JP2014063158A - Coloring composition and color filter using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter coloring composition capable of forming a highly bright, heat resistant, and chemical resistant film or micropattern.SOLUTION: A color filter coloring composition contains β-hydroxyalkylamide (A), carboxyl group-containing polymer (B), and a colorant containing a dye (C), where the dye (C) is a salt-forming compound (C1) comprising a triarylmethane-based basic dye and a counter compound having a molecular weight of 200 to 3500.

Description

  The present invention relates to a coloring composition for a color filter, which can obtain a film or a fine pattern excellent in heat resistance and solvent resistance by performing exposure and heat treatment. The color composition for color filter of the present invention is a color filter used for color liquid crystal display devices, color image pickup tube elements, etc., black matrix, color filter protective film, photo spacer, protrusion for liquid crystal alignment, micro lens, insulating film for touch panel It can be used for adhesives for electronic materials, adhesive sheets and the like around flexible printed wiring boards.

  The color filter is provided with a grid-like light-shielding film black matrix (hereinafter referred to as BM) for the purpose of preventing color mixture of transmitted light and increasing display contrast on a transparent substrate such as a glass plate, and then a plurality of colors (usually red, Green and blue) filter segments are provided. The filter segments are as fine as several microns to several hundreds of microns, and the filter segments are arranged in the form of fine bands (stripes) of two or more different hues (stripe arrangement), or are arranged vertically and horizontally. (Delta arrangement) etc.

  In a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is formed thereon. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

The quality required for a color liquid crystal display device includes high image quality, low power consumption, and the like, and color filters with high brightness, high contrast, and high resolution are required to achieve them.
In particular, in recent years, from the viewpoint of power consumption, the brightness of color filters has been increasing. When a color filter with high brightness is used, the light transmittance is high, so that the number of backlights that are light sources can be reduced and power consumption can be reduced.

  Conventional color filters have been able to achieve high brightness and a wide color display area by combining a blue filter segment with a copper phthalocyanine pigment and a dioxazine pigment. However, as described above, higher brightness is required for the color filter.

  On the other hand, a technique for dissolving a dye, not a pigment, in a resin or the like as a colorant has been proposed (see, for example, Patent Document 1). In addition, an ink for a color filter containing a phthalocyanine dye and a xanthene dye has been studied. In particular, it was a combination of a direct dye and an acid dye, but although the color developability was good, it was inferior in heat resistance and light resistance and was not satisfactory. (For example, see Patent Document 2)

  Furthermore, in order to improve heat resistance, light resistance, and solvent resistance, use a salt of triarylmethane basic dye and aromatic sulfonic acid or triarylmethane basic dye as a color filter colorant. Has also been proposed (see, for example, Patent Document 3). However, a salt-forming compound of a triarylmethane-based basic dye and an aromatic monosulfonic acid has a drawback that its durability is poor because its molecular weight is small.

JP-A-6-75375 JP-A-8-327811 JP-A-20-304766

  The present invention has been made in view of the above situation, and provides a coloring composition for a color filter that can form a film or a fine pattern that has high brightness and satisfies heat resistance and chemical resistance. This is the issue.

  In order to solve the above-mentioned problems, the present inventors have intensively studied to give high brightness, heat resistance and chemical resistance by using β-hydroxyalkylamide having a specific structure and a dye. It discovered that the coloring composition for filters solved the said subject, and came to complete this invention.

  That is, this invention is a coloring composition for color filters containing (beta) -hydroxyalkylamide (A), the polymer (B) containing a carboxyl group, and the coloring agent containing dye (C), The dye composition (C) is a salt-forming compound [C1] comprising a triarylmethane basic dye and a counter compound having a molecular weight in the range of 200 to 3,500. ,

  In addition, the present invention relates to the colored composition for a color filter, wherein at least one of β-hydroxyalkylamide (A) or a polymer (B) containing a carboxyl group contains a photopolymerizable functional group. .

  Moreover, this invention relates to the said coloring composition for color filters which contains a photopolymerizable monomer (D) and / or a photoinitiator (E) further.

  The present invention also relates to the color filter coloring composition, wherein the β-hydroxyalkylamide (A) is a compound represented by the following general formula (1).

［［式中、Ｘは炭素、水素、酸素、窒素、硫黄、又はハロゲンからなるｎ価の基であり、ｎは２〜６の整数であり、Ｒ¹およびＲ²は、それぞれ独立に、水素原子、脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、一般式（２）で表される基、または一般式（３）で表される基を表し、１以上の窒素原子に結合する１以上のＲ¹およびＲ²のうち、少なくとも１つは一般式（２）で表される基である。］ General formula (1)

[Wherein X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, n is an integer of 2 to 6, and R ¹ and R ² are each independently hydrogen Represents an atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or a group represented by the general formula (3), and one or more nitrogen At least one of the one or more R ¹ and R ² bonded to the atom is a group represented by the general formula (2). ]

General formula (2)

［式中、Ｒ³〜Ｒ⁶はそれぞれ独立に水素原子、炭化水素基、またはヒドロキシル基で置換された炭化水素基を表し、Ｒ⁷はヒドロキシル基と反応しうる官能基を有する化合物の残基を表す。］］ General formula (3)

[Wherein R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group, and R ⁷ is a residue of a compound having a functional group capable of reacting with a hydroxyl group. Represents. ]]

  In the present invention, in the compound having a functional group capable of reacting with the hydroxyl group, the functional group capable of reacting with the hydroxyl group is a carboxyl group, an isocyanate group, a carboxylic acid anhydride group, an acid halide group, or a carboxylic acid. The present invention relates to the coloring composition for a color filter, which is at least one selected from the group consisting of a tertiary alkyl ester group, a hydroxymethylamino group, an alkoxysilyl group and an epoxy group.

  In addition, the present invention relates to the coloring composition for a color filter, wherein the compound having a functional group capable of reacting with a hydroxyl group is a monofunctional isocyanate or a monofunctional carboxylic acid.

  In the present invention, the compound having a functional group capable of reacting with the hydroxyl group is represented by at least one selected from the group consisting of the following general formula (4), general formula (5) and general formula (6). It is related with the said coloring composition for color filters characterized by the above-mentioned.

［式中、Ｒ⁸は炭素数２〜１８の直鎖状、環状または分岐状の飽和または不飽和炭化水素基である。］ General formula (4)

[Wherein, R ⁸ represents a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]

［式中、Ｒ⁹は水素原子またはメチル基であり、Ｒ¹⁰は炭素数２〜８の直鎖状もしくは分岐状のアルキレン基、２価の脂環族炭化水素基、または２価の芳香族炭化水素基であり、Ｒ¹¹は炭素数２〜８の直鎖状もしくは分岐状のアルキレン基、２価の脂環族炭化水素基、または２価の芳香族炭化水素基である。］ General formula (5)

[Wherein R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic group. A hydrocarbon group, and R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. ]

［［式中、Ｒ¹²は水素原子またはメチル基であり、Ｒ¹³は一般式（７）で表される基、または一般式（８）で表される基である。］ General formula (6)

[In the formula, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a group represented by the general formula (7) or a group represented by the general formula (8). ]

［式中、ｎ¹は１〜２の整数である。］ General formula (7)

Wherein, n ¹ is an integer of 1-2. ]

［式中、Ｒ¹⁴は炭素数２〜８の直鎖状もしくは分岐状のアルキレン基、２価の脂環族炭化水素基、または２価の芳香族炭化水素基であり、Ｒ¹⁵は炭素数６〜１３の直鎖状もしくは分岐状のアルキレン基、２価の脂環族炭化水素基、または２価の芳香族炭化水素基である。］］ General formula (8)

[Wherein R ¹⁴ represents a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group, and R ¹⁵ represents the number of carbon atoms. 6-13 linear or branched alkylene groups, divalent alicyclic hydrocarbon groups, or divalent aromatic hydrocarbon groups. ]]

  In addition, the present invention relates to the colored composition for a color filter, wherein the compound having a functional group capable of reacting with a hydroxyl group has a photopolymerizable functional group.

  The present invention also provides that the β-hydroxyalkylamide (A) is (a-1) a divalent or higher carboxylic acid or derivative thereof, and (a-2) a primary or at least one hydroxyl group at the β-position. A part of the hydroxyl group of (a-3) β-hydroxyalkylamide obtained by amidation with a secondary amine is reacted with (a-4) a compound having one or more functional groups capable of reacting with the hydroxyl group. It is related with the said coloring composition for color filters characterized by the above-mentioned.

