at the same temperature for 30 minutes, and further stirred at the same temperature for 3 hours while the dropwise addition was completed. Thereafter, after cooling the reaction solution to room temperature, 60 g of acetone was added to prepare a homogeneous solution, which was added dropwise to 1.1 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C to obtain 8.02 g of a polymer represented by the following structural formula. The obtained polymer had Mw of 7,500 and Mn of 3,300, and it was confirmed by ¹ H-NMR analysis that the ratio of p to r was 1/2.6 in terms of molar ratio (p/r). This was taken as the polymer (3).

(Synthesis of Polymer C)

In the synthesis of the polymer A, 2.43 g of the polymerization represented by the following structural formula was obtained in the same manner as in the synthesis example 1 except that the polymer (3) was used instead of the polymer (1). Object C. Polymer C corresponds to the present colorant.

Synthesis Example 4 (Synthesis of polymer (4))

To the reaction vessel equipped with the condenser, 6.11 g of the compound (2) shown below, 3.85 g of methyl methacrylate, 0.130 g of α-thioglycerol, and 20 g of cyclohexanone were dissolved. The solution was heated to 100 ° C while stirring under a nitrogen stream. A solution obtained by dissolving 98.0 mg of α,α'-azobisisobutyronitrile in 10.4 g of cyclohexanone was added dropwise thereto under stirring at the same temperature for 30 minutes, and further stirred at the same temperature for 3 hours while the dropwise addition was completed. Thereafter, after cooling the reaction solution to room temperature, 60 g of acetone was added to prepare a homogeneous solution, which was added dropwise to 1.1 L of hexane. The resulting precipitate was collected by filtration and washed with hexane. The obtained solid was dried under reduced pressure at 50 ° C to obtain 8.25 g of a polymer represented by the following structural formula. The obtained polymer had Mw of 8,000 and Mn of 4100. It was confirmed by ¹ H-NMR analysis that the ratio of p to r was 1/1.9 in terms of molar ratio (p/r). This was taken as the polymer (4).

(Synthesis of Polymer D)

In the synthesis of the polymer A, 2.65 g of the following structure was obtained in the same manner as in the synthesis example 1 except that the polymer (4) compound (1) was used instead of the polymer (1). Polymer D represented by the formula. Polymer D corresponds to the present colorant.

Synthesis Example 5~15 (Synthesis of polymer E~O)

In the synthesis of the polymer A, the polymer E to O was obtained in the same manner as in the synthesis example 1 except that the reaction was carried out in the combination of the materials shown in Table 1. The polymers E to O are equivalent to the present colorant.

Further, the structure of the compound given the C.I. number used as a raw material is as follows.

Synthesis Example 16

To a 100 mL Erlenmeyer flask equipped with a stirrer, 5.21 g of the compound (1) represented by the following formula and 4.31 g of bis(trifluoromethanesulfonate) were added. Lithium hydrazide was added with 50 mL of chloroform and 25 mL of ion-exchanged water at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and the organic layer was washed twice with ion-exchanged water. After concentrating the organic layer under reduced pressure, the residue was dried under reduced pressure at 50 ° C for 12 hours to give 7.42 g of the compound of the formula. The obtained compound was designated as Dye A. Dye A is not the present colorant.

Preparation Examples 1 to 16

The polymer A~O, dye A and propylene glycol monomethyl ether acetate obtained by mixing according to Table 2 were prepared to prepare a polymer solution or a dye solution. In Table 2, propylene glycol monomethyl ether acetate is abbreviated as PGMEA.

Preparation Example 17

As a coloring agent, 15 parts by mass of CI Pigment Green 58 was used, and as a dispersing agent, 12.5 parts by mass (solid content concentration: 40% by mass) BYK-LPN 21116 (BYK-Chemie (BYK)) was used as a solvent, and 72.5 mass was used. The propylene glycol monomethyl ether acetate was treated with a bead mill to prepare a pigment dispersion liquid (a-1).

Preparation Example 18

15 parts by mass of CI Pigment Yellow 138 was used as a coloring agent, and 12.5 parts by mass (solid content concentration: 40% by mass) BYK-LPN21116 (BYK-Chemie (BYK)) was used as a dispersing agent, and 72.5 parts by mass was used as a solvent. Propylene glycol monomethyl ether acetate was treated with a bead mill to prepare a pigment dispersion (a-2).