  Furthermore, the present invention relates to a color filter comprising a filter segment or a black matrix formed from the colored composition on a transparent substrate.

  The coloring composition of the present invention can provide a color filter having high brightness and high heat resistance and chemical resistance by containing a polymer containing a β-hydroxyalkylamide and a carboxyl group and a dye. I can do it.

  The present invention is described in detail below.

<Combination of elements constituting the color filter coloring composition>
First, the combination of the elements constituting the color filter coloring composition of the present invention will be described.
The characteristics of the coloring composition for a color filter of the present invention are:
1. 1. A fine pattern can be formed by having a color filter coloring composition having alkali developability due to a carboxyl group. Homogeneous cross-linking structure is achieved by heat curing in which a β-hydroxyalkylamide group and a carboxyl group undergo a condensation reaction and photocuring in which a photopolymerizable functional group is polymerized by a photopolymerization initiator in a uniform composition. Is formed, and a film and a pattern excellent in heat resistance and chemical resistance are formed.
In addition, the coloring composition for color filters of this invention can also be used for forming a fine pattern by solvent image development, or forming as a film | membrane or a molding without developing. In that case, the carboxyl group is utilized for the cross-linking of Feature 2.

  In order to embody it, the coloring composition for a color filter of the present invention contains β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, and a dye (C) as essential components. And a photopolymerizable monomer (D) and / or a photoinitiator (E) are contained as a component as needed.

  Furthermore, in order to impart photosensitivity, at least one of these components must contain a photopolymerizable functional group. When (beta) -hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group contain both photopolymerizable functional groups, when any one is included, all the cases where neither is included belong to this invention. . Only when the β-hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group do not contain any photopolymerizable functional group, the photopolymerizable monomer (D) is further added as an essential component. To do.

  That is, the constituents of the coloring composition for photosensitive color filter of the present invention include the following combinations (1) to (7).

(1) β-hydroxyalkylamide (A) containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
Dye (C)
(2) β-hydroxyalkylamide (A) containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
A dye (C);
Photopolymerizable monomer (D)
(3) β-hydroxyalkylamide (A) containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group;
Dye (C)
(4) β-hydroxyalkylamide (A) containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group;
A dye (C);
Photopolymerizable monomer (D)
(5) β-hydroxyalkylamide (A) not containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
Dye (C)
(6) β-hydroxyalkylamide (A) not containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group containing a photopolymerizable functional group;
A photopolymerization initiator (C);
Photopolymerizable monomer (D)
(7) β-hydroxyalkylamide (A) not containing a photopolymerizable functional group;
A polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group;
A photopolymerization initiator (C);
Photopolymerizable monomer (D)

<Β-Hydroxyalkylamide (A)>
The structure of the β-hydroxyalkylamide (A) used in the present invention is not particularly limited as long as it is soluble in an organic solvent. For example, polymer derivatives obtained by polymerizing β-hydroxyethylacrylamide, tris (2-hydroxyethyl) isocyanurate derivatives, and the like can be mentioned. Preferably, it is a compound represented by general formula (1).

式中、Ｘは炭素、水素、酸素、窒素、硫黄、又はハロゲンからなるｎ価の基であり、ｎは２〜６の整数である。Ｘとして、具体的には、炭素数２以上のｎ価の脂肪族炭化水素基、脂環式炭化水素基、芳香族炭化水素基、及びヘテロ原子を有する基が挙げられる。 General formula (1)

In the formula, X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, and n is an integer of 2-6. Specific examples of X include an n-valent aliphatic hydrocarbon group having 2 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group having a hetero atom.

  Examples of the halogen include fluorine, chlorine, bromine and iodine, and fluorine is preferable from the viewpoint of transparency. From the viewpoint of imparting flame retardancy, chlorine and bromine are preferred.

  An n-valent group is a group obtained by removing n hydrogen atoms from a compound. Hereinafter, this is referred to as an n-valent group derived from the compound.

  Examples of the n-valent aliphatic hydrocarbon group include n-valent groups derived from alkanes, alkenes, and alkynes.

  Examples of alkanes include ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentaden, heptadecane, hexadecane, octadecane, nonadecane, icosane, heicosan, docosan, isobutane, isopentane, Neopentane, methylpentane, dimethylpentane, ethylmethylpentane, diethylpentane, methylhexane, tetramethylheptane, and the like. As the n-valent group derived from alkane, for example, 1,6-hexyl group, 1,7-heptyl group, 1,8-octyl group, 1,9-nonyl group, 1,10-decyl group, 1,11 -Undecyl group, 1,12-dodecyl group, 1,13-tridecyl group, 1,14-tetradecyl group, 1,15-pentadecyl group, 1,16-hexadecyl group, 1,17-heptadecyl group, 1,18- Octadecyl group, 1,19-nonadecyl group, 1,3,6-hexyl group, 1,4,7-heptyl group, 1,2,8-octyl group, 1,3,9-nonyl group, 1,3, Examples include 4,6-hexyl group, 1,4,6,7-heptyl group, 1,4,5,6,7-heptyl group and 1,2,3,4,5,6-hexyl group.

  Alkenes include ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, docene, tridecene, tetracene, pentadecene, heptadecene, hexadecene, octadecene, nonadecene, icosene, heicocene, dococene, methylpentene, etc. Is mentioned. Examples of the n-valent group derived from an alkene include a 1,6- (2-hexenyl) group, a 1,7- (2-heptenyl) group, a 1,8- (2-octenyl) group, and a 1,9- (2-nonenyl) group, 1,10- (2-decenyl) group, 1,11- (2-undecenyl) group, 1,12- (2-dodecenyl) group, 1,13- (2-tridecenyl) group 1,14- (2-tetradecenyl) group, 1,15- (2-pentadecenyl) group, 1,16- (2-hexadecenyl) group, 1,17- (2-heptadecenyl) group, 1,18- ( 2-octadecenyl) group, 1,19- (2-nonadecenyl) group, 1,3,6- (2-hexenyl) group, 1,4,7- (3-heptenyl) group, 1,2,8- ( 4-octenyl) group, 1,3,9- (5-nonenyl) group, 1,3,4,6- (2-hex) ) Group, 1,4,6,7- (3-Hepuseniru) group, 1,4,5,6,7- (3- Hepuseniru) group.

  Examples of alkynes include ethyne, propyne, butyne, pentyne, hexyne, peptin, octyne, nonin, decyne, undecine, dodecin, tridecine, icosin, heicosin, docosin, and the like. Examples of the n-valent group derived from alkyne include 1,6- (2-hexynyl) group, 1,7- (2-hepsinyl) group, 1,8- (2-oxynyl) group, 1,9- (2-nonyl) group, 1,10- (2-decynyl) group, 1,11- (2-undecynyl) group, 1,12- (2-dodecynyl) group, 1,13- (2-tridecynyl) group 1,14- (2-tetradecynyl) group, 1,15- (2-pentadecynyl) group, 1,16- (2-hexadecynyl) group, 1,17- (2-heptadecynyl) group, 1,18- ( 2-octadecynyl) group, 1,19- (2-nonadecynyl) group, 1,3,6- (2-hexynyl) group, 1,4,7- (3-hepsinyl) group, 1,2,8- ( 4-octynyl) group, 1,3,9- (5-nonyl) group, 1,3,4,6- (2-hexini) ) Group, 1,4,6,7- (3-Hepushiniru) group, and 1,4,5,6,7- (3- Hepushiniru) group.

  Examples of the n-valent alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclohexene, methylcyclohexene, norbornane, norbornene, and bicyclo And n-valent groups derived from octene, decahydronaphthalene, adamantane, dimethyladamantane, and the like. For example, 1,1-cyclohexyl group, 1,2-cyclohexyl group, 1,3-cyclohexyl group, 1,4-cyclohexyl group, 1,2,4-cyclohexyl group, 1,3,5-cyclohexyl group, 1, Examples include 2,4,5-cyclohexyl group, 1,2,3,4,5,6-cyclohexyl group, 2,6-decahydronaphthyl group, 1,3-adamantyl group, 1,3,5-adamantyl group. .

  Examples of n-valent aromatic hydrocarbon groups include n-valent aromatic hydrocarbon groups derived from benzene, naphthalene, biphenyl, anthracene, toluene, xylene, ethylbenzene, tert-butylbenzene, diphenylethane, diphenylacetylene, 9,9-diphenylfluorene, and the like. Groups. For example, examples of the group in which an aromatic ring contains a carbon atom bonded to a carbonyl group include a phenylene group and a tolylene group. Examples of the group in which the carbon atom bonded to the carbonyl group is not contained in the aromatic ring include toluene-α, α-diyl group, ethylbenzene-α, β-diyl group, ethylbenzene-β, β-diyl group, 1,2-diphenyl. And ethane-1,2-diyl group.

  N-valent groups having heteroatoms (oxygen, sulfur, nitrogen, halogen atoms) include ethanol, ethylene glycol, ethylene diacetate, ethylene dipivalate, ethylene dibenzoate, ethylene bis (methyl benzoate), ethylene bis (methoxy Benzoate), propanol, isopropanol, ethyl acetate, erythritol, ethylene oxide, acetaldehyde, acetone, dipropyl ketone, γ-pentadecanolactone, 1,2-cyclohexane, γ-butyrolactone, ethylamine, ethylmethylamine, propylamine, N- Propylacetamide, ethanethiol, ethanedithiol, tetrafluoroethane, dibromoethane, hexafluoropropane, octofluorobutane, dodecafluorohexane, hexadecaf Fluorooctane, 1,2,3,4,7,7-hexachloronorbornene, anisole, fluorobenzene, tetrafluorobenzene, trifluoromethylbenzene, chlorobenzene, dichlorobenzene, tetrafluorobenzene, bromobenzene, tetrabromobenzene, nitrobenzene, phenol Aniline, benzenesulfonic acid, anthraquinone, butanephosphonic acid, triethyltriazine, tripropyltriazine, triethylisocyanurate, tripropylisocyanurate, benzophenone, thiophene, diethylsulfide, diphenylsulfone, 2,2-diphenyl-1,1,1 , 3,3,3-hexafluoropropane, diphenyl ether, and the like.

  Among these, as X, from the viewpoint of reactivity, it is preferable that the atom in X that is directly bonded to the carbonyl group is a carbon atom that is not included in the aromatic ring. Further, a linear aliphatic hydrocarbon group having 6 to 18 carbon atoms or an alicyclic hydrocarbon group is preferable, and more preferably a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms, or It is an alicyclic hydrocarbon group, More preferably, it is a C6-C12 linear aliphatic hydrocarbon group.

In the formula, R ¹ and R ² are each independently a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrogen group, an aromatic hydrocarbon group, a group represented by the general formula (2), or a general formula Representing the group represented by (3), at least one of one or more R ¹ and R ² bonded to one or more nitrogen atoms is a group represented by the general formula (2).

General formula (2)

General formula (3)

  Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

  As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group , Dodecyl group, pentadecyl group, and octadecyl group.

  Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group and 1-octadecenyl group. Groups.

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. .

  The alicyclic hydrocarbon group includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-indeno group, decahydronaphthyl group, adamantyl group, dicyclopenta And a cycloalkyl group such as a nyl group.

Examples of the aromatic hydrocarbon group include a single ring, a condensed ring, and a ring assembly aromatic hydrocarbon group. The monocyclic aromatic hydrocarbon group includes monocyclic aromatic groups such as phenyl group, benzyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group and mesityl group. Group hydrocarbon group.
As the condensed ring aromatic hydrocarbon group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, Examples thereof include condensed ring aromatic hydrocarbon groups such as 2-azurenyl group, 1-pyrenyl group and 2-triphenylyl group.
Examples of the ring-assembled aromatic hydrocarbon group include ring-assembled aromatic hydrocarbon groups such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group.

Among them, R ¹ and R ² other than the general formula (2) and the general formula (3) are preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon, or a monocyclic aromatic hydrocarbon group, and more An aliphatic hydrocarbon group and an alicyclic hydrocarbon are preferable, and an aliphatic hydrocarbon group having 4 or more carbon atoms is more preferable.

R ^{3 to} R ^{6 in the} groups represented by the general formulas (2) and (3) each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group partially substituted with a hydroxyl group, and R ⁷ represents a hydroxyl group Represents a residue of the compound (a3) having a functional group capable of reacting with the group.

The hydrocarbon groups are the same as those described above for R ¹ and R ² . Examples of the hydrocarbon group substituted with a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxyphenyl group, a hydroxycyclohexyl group, and the like.

  The residue of the compound (a3) having a functional group capable of reacting with a hydroxyl group is not particularly limited, but isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol An ester, an amino resin, a compound having an epoxy, and the like can be mentioned, and isocyanate, carboxylic acid, carboxylic acid halide, and carboxylic anhydride are preferable, and monofunctional isocyanate or monofunctional carboxylic acid is more preferable.

Among these, from the viewpoint of easy production, it is more preferable to obtain β-hydroxyalkylamide (A) in which R ⁷ in the general formula (3) is represented by the following general formula (9).

General formula (9)

here,
R ¹⁶ is a single bond, a (m 1 + 1) -valent hydrocarbon group, or a urethane bond, a urea bond, an allophanate bond, a biuret bond, or an isocyanurate ring, and a carbon atom or a hydrogen atom (m 1 + 1). Valent group,
A ¹ represents a single bond, a urethane bond or a urea bond,
R ¹⁷ represents a divalent hydrocarbon group,
A ² represents an ether bond or an ester bond,
R ¹⁸ represents a monovalent hydrocarbon group,
m ¹ represents an integer of ¹ to 5,
p ¹ represents an integer of 0 to 100.

Further, from the viewpoint of easy production, it is more preferable to obtain β-hydroxyalkylamide (A) in which R ⁷ in the general formula (3) is represented by the following general formula (10).

General formula (10)

here,
R ¹⁹ represents a single bond, a (m 2 + 1) -valent hydrocarbon group, or a (m 2 + 1) -valent group consisting of a carbon atom, a hydrogen atom, or an oxygen atom,
A ³ represents a single bond, an ester bond or an amide bond,
R ²⁰ represents a divalent hydrocarbon group,
A ⁴ represents an ether bond or an ester bond,
R ²¹ represents a monovalent hydrocarbon group,
m ² represents an integer of 1 to 5,
p ² is an integer of 0 to 100.

(Method for producing β-hydroxyalkylamide (A))
Although the compound represented by the general formula (1) can be produced by various methods, main production methods [1] to [4] are listed below.

(1) When at least one of R ¹ and R ² is a group represented by the general formula (3):

[1] β-hydroxyalkylamide (A1) obtained by amidating a carboxylic acid having a valence of 2 or more or a derivative thereof (a1) and a primary or secondary amine (a2) having one or more hydroxyl groups at the β-position ) Is reacted with a compound (a3) having one or more functional groups capable of reacting with the hydroxyl group.

[2] Reacting a compound (a3) having one or more functional groups capable of reacting with a hydroxyl group on a part of the hydroxyl group of a primary or secondary amine (a2) having one or more hydroxyl groups at the β-position Then, it is amidated with a divalent or higher carboxylic acid or derivative thereof (a1).

[3] A compound (a3) having at least one functional group capable of reacting with a hydroxyl group is reacted by protecting the amino group of a primary or secondary amine (a2) having at least one hydroxyl group at the β-position. After removing the protecting group of this compound, it is amidated with a divalent or higher carboxylic acid or derivative (a1) thereof.

  The method [1] is preferable in view of production cost, ease of reaction, and the like.

  When β-hydroxyalkylamide is available, it undergoes a reaction between a divalent or higher carboxylic acid or derivative thereof (a1) and a primary or secondary amine (a2) having one or more hydroxyl groups at the β-position. Alternatively, a method may be used in which a part of the hydroxyl group of β-hydroxyalkylamide is reacted with the compound (a3) having one or more functional groups capable of reacting with the hydroxyl group.

(2) When R ¹ and R ² are not a group represented by the general formula (3):

[4] Amidation of a divalent or higher carboxylic acid or derivative thereof (a1) and a primary or secondary amine (a2) having one or more hydroxyl groups at the β-position.

  β-hydroxyalkylamide (A) may or may not contain a photopolymerizable functional group. Divalent or higher carboxylic acid or derivative thereof (a1), primary or secondary amine (a2) having one or more hydroxyl groups at β-position, or compound (a3) having one or more functional groups capable of reacting with hydroxyl groups ), A photopolymerizable functional group can be introduced by using a compound containing a photopolymerizable functional group. In view of stability during synthesis, it is preferable that the compound (a3) having one or more functional groups capable of reacting with a hydroxyl group contains a photopolymerizable functional group.