<Synthesis of binder resin> Synthesis Example 17

Into a flask equipped with a condenser and a stirrer, 100 parts by mass of propylene glycol monomethyl ether acetate was charged and replaced with nitrogen. The mixture was heated to 80 ° C, and the following mixed solution was added dropwise at the same temperature for 1 hour. The mixed solution was 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 5 parts by mass. Benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of succinic acid A mixed solution of (2-propenyloxyethyl)ester and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was carried out for 1 hour, thereby obtaining a binder resin solution (solid content concentration 33 mass) %). The obtained binder resin had an Mw of 12,200 and an Mn of 6,500. This binder resin is referred to as "adhesive resin (B1)".

[Preparation of colored composition for evaluation of transferability] Preparation Example 19

30.5 parts by mass of the pigment dispersion liquid (a-1) as the coloring agent (A) and 25.0 parts by mass of the pigment dispersion liquid (a-2), and 26.3 parts by mass of the binder resin (B1) solution as the (B) binder resin 9.9 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as (C) polymerizable compound, as photopolymerization 2-benzyl-2-dimethylamino-1-(4- 1.8 parts by mass of NPI-930 (manufactured by Adeka Co., Ltd.), and 0.1 parts by mass of NCI-930 (manufactured by Ciba Specialty Chemicals Co., Ltd.), MEGAFAC F- as a fluorine-based surfactant 554 (manufactured by DIC Corporation) 0.05 parts by mass and propylene glycol monomethyl ether acetate as a solvent, and a green colored composition (G) having a solid content concentration of 20% by mass was prepared.

<Preparation and evaluation of coloring composition> Example 1

7.2 parts by mass of the polymer solution (A-1) as the coloring agent (A), 9.9 parts by mass of the binder resin (B1) solution as the (B) binder resin, and di-new pentane as the (C) polymerizable compound Mixture of tetraol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) 15.4 parts by mass, 2-benzyl-2-dimethyl group as photopolymerization initiator Amino-1-(4- 1.8 parts by mass of NPI-930 (manufactured by Adeka Co., Ltd.), 0.1 parts by mass of NPI-A-butane-1-one (trade name: IRGACURE 369, manufactured by Ciba Specialty Chemicals Co., Ltd.), and MEGAFAC F- as a fluorine-based surfactant 554 (manufactured by DIC Corporation) 0.05 parts by mass, and propylene glycol monomethyl ether acetate as a solvent, a coloring composition (S-1) having a solid content concentration of 20% by mass was prepared.

[Evaluation of heat resistance]

The colored composition (S-1) was applied onto a soda glass substrate having a SiO ₂ film on which a sodium ion eluted on the surface was formed by a spin coater, and then prebaked for 2 minutes using a hot plate at 90 ° C to form a film thickness of 2.5 μ. The coating film of m.

Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each of the coating films through a photomask using a high pressure mercury lamp at an exposure amount of 400 J/m ² . Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a clean oven at 200 ° C for 30 minutes to form a dot pattern on the substrate.

Using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system were measured for the obtained dot pattern under a C light source and a 2 degree field of view. .

Next, the substrate was baked at 230 ° C for 90 minutes, and then the chromaticity coordinate value (x, y) and the stimulating value (Y) were measured, and the chromaticity change before and after the additional baking, that is, ΔE ^* ab was evaluated. As a result, the case where the value of ΔE ^* ab was less than 2.0 was evaluated as "◎", the case of 2.0 or more and less than 4.0 was evaluated as "○", and the case of 4.0 or more and less than 6.0 was evaluated as "△", and 6.0 was obtained. The above situation was evaluated as "X". The evaluation results are shown in Table 3. Further, the smaller the ΔE ^* ab value, the better the heat resistance.

[Evaluation of solvent resistance]

The coloring composition (S-1) was applied onto a SiO ₂ film soda glass substrate having a surface on which a sodium ion was prevented from eluting using a spin coater, and then prebaked for 2 minutes using a hot plate at 90 ° C to form a film thickness of 2.5 μm. Coating film.

Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each of the coating films through a photomask using a high pressure mercury lamp at an exposure amount of 400 J/m ² . Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a cleaning oven at 230 ° C for 30 minutes to form a dot pattern on the substrate. Using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system were measured for the obtained dot pattern under a C light source and a 2 degree field of view. .