  Among divalent or higher carboxylic acids or derivatives thereof (a1), examples of divalent or higher carboxylic acids include the following. (Hereinafter, the same compound is expressed by <<). Linear saturated aliphatic dicarboxylic acid: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid,

Branched saturated aliphatic dicarboxylic acids: methyl malonic acid, dimethyl malonic acid, ethyl malonic acid, dipropyl malonic acid, isopropyl malonic acid, methyl succinic acid, dimethyl succinic acid, butyl succinic acid, octyl succinic acid, decyl succinic acid, dodecyl succinic acid, tetra Decyl succinic acid, hexadecyl succinic acid, octadecyl succinic acid, methyl glutaric acid, dimethyl glutaric acid, ethyl methyl glutaric acid, diethyl glutaric acid, methyl adipic acid, tetramethyl pimelic acid,

Unsaturated aliphatic dicarboxylic acids: allyl succinic acid, methallyl succinic acid, hexenyl succinic acid, octenyl succinic acid, dodecenyl succinic acid, dococenyl succinic acid, decadiene-1,2-dicarboxylic acid, fumaric acid, maleic acid, acetylenedicarboxylic acid, muconic acid, itaconic acid Citraconic acid, mesaconic acid,

Alicyclic dicarboxylic acids: cyclopropanedicarboxylic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, camphoric acid, cyclohexanedicarboxylic acid, methylcyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, methylcyclohexenedicarboxylic acid, norbornanedicarboxylic acid, norbornenedicarboxylic acid, bicyclo [2.2.2] Oct-5-ene-2,3-dicarboxylic acid, adamantanedicarboxylic acid, cyclopentylmalonic acid, cyclopentanediacetic acid, cyclohexanediacetic acid, adamantanediacetic acid,

Aliphatic dicarboxylic acid having an aromatic ring (the carbon atom bonded to the carboxyl group does not form an aromatic ring): phenylmalonic acid, benzylmalonic acid, thiophenmalonic acid, phenylsuccinic acid, diphenylsuccinic acid,

Aliphatic or cycloaliphatic carboxylic acids containing oxygen atoms in addition to carboxyl groups: tartaric acid, diacetyltartaric acid, dipivaloyltartaric acid, dibenzoyltartaric acid, ditoluoyltartaric acid, di (p-anisoyl) tartaric acid, malic acid, acetylmalic acid, citric acid, citramal Acid, hydroxymethylglutaric acid, galactaric acid, epoxysuccinic acid, oxalacetic acid, oxoglutaric acid, oxoazelaic acid, 4,5-dicarboxy-γ-pentadecanolactone, 3,6-epoxy-1,2,3 6-hexahydrophthalic acid, butyrolactone dicarboxylic acid,

Aliphatic or alicyclic dicarboxylic acids containing nitrogen atom: aspartic acid, N-methylaspartic acid, N- (tert-butoxycarbonyl) -aspartic acid, N- (benzyloxycarbonyl) aspartic acid, N-carbamoylaspartic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] aspartic acid, glycylaspartic acid, 3-hydroxyaspartic acid, glutamic acid, N-acetylglutamic acid, N- (tert-butoxycarbonyl) -glutamic acid, N- (benzyl Oxycarbonyl) glutamic acid, N-benzoylglutamic acid, N- (4-aminobenzoyl) glutamic acid, N-[(9H-fluoren-9-ylmethoxy) carbonyl] glutamic acid, methylglutamic acid, glycylglutamic acid Grayed azide Nino glutaric acid, N- phthalyl glutamic acid, amino adipic acid, aminopimelic acid, diaminopimelic acid, aminosuberic acid, folic acid, methotrexate,

Aliphatic or alicyclic dicarboxylic acids containing sulfur atoms: dimercaptosuccinic acid, thiomalic acid,

Aliphatic or alicyclic dicarboxylic acid containing a halogen atom: tetrafluorosuccinic acid, dibromosuccinic acid, hexafluoroglutaric acid, octafluoroadipic acid, dodecafluorosuberic acid, hexadecafluorosebacic acid, chlorendic acid «Het acid»,

Aromatic dicarboxylic acids: phthalic acid, methylphthalic acid, tert-butylphthalic acid, ethynylphthalic acid, (phenylethynyl) phthalic acid, methoxyphthalic acid, fluorophthalic acid, tetrafluorophthalic acid, trifluoromethylphthalic acid, chlorophthalic acid, dichloro Phthalic acid, tetrachlorophthalic acid, bromophthalic acid, tetrabromophthalic acid, nitrophthalic acid, hydroxyphthalic acid, aminophthalic acid, sulfophthalic acid, isophthalic acid, methylisophthalic acid bromoisophthalic acid, nitroisophthalic acid, hydroxyisophthalic acid, aminoisophthalic acid , Aminotriiodoisophthalic acid, sulfoisophthalic acid, terephthalic acid, dimethylterephthalic acid, tetrafluoroterephthalic acid, dichloroterephthalic acid, tetrachloroterephthalic acid, bromoterephthalic acid Tetrabromoterephthalic acid, nitroterephthalic acid, dihydroxyterephthalic acid, aminoterephthalic acid, sulfoterephthalic acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, anthraquinone dicarboxylic acid, 1,3-dibenzyl-2-oxo-4,5-imidazolidine dicarboxylic acid Acid, thiophene dicarboxylic acid,

Aliphatic or alicyclic tricarboxylic acid: 1,2,3-propanetricarboxylic acid «tricarballylic acid», anicotic acid, butenetricarboxylic acid, cyclohexanetricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 3- Butene-1,2,3-tricarboxylic acid, cyclohexanetricarboxylic acid, pentanetricarboxylic acid, tris (2-carboxyethyl) -1,3,5-triazine, tris (3-carboxypropyl) -1,3,5-triazine , Isocyanuric acid tris (2-carboxyethyl), isocyanuric acid tris (3-carboxypropyl),

Aromatic tricarboxylic acid: trimellitic acid, hemimellitic acid, benzene-1,3,5-tricarboxylic acid, benzophenone tricarboxylic acid,

Aliphatic or alicyclic tetracarboxylic acid: butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, thiodisuccinic acid, tetrahydrofurantetracarboxylic acid, bicyclo [2.2.2] oct-7 -Ene-2,3,5,6-tetracarboxylic acid, 5- (1,2-dicarboxyethyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid, 4- (1,2-dicarboxylic acid) Carboxyethyl) 1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid,

Aromatic tetracarboxylic acid: pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenylsulfonetetracarboxylic acid, oxydiphthalic acid, hexafluoroisopropylidenediphthalic acid, naphthalenetetracarboxylic acid, fluorene-9,9-bisphthalate acid,

Aliphatic or cycloaliphatic pentacarboxylic acid or hexacarboxylic acid: cyclohexane hexacarboxylic acid,

Aromatic pentacarboxylic acid or hexacarboxylic acid: benzene pentacarboxylic acid, merit acid,

In addition, as a divalent or higher carboxylic acid, polyester, polybutadiene, polyisoprene, acrylic oligomer having a carboxylic acid at the terminal and / or side chain, or polyether polyol, polyester polyol, polycarbonate polyol, polybutadiene polyol, polyisoprene polyol, poly It is obtained by modifying polyols such as acrylic polyol with acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Also included are compounds.

  Examples of carboxylic acid derivatives include acid anhydrides, acid chlorides, acid bromides, methyl esters, ethyl esters, phenyl esters, and tert-butyl esters of the above carboxylic acids.

  Examples of the primary or secondary amine (a2) having one or more hydroxyl groups at the β-position include the following.

Primary amine: ethanolamine, 1-amino-2-propanol <isopropanolamine>, 2-amino-1-propanol, 2-amino-1-butanol, 2-amino-2-phenyl-ethanol, 2-amino-2 -Methyl-1-propanol, isoleucinol << 2-amino-3-methyl-1-pentanol >>, 2-isopropylamino-3-methyl-1-butanol, leucinol << 2-amino-4-methyl-1-pentanol , Tert-leucinol << 2-amino-3,3-dimethyl-1-butanol >>, phenylalaninol << 2-amino-3-phenyl-1-propanol >>, 1-amino-2-butanol, 2-amino- 1-phenylethanol, 2-amino-1-phenyl-1-propanol,

One of the substituents on the nitrogen atom is a hydrocarbon group and the other is a secondary amine represented by the general formula (2): N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N- tert-butylethanolamine, 3-tert-butylamino-1,2-propanediol, N-cyclohexylethanolamine, N-phenylethanolamine, N-benzylethanolamine,

Secondary amines in which both substituents on the nitrogen atom are represented by the general formula (2): diethanolamine, diisopropanolamine, R ^{3 to} R ⁶ containing a hydroxyl group-substituted hydrocarbon group: 2- [ (Hydroxymethyl) amino] ethanol, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, tris (hydroxymethyl) aminomethane, 3-amino-1,2- Propanediol, 3- (methylamino) -1,2-propanediol, N-methylglucamine << 6- (methylamino) -1,2,3,4,5-hexanepentaol >>, 1,3-bis [Tris (hydroxymethyl) methylamino] propane, 2-amino-1-phenyl-1,3-propanediol, phenylephrine << 1- (3-hydroxy Phenyl) -2- (methylamino) ethanol, ethylephrine << 2-ethylamino-1- (3-hydroxyphenyl) ethanol >>, other than the above: 2- (2-aminomethylaminoethanol), 2-amino-1- (4-nitrophenyl) -1,3-propanediol, serine, serine methyl ester, N- (2,4-dinitrophenyl) serine, methioninol << 2-amino-4-methylthio-1-butanol >>, N- ( 5-nitro-2-pyridyl) alaninol, pyrrolinol <2- (hydroxymethyl) piperidine>, 4-amino-3-hydroxybutyric acid, 3-hydroxypiperidine, isoserine, 2-aminocyclohexanol, threonine, 1-amino-2 -Indanol, glucosamine, 1,3-diamino-2-propanol, ate Norol, adrenaline, α, α-diphenyl-2-pyrrolidinemethanol.