Thereafter, the substrate was immersed in propylene glycol monomethyl ether acetate at 80 ° C for 40 minutes. The chromaticity coordinate value (x, y) and the stimulating value (Y) were measured for the dot pattern after immersion, and the chromaticity change before and after immersion, that is, ΔE ^* ab was evaluated. As a result, the case where the value of ΔE ^* ab was less than 3.0 was evaluated as "○", the case of 3.0 or more and less than 5.0 was evaluated as "Δ", and the case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. Further, the smaller the ΔE ^* ab value, the better the solvent resistance.

[Evaluation of transferability]

The green colored composition (G) was applied onto a soda glass substrate having a SiO ₂ film on the surface where sodium ions were prevented from eluting using a spin coater, and then prebaked for 2 minutes using a hot plate at 90 ° C to form a film thickness of 2.4 μm. Coating film.

Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each coating film at a exposure amount of 400 J/m ² using a high pressure mercury lamp. Thereafter, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development for 90 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and further baked in a cleaning oven at 230 ° C for 30 minutes to form a green cured film (T-1) on the substrate. Using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) in the CIE color system was measured on the obtained green cured film (T-1) under a C light source and a 2 degree field of view. And the stimulus value (Y).

Next, the colored composition (S-1) was applied onto the green cured film (T-1) by a spin coater, and then prebaked in a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 2.5 μm. After the substrate was cooled to room temperature, a developing solution composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing a 90 second spray. Drip development. Thereafter, the substrate was washed with ultrapure water and air-dried. The step of applying the coloring composition (S-1) to the air drying series is referred to as "(step-1)". The chromaticity coordinate value (x, y) and the stimulation value (Y) of the green cured film (T-1) after (Step-1) were measured, and the change in the stimulation value before and after (Step-1), that is, ΔY was evaluated. As a result, the case where the value of ΔY is less than 0.2 is evaluated as “○”, the case where 0.2 or more and less than 0.7 is evaluated as “Δ”, and the case where 0.7 or more is evaluated as “×”. The evaluation results are shown in Table 3. Further, the smaller the ΔY value, the more the transferability is suppressed.

Examples 2 to 14 and Comparative Examples 1 to 2

In the same manner as in Example 1, except that the type and amount of the colorant and the binder resin solution were changed as shown in Table 1, the colored composition (S-2) to (S-16) was prepared. ). Then, the obtained coloring composition was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Claims (6)

A coloring composition comprising (A) a coloring agent and (C) a coloring composition of a polymerizable compound, wherein the coloring agent contains a polymer having a structural unit represented by the following formula (1), In the formula (1), R ⁰ represents a hydrogen atom or a methyl group, and X represents a halogen group, a halogenated hydrocarbon group, or a linking group having an atom other than a carbon atom, a hydrogen atom or a halogen atom between CC bonds of a halogenated hydrocarbon group. The group of Y represents a single bond or a divalent organic group, and Z ⁺ represents a triarylmethane-based cationic chromophore represented by the following formula (2-1), and the following formula (2-2) a triarylmethane-based cationic chromophore, a methine-based cationic chromophore, an azo-based cationic chromophore, a diarylmethane-based cationic chromophore, and a quinone imine Cationic chromophore, lanthanide cationic chromophore, cation chromophore of phthalocyanine At least one cationic chromophore of the cationic chromophore, In the formula (2-1), R ¹ to R ⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkane having 3 to 8 carbon atoms. a group or a substituted or unsubstituted aryl group, R ⁷ to R ⁹ independently of each other represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and l and m each independently represent an integer of 0 to 4, and n represents 0 to 0. An integer of 6, where l, m, and n are not 0 at the same time, In the formula (2-2), R ¹¹ to R ¹⁶ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkane having 3 to 8 carbon atoms. The group or the substituted or unsubstituted aryl group, R ¹⁷ to R ¹⁹ independently of each other represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom, and s, t and u each independently represent an integer of 0 to 4. The colored composition of claim 1, wherein the Y-based divalent hydrocarbon group, the combination of a divalent hydrocarbon group and a linking group containing a carbon atom and an atom other than a hydrogen atom, or a hydrogen atom of the group A part of a divalent group substituted by a halogen atom. The coloring composition of claim 1 or 2, wherein the Z ⁺ is selected from the group consisting of a cationic chromophore of the triarylmethane group represented by the formula (2-1) and a cation of a triarylmethane group represented by the formula (2-2) Sexual chromophores, methacrylic cationic chromophores, and At least one cationic chromophore of the cationic chromophore. The colored composition of claim 1 or 2 further comprising (B) a binder resin. A colored hardening film formed using the colored composition of any one of claims 1 to 4. A display element comprising the colored cured film of claim 5.