  Examples of the compound (a3) having at least one functional group capable of reacting with a hydroxyl group are isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol ester, amino resin, The compound which has an epoxy group is mentioned. Among these, from the viewpoint of reactivity, an isocyanate group, a carboxyl group, a carboxylic acid anhydride group, and a carboxylic acid halide group are particularly preferable, and a carboxyl group and an isocyanate group are more preferable.

  Examples of the isocyanate include the following.

Monofunctional isocyanate: methyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, lauryl isocyanate, stearyl isocyanate, phenyl isocyanate, cyclopropyl isocyanate, phenethyl isocyanate, tosyl isocyanate, acryloyloxyethyl isocyanate, methacryloyloxyethyl isocyanate, vinyl isocyanate, allyl isocyanate 2- (2-acryloyloxyethyloxy) ethyl isocyanate, 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 1,1-bis (methacryloyloxymethyl) Ethyl isocyanate,

  Bifunctional isocyanates: tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, phenylene diisocyanate, trizine diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate Isopropylidenebis (cyclohexyl isocyanate), 3- (2′-isocyanatocyclohexyl) propyl isocyanate, dianisidine isocyanate, diphenyl ether diisocyanate, dimer isocyanate, tetramethylxylylene diisocyanate,

Trifunctional isocyanate: lysine triisocyanate, tris (isocyanatophenyl) methane, tris (isocyanatophenyl) thiophosphate,

  Further, biurets, uretdiones, isocyanurates, and adducts of the above polyfunctional isocyanates are also included.

  Isocyanate selected from the above-mentioned polyfunctional isocyanate, biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct, methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, methyl Activities such as amine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone Compounds obtained by reacting a silicon compound, also cited.

  Among the above, considering the solubility, storage stability, ease of production, etc., the above monofunctional isocyanate, or one of the polyfunctional isocyanate or biuret of polyfunctional isocyanate, uretdione, isocyanurate, adduct It is preferable to use a monofunctional isocyanate which is obtained by leaving a group and reacting the remainder with an active hydrogen compound.

Among them, since the photosensitivity is improved, that the R ⁷ to obtain a β- hydroxyalkylamide is represented by the general formula (9) (A) with a compound represented by the following general formula (6) preferable. Furthermore, since the solubility to an organic solvent and photosensitivity become favorable, it is preferable to use together the compound represented by General formula (4) mentioned later.

［式中、Ｒ ¹²は水素原子またはメチル基であり、Ｒ¹³は一般式（７）で表される基、または一般式（８）で表される基である。］ General formula (6)

[Wherein, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a group represented by the general formula (7) or a group represented by the general formula (8). ]

［ｎ１は１〜２の整数である。］ General formula (7)

[N1 is an integer of 1-2. ]

［Ｒ¹⁴は炭素数２〜８の直鎖状もしくは分岐状のアルキレン基、２価の脂環族炭化水素基、または２価の芳香族炭化水素基であり、Ｒ¹⁵は炭素数６〜１３の直鎖状もしくは分岐状のアルキレン基、２価の脂環族炭化水素基、または２価の芳香族炭化水素基である。］ General formula (8)

[R ¹⁴ is a straight or branched alkylene group, a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, having 2 to 8 carbon atoms, R ¹⁵ is a carbon number 6 to 13 A linear or branched alkylene group, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. ]

Examples of the carboxylic acid, that is, the compound having a carboxyl group include the following.
Aliphatic saturated monofunctional carboxylic acids: formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid <pentanoic acid>, 2-methylbutyric acid, isovaleric acid <3-methylbutyric acid>, pivalic acid <2,2-dimethyl Propionic acid, caproic acid <hexanoic acid>, methylvaleric acid, dimethylbutyric acid, ethylbutyric acid, enanthic acid <heptanoic acid>, caprylic acid <octanoic acid>, 2-ethylhexanoic acid, pelargonic acid <nonanoic acid>, capric acid << decanoic acid >>, undecanoic acid, lauric acid << dodecanoic acid >>, tridecanoic acid, myristic acid << tetradecanoic acid >>, pentadecanoic acid, palmitic acid << hexadecanoic acid >>, margaric acid << heptadecanoic acid >>, stearic acid << octadecanoic acid >>, isostearic acid Acid "2-heptylundecanoic acid", nonadecanoic acid, arachidic acid "icosanoic acid", henicosa Acid, behenic acid "docosanoate", tricosanoic acid, lignoceric acid "tetracosanoic acid", pentacosanoic acid, cerotic acid "hexacosanoic acid", heptacosanoic acid, montanic acid "octacosanoic", nonacosanoic acid, melissic acid "triacontanoic"

  Aliphatic unsaturated monofunctional carboxylic acids: acrylic acid, methacrylic acid, crotonic acid, undecenoic acid, palmitoleic acid <9-hexadecenoic acid>, petrothelic acid <6-octadecenoic acid>, oleic acid <9-octadecenoic acid>, elaidic acid << 9-octadecenoic acid >>, vaccenic acid, linoleic acid << 9,12-octadecadienoic acid >>, linolenic acid << 9,12,15-octadecatrienoic acid >>, gamma-linolenic acid << 6,9,12-octa Decatrienoic acid, eleostearic acid, araguidonic acid << 5,8,11,14-eicosatetraenoic acid >>, 5,8,11,14,17-eicosapentaenoic acid, erucic acid << 13-docosenoic acid >> Docosahexaenoic acid, 22-tricosenoic acid, 15-tetracosenoic acid, nervonic acid,

  Alicyclic monofunctional carboxylic acids: cyclopropanecarboxylic acid, dimethylcyclopropanecarboxylic acid, tetramethylcyclopropanecarboxylic acid, mercaptomethylcyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclopentylacetic acid, aminocyclopentanecarboxylic acid , Cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexylpropionic acid, cyclohexylbutyric acid, methylcyclohexanecarboxylic acid, propylcyclohexanecarboxylic acid, isopropylcyclohexanecarboxylic acid, butylcyclohexanecarboxylic acid, tert-butylcyclohexanecarboxylic acid, hydroxycyclohexanecarboxylic acid , (Hydroxymethyl) cyclohexanecarboxylic acid, cyclohexenecarbo Acid, norbornene carboxylic acid, norbornane carboxylic acid, noradamantane carboxylic acid, adamantane carboxylic acid,

  Monofunctional carboxylic acid having an oxygen atom in addition to the carboxyl group: glycolic acid, lactic acid, hydroxypalmitic acid, ricinoleic acid, hydroxystearic acid, alloyed acid <trihydroxyhexadecanoic acid>, jasmonic acid <3-oxo-2- (2- Pentenyl) cyclopentaneacetic acid, cucurbic acid << 3-hydroxy-2- (2-pentenyl) cyclopentaneacetic acid >>, 3-oxobutanoic acid and the like, and (a-1) a divalent or higher valent acid And compounds listed as carboxylic acids.

  Examples of the carboxylic acid, that is, a compound having a carboxyl group, include compounds obtained by esterifying or amidating a part of a compound mentioned as a divalent or higher carboxylic acid or a derivative thereof with an alcohol or an amine. For example, methanol, ethanol, propanol, butanol, pentanol, phenol, benzyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Such as (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, methylamine, ethylamine, dibutylamine, polyethylene glycol monoalkyl ether, polypropylene glycol monoalkyl ether, polycaprolactone, etc. Alcohol, amine, and (a-1) a compound enumerated with a divalent or higher carboxylic acid are partially esterified to leave a single carboxyl group in the molecule. Ability carboxylic acid, and the like. In particular, it is preferable to use a cyclic carboxylic acid anhydride of a divalent carboxylic acid because one carboxyl group is generated after reacting with a hydroxyl group or an amino group in a 1: 1 ratio.

  Further, acid anhydrides, acid halides, methyl esters, ethyl esters, phenyl esters, and tert-butyl esters of the above compounds having a carboxyl group are also included.

  Among the above, in consideration of solubility, storage stability, ease of production, etc., some of the monofunctional carboxylic acid, acid halide, acid anhydride, or polyfunctional carboxylic acid or derivative thereof Monofunctional carboxylic acid or derivative thereof in which carboxylic acid is reacted with alcohol or amine to leave one carboxyl group, or monofunctional carboxylic acid produced by reacting monofunctional alcohol or amine with a cyclic acid anhydride of divalent carboxylic acid Is preferably used.

  Especially, since it is easy to provide the solubility to an organic solvent, it is preferable to use the compound represented by following General formula (4), and since photocurability becomes favorable, in following General formula (5) It is preferable to use the compound represented.

［式中、Ｒ⁸は炭素数２〜１８の直鎖状、環状または分岐状の飽和または不飽和炭化水素基である。］ General formula (4)

[Wherein, R ⁸ represents a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]

General formula (5)

[Wherein, R ⁹ is a hydrogen atom or a methyl group, R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ]
These compounds may be used alone or in combination.

  Silanol is a compound having a Si—OH structure in the molecule, and OH in the silanol reacts with a hydroxyl group. Further, alkoxysilane, sulfuric acid of silanol, sulfonic acid ester, and halogenated silane (hereinafter collectively referred to as “silanol derivatives”) generate silanol by hydrolysis, and thus can be used in the same manner as silanol. A silanol derivative is commercially available from the viewpoint of storage stability.

  The following are mentioned as a silanol derivative.

  Monofunctional silanol derivatives: trimethylsilyl triflate, triethylsilyl triflate, tert-butyldimethylsilyl triflate, diethylisopropylsilyl triflate, tripropylsilyl triflate, bis (trimethylsilyl) sulfate, chlorotrimethylsilane, chlorotriethylsilane, trimethylmethoxysilane,

  Multifunctional silanol derivatives: dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, vinyltriethoxysilane , Vinyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycosoxypropyltriethoxy Silane, p-styryltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxy Propylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminomethyl) -3-aminopropyltrimethoxysilane, N- (2-aminomethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxy Silane, 3-chloro B pills trimethoxysilane, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane,

  Among these, considering the solubility, storage stability, ease of production, etc., it is preferable to use the monofunctional silanol derivative.

  An amino resin is a compound having a hydroxymethylamino group in which an electron-withdrawing group is bonded to a nitrogen atom, and reacts with a hydroxyl group to form an ether bond. Examples of the electron withdrawing group include a carbonyl group, a thiocarbonyl group, and a triazine ring. A compound having an alkoxymethylamino group in which the hydroxyl group is capped with an alcohol can also be used because it generates a hydroxyl group by hydrolysis.

The following are mentioned as an amino resin.

  Monofunctional amino resin: N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, N-hydroxymethylacetamide, N-hydroxymethylurea, 1- (hydroxymethyl) -5,5-dimethylhydantoin, N- (hydroxymethyl) nicotinamide,

  Multifunctional amino resin: N, N′-dimethylolurea, 1,3-bis (hydroxymethyl) -5- [1,3-bis (hydroxymethyl) ureido] hydantoin, 1,3,4,6-tetrakis (methoxy) Methyl) glycoluril, hexamethylolmelamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, etc., nitrogen, hydroxyl, methoxymethyl, butoxymethyl groups are substituted, urea, melamine, benzoguanamine, glycoluril, etc. Is mentioned.

  Among the above, in consideration of solubility, storage stability, ease of production, etc., it is preferable to use the monofunctional amino resin.

  Examples of the compound having an epoxy group include the following.

  Monofunctional epoxy: allyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, phenyl glycidyl ether, phenylphenol glycidyl ether, sec-butylphenol monoglycidyl ether, polyethylene glycol monophenyl ether monoglycidyl ether, N-glycidyl phthalimide, styrene oxide 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexane-1-carboxylic acid ester, 3,4-epoxycyclohexane-1-methanol, 3,4-epoxycyclohexane-1-carbaldehyde, 4, 5-epoxy-1,2-dicarboxylic acid ester,

  Multifunctional epoxy: sorbitol polyglycidyl ether, polyglycerin polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerin polyglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether Propyl) propane diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tert-butylphenol glycidyl ether, polybutadiene diglycidyl ether, diglycidyl phthalate, diglycidyl cyclohexanedicarboxylate, glycidyl terephthalate, hydroquinone diglycidyl ether, dibromopheno Rudiglycidyl ether, dibromoneopentyl glycol diglycidyl ether, condensate of bisphenol A and epichlorohydrin, condensate of bisphenol F and epichlorohydrin, phenol novolac polyglycidyl ether, cresol novolac polyglycidyl ether, brominated bisphenol A And epichlorohydrin condensate, N, N, N ′, N′-tetraglycidyl bis (aminophenyl) methane, diglycidyl dimer, hydrogenated bisphenol A and epichlorohydrin condensate, di-tert-butyl Hydroquinone diglycidyl ether, tetramethylbisphenol F diglycidyl ether, bis (N, N-diglycidylaminomethyl) benzene, bis (N, N-diglycidylaminomethyl) cyclohexane, and the like. It is done.

  Among the above, in consideration of solubility, storage stability, ease of production, etc., it is preferable to use the above monofunctional epoxy.

(Amidation)
There are various methods for amidating a divalent or higher carboxylic acid or derivative thereof (a1) and a primary or secondary amine (a2) having one or more hydroxyl groups at the β-position, but a divalent or higher carboxylic acid is available. Alternatively, the reaction can proceed by removing water when the derivative (a1) is a carboxylic acid, removing alcohol in the case of a carboxylic acid ester, and removing an acid in the case of a carboxylic acid anhydride or halide. In the case of water or alcohol, it is prepared to be removed from the reaction system by heating. In the case of acid, triethylamine, tributylamine, dimethylbenzylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. The basic compound can be removed.

A catalyst can be used in the amidation. For example, acid catalysts such as sulfuric acid, hydrochloric acid, methanesulfonic acid, p-toluenesulfonic acid, base catalysts such as sodium hydroxide, sodium carbonate, sodium methoxide (hereinafter referred to as “base catalyst”), triethylamine,
Amine catalysts such as tributylamine, trioctylamine, tetramethylethylenediamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, N-methylimidazole (hereinafter “ Amine catalysts ”), salts and complexes containing metal ions such as iron (III), zirconium (IV), scandium (III), titanium (IV), tin (IV), hafnium (IV), diphenylammonium triflate, And ammonium salts such as pentafluorophenylammonium triflate.

  A solvent can be used in the amidation reaction. The solvent to be used can be used as long as it is other than a solvent that reacts with a reaction substrate such as alcohol, amine, or carboxylic acid. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc. It is done.

  In particular, the amidation with carboxylic acid can be performed using a condensing agent. A condensing agent activates a carboxylic acid or an amine, and the esterification reaction can be carried out under mild conditions. At the same time, the by-product water is combined with the condensing agent to form another compound. And a compound having a water removing action. Such condensing agents include, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, p-toluenesulfonyl chloride, 1-ethyl-3- (N, N-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldiimidazole, ethyl chloroformate, chloroformate Acid isobutyl, 2,4,6-trichlorobenzoic acid chloride, 2-methyl-6-nitrobenzoic anhydride, O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′— Examples thereof include tetramethyluronium hexafluorophosphate.

(Denaturation)
When a part of the hydroxyl group of β-hydroxyalkylamide (A1) is reacted with the compound (a3) having one or more functional groups capable of reacting with the hydroxyl group, the reaction is carried out under conditions suitable for each functional group. What is necessary is just to make it react.

  When the compound (a3) having one or more functional groups capable of reacting with a hydroxyl group is an isocyanate, the reaction proceeds by adding a non-catalyst or an appropriate catalyst and heating. Suitable catalysts include, for example, amines such as triethylamine, tributylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, and salts thereof, tetrabutyl titanate, dibutyltin dilaurate, tin octylate. And metal salts and complexes.

  When the compound (a3) having at least one functional group capable of reacting with a hydroxyl group is a carboxylic acid, the dehydration condensation reaction proceeds by heating to 100 ° C. or higher, preferably 140 ° C. or higher without a catalyst. Alternatively, the reaction can be allowed to proceed at a lower temperature by adding an appropriate catalyst. The catalysts, condensing agents, etc. described for the amidation reaction can be used for this reaction.

  When the compound (a3) having at least one functional group capable of reacting with a hydroxyl group is a carboxylic acid anhydride or a carboxylic acid halide, it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

  When the compound (a3) having one or more functional groups capable of reacting with a hydroxyl group is silanol, it is preferable to add a base catalyst or an amine catalyst and react at 0 to 100 ° C. At this time, it is preferable to use 1 mol or more of the base catalyst or amine catalyst with respect to 1 mol of carboxylic acid anhydride or carboxylic acid halide.

  When the compound (a3) having at least one functional group capable of reacting with a hydroxyl group is an amino resin, methanesulfonic acid, p-toluenesulfonic acid, ammonium salt or amine salt thereof is used as a catalyst, and 0 to 200 The reaction is preferably carried out at ° C.

  When the compound (a3) having at least one functional group capable of reacting with a hydroxyl group is an epoxy group, a strong base such as potassium hydroxide, sodium hydroxide, sodium methoxide, sodium ethoxide, sodium hydride The reaction is preferably performed at 0 to 200 ° C. using a catalyst or a metal catalyst such as tetrafluoroboric acid or tin (IV) chloride.

  When the compound represented by the general formula (1) contains a photopolymerizable functional group, a gas having a polymerization inhibitory effect is introduced into the reaction system during the reaction, or a polymerization inhibitor is added. May be. By introducing a gas having a polymerization inhibition effect into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented.

  Examples of the gas having an effect of inhibiting radical polymerization include a gas containing oxygen that does not enter the explosion range of the substance in the system, for example, air.

  As the radical polymerization inhibitor, known ones can be used and are not particularly limited. For example, hydroquinone, methoquinone, 2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), phenothiazine and the like. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor to be used is preferably 0.005 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the total solids in the reaction system. Most preferred is 1.5 parts by weight. If the polymerization inhibitor is less than 0.005 parts by weight, the polymerization inhibition effect may not be sufficient. On the other hand, if it exceeds 5 parts by weight, the exposure sensitivity may decrease. Moreover, it is more preferable to use a gas having a polymerization inhibiting effect in combination with the polymerization inhibitor because the amount of the polymerization inhibitor to be used can be reduced or the polymerization inhibiting effect can be enhanced.

<Polymer containing carboxyl group (B)>
The polymer (B) containing a carboxyl group of the present invention has two purposes: imparting alkali developability to the color filter coloring composition and thermosetting reaction with β-hydroxyalkylamide (A). It is a polymer that has a carboxyl group at the end and / or side chain of the polymer. It may or may not contain a photopolymerizable functional group. The polymer may be linear, branched or star-shaped, and may be thermoplastic or thermosetting.
Examples of the polymer (B) containing a carboxyl group that does not contain a photopolymerizable functional group include, for example, carboxy-terminated polyester, polyamide, polyester amide, polyether ester, acrylic, polybutadiene, polyisoprene, and carboxyl group side chain polyurethane, Examples thereof include carboxylic acid-added cellulose, (meth) acrylate copolymer containing a carboxyl group, and a carboxylic acid anhydride adduct of a phenol resin.

In the polymer (B) containing a carboxyl group used in the present invention, radically polymerizable, cationically polymerizable, and anionic polymerizable photopolymerizable functional groups can be introduced. From the viewpoint of stability, radically polymerizable It is preferable to contain the photopolymerizable functional group. Examples of the method include the following methods.
(B-1) A method of introducing a photopolymerizable functional group into a polymer containing a carboxyl group (B-2) A method of introducing a photopolymerizable functional group into a polymer not containing a carboxyl group, and introducing a carboxyl group. Can be mentioned. Moreover, it is not limited about the polymer which has these functional groups, It is possible to use each polymer, such as an acrylic type, a urethane type, a polyester type, a polyolefin type, a polyether type, a natural rubber, a block copolymer rubber, and a silicone type. it can.

As a method of introducing the photopolymerizable functional group used in (B-1) and (B-2),
(B-11) A carboxyl group, a hydroxyl group, a mercapto group, an amino group, an active methylene group, etc. in a polymer containing a carboxyl group, a hydroxyl group, a mercapto group, an amino group, an active methylene group, etc., an epoxy group, an isocyanate group, an aldehyde A method of reacting an epoxy group, an isocyanate group, an aldehyde group or the like in a compound containing a group or the like and a photopolymerizable functional group,
(B-12) Epoxy groups, isocyanate groups, aldehyde groups, and the like in polymers containing epoxy groups, isocyanate groups, aldehyde groups, carboxyl groups, hydroxyl groups, mercapto groups, amino groups, active methylene groups, and the like, and photopolymerizability. Examples thereof include a method of reacting a carboxyl group, a hydroxyl group, a mercapto group, an amino group, an active methylene group and the like in a compound containing a functional group.

As a method of introducing the carboxyl group used in (B-2),
(B-13) A method in which an acid anhydride group in a polybasic acid anhydride is reacted with a hydroxyl group, an amino group, or the like in a polymer containing a hydroxyl group, an amino group, or the like.

As a method of simultaneously introducing a photopolymerizable functional group and a carboxyl group used in (B-2),
(B-14) A method in which an acid anhydride group in a polymer containing a carboxylic acid anhydride group is reacted with a hydroxyl group or the like in a compound containing a photopolymerizable functional group (B-15) Examples thereof include a method of reacting an acid anhydride group in a compound containing a photopolymerizable functional group with a hydroxyl group or amino group in a polymer containing a group.

  The polymer (B) containing a carboxyl group can be used alone or in combination of two or more. The ratio of the carboxyl group in the polymer (B) containing a carboxyl group and the hydroxyl group in the β-hydroxylamide group is preferably 10/1 to 1/10 in terms of molar ratio, and more preferably 3/1 to 1/3. Further, 1.5 / 1 to 1 / 1.5 is preferable. When it is out of the range of 10/1 to 1/10, the hydroxyl group in the carboxyl group or β-hydroxyalkylamide group is excessive in the cured film or fine pattern, and the chemical resistance and heat resistance are insufficient. There is a risk.

  The concentration of the carboxyl group in the polymer (B) containing a carboxyl group is preferably an acid value of 10 to 250 mgKOH / g, more preferably 20 to 200 mgKOH / g, and further preferably 40 to 100 mgKOH / g. If it is less than 10 mgKOH / g, the functional group (carboxyl group) that can react with the hydroxyl group in β-hydroxyalkylamide (A) decreases, and chemical resistance and heat resistance may not be obtained satisfactorily. If it exceeds 250 mgKOH / g, the viscosity of the coating agent is high, and the storage stability may deteriorate.

  In addition to the carboxyl group, an active methylene group such as a phenolic hydroxyl group, an aromatic mercapto group, or a β-diketone can be used as the functional group capable of reacting with the β-hydroxyalkylamide (A). The functional group can be introduced into the polymer (B) containing a carboxyl group. You may contain in (beta) -hydroxyalkylamide (A) and a photopolymerizable monomer (D).

  As a method of obtaining a (meth) acrylic copolymer containing a carboxyl group, a method of copolymerizing (meth) acrylic acid or a (meth) acrylate containing a carboxyl group with another monomer, or a hydroxyl group (meta ) A method of reacting a hydroxyl group in a polymer obtained by copolymerizing an acrylate with another monomer with an acid anhydride group in a polybasic acid anhydride.

  Moreover, as a method for obtaining a (meth) acrylate copolymer containing a photopolymerizable functional group and a carboxyl group, there are the methods (B-1) and (B-2) described above. ) To (B-15). Specifically, a method of reacting a part of carboxyl groups in a (meth) acrylic copolymer containing a carboxyl group with an epoxy group in a (meth) acrylate containing an epoxy group, containing an epoxy group The epoxy group in the (meth) acrylic copolymer is reacted with the carboxyl group in the (meth) acrylate containing (meth) acrylic acid or a carboxyl group, and the acid of the polybasic acid anhydride with respect to the generated hydroxyl group Method of reacting anhydride group, hydroxyl group in (meth) acrylic copolymer containing carboxyl group and hydroxyl group, isocyanate group or acid anhydride group in (meth) acrylate or unsaturated acid anhydride containing isocyanate group And the like.

Examples of the (meth) acrylate containing a carboxyl group include acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethylhexa. Examples include hydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, and ω-carboxypolycaprolactone (meth) acrylate. Itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) acrylic acid, α- (hydroxymethyl) methacrylic acid, p-vinylbenzoic acid and the like can also be used.
(Meth) acrylic acid is preferred from the viewpoints of copolymerizability and availability.

  As for the weight average molecular weight (Mw) of the polymer (B) containing a carboxyl group, 2000-25000 are preferable, More preferably, it is 4000-15000. When the weight average molecular weight (Mw) is less than 2,000, the heat resistance may be deteriorated, and when the weight average molecular weight (Mw) exceeds 25,000, the viscosity becomes high and coating may be difficult.

  When the polymer (B) containing a carboxyl group of the present invention is used as a coloring composition for a color filter, high transparency is required. Therefore, the transmittance in the entire wavelength region of 400 to 700 nm in the visible light region. Is preferably 80% or more, more preferably 95% or more. From the viewpoint of transparency, a (meth) acrylic copolymer containing a carboxyl group is preferably used.

  The total amount of the β-hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group is 1 to 400 parts by weight, preferably 1 to 250 parts by weight, based on 100 parts by weight of the pigment in the color filter coloring composition. It can be used in parts.

<Dye (C)>
The coloring composition for a color filter of the present invention contains a dye (C) as an essential component. Moreover, it is also preferable that the colored composition for a color filter of the present invention is used in combination with an organic pigment (F). Below, the dye (C) which is an essential component of the coloring composition for color filters of this invention is demonstrated.

  The dye (C) of the present invention is a salt-forming compound [C1] composed of a triarylmethane-based basic dye and a counter compound having a molecular weight in the range of 200 to 3,500.

[Salt-forming compound [C1]]
The salt-forming compound [C1] is composed of a triarylmethane basic dye and a counter compound having a molecular weight in the range of 200 to 3500, and exhibits blue, purple, green, and yellow. A basic dye and a counter compound can be reacted by dissolving both in an aqueous solution, an alcohol solution or the like to obtain a salt-forming compound. Or it is also possible to obtain by melt-kneading both, heating. By using such a salt-forming compound [C1], even when it is used in an image display apparatus using a color filter that has excellent light resistance and heat resistance and requires high reliability while having good spectral characteristics. , Its characteristics will be sufficient.
The triarylmethane basic dye will be described in detail below.

(Triarylmethane basic dye)
The triarylmethane basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminoarylmethane-based basic dye is preferable in terms of good blue, red and green coloring.
a) Diaminotriarylmethane basic dye b) Triaminotriarylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriarylmethane basic dye, diaminotriarylmethane basic dye The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable. Further, diphenylnaphthylmethane basic dye and / or triarylmethane basic dye are preferable.

  A blue triarylmethane basic dye is preferable because it has spectral characteristics with high transmittance at 400 to 440 nm.

  Specifically, triarylmethane basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like. Among them, C.I. I. Basic Blue 7, Green 4, Green 1, and Violet 3 are preferably used.

(Counter compound)
In the present invention, the counter compound as an anion component that can be preferably used is an anionic compound having a molecular weight in the range of 200 to 3,500, specifically, organic sulfonic acids such as heteropolyacids and aromatic sulfonic acids. Organic acids such as aromatic carboxylic acids and organic carboxylic acids such as fatty acids, and acid dyes.

The molecular weight of the counter compound is preferably in the range of 200 to 750. When the molecular weight of the counter compound is smaller than 200, the heat resistance and light resistance are lowered, and when the molecular weight of the counter compound is larger than 3500, the ratio of the coloring component per molecule is lowered and sufficient color development is achieved. It becomes impossible to do so.
Furthermore, modification with a resin having an acid group is also preferable.

  Among these, it is preferable that the counter compound as an anion component has the form of organic sulfonic acid, organic carboxylic acid, and acid dye. Of these, the organic sulfonic acid and acid dye forms are preferred. In this case, the preferred molecular weight range of the counter compound is 200 to 750.

The molecular weight and average molecular weight defined in the present invention are expressed by theoretical values converted from atomic weights. The first decimal place was calculated as a significant figure, and the calculated value was rounded off to exclude the minority.
When the counter compound is used as a sodium salt, the molecular weight is taken into account after replacing Na with H.

《Heteropoly acid》
The heteropoly acid, phosphotungstic acid _{H 3 (PW 12 0 40)} · nH 2 O (n ≒ 30:. ≒ is representative of the the nearly equal) (molecular weight 3421), silicotungstic acid _{H 4 (SiW 12 0 40)} · _{nH 2 O (n ≒ 30)} ( molecular weight 3418), phosphomolybdate _{H 3 (PMo 12 0 40)} · nH 2 O (n ≒ 30) ( molecular weight 2205), silicomolybdic acid _{H 3 (SiMo 12 0 40)} · nH ₂ O (n≈30) (molecular weight 2202), phosphotungstomolybdic acid H ₃ (PW _{12 -X} Mo _X 0 ₄₀ ) · nH ₂ O (n≈30) (6 <X <12), phosphovanadomolybdic acid _{H 15-X (PV 12 -} X Mo X 0 40) · nH 2 O (n ≒ 30) , and the like.
In addition, the molecular weight of phosphotungstomolybdic acid, phosphovanadomolybdic acid, and cytungstomolybdic acid is adjusted within the range of 2202 to 3421 by changing the composition ratio of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, silicomolybdic acid, and the like. be able to.
Moreover, when using a heteropolyacid as a counter compound, it is preferable that the average molecular weights are the range of 2820-3421. This is because, when molybdenum and tungsten are included, the proportion of tungsten is preferably more than 50%. In the case of phosphotungstomolybdic acid, a colorant having excellent transparency can be obtained by reducing the Mo content and including a large amount of W.

《Organic acid》
Examples of the organic acid include organic sulfonic acids such as aromatic sulfonic acids, and organic carboxylic acids such as aromatic carboxylic acids and fatty acids.

  In the case of an organic acid, a more preferable molecular weight range is 200 to 400. More preferably, it is the range of 250-400. By setting the molecular weight within this range, it is possible to obtain a colorant having a good balance between resistance and coloring power, which is preferable.

  Preferred compounds as the aromatic sulfonic acid include 1-naphthylamine-4,8-disulfonic acid (molecular weight 303), 1-naphthylamine-3,8-disulfonic acid (molecular weight 303), 1-naphthylamine-5,7-disulfonic acid ( Molecular weight 303), 1-naphthylamine-3,6-disulfonic acid (molecular weight 303), 1-naphthylamine-3,6,8-trisulfonic acid (kofoic acid) (molecular weight 383), 2-naphthylamine-6,8-disulfone Acid (molecular weight 303), 2-naphthylamine-1,6-disulfonic acid (molecular weight 303), 2-naphthylamine-4,8-disulfonic acid (molecular weight 303), 2-naphthylamine-3,6-disulfonic acid (amino-R) Acid) (molecular weight 303), 2-naphthylamine-5,7-disulfonic acid (amino J acid) (molecular weight 303) 1-naphthol-4,8-disulfonic acid (molecular weight 304), 1-naphthol-3,8-disulfonic acid (ε acid) (molecular weight 304), 1-naphthol-3,6-disulfonic acid (molecular weight 304), 1 -Naphthol-3,6,8-trisulfonic acid (molecular weight 384), 2-naphthol-6,8-disulfonic acid (molecular weight 304), 2-naphthol-3,6-disulfonic acid (R acid) (molecular weight 304) 2-naphthol-3,6,8-trisulfonic acid (molecular weight 384), N-phenyl-1-naphthylamine-8-sulfonic acid (molecular weight 299), Np-tolyl-1-naphthylamine-8-sulfonic acid (Molecular weight 313), N-phenyl-1-naphthylamine-5-sulfonic acid (molecular weight 299), N-phenyl-2-naphthylamine-6-sulfonic acid (molecular weight 29) 9), N-acetyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-7-amino-1-naphthol-3-sulfonic acid (molecular weight 315), N-acetyl-6 -Amino-1-naphthol-3-sulfonic acid (molecular weight 281), N-phenyl-6-amino-1-naphthol-3-sulfonic acid (molecular weight 315), 1,8-dihydro-3,6-disulfonic acid ( Chromotropic acid) (molecular weight 320), 8-amino-1-naphthol-3,6-disulfonic acid (molecular weight 319), 8-amino-1-naphthol-5,7-disulfonic acid (molecular weight 319), 1,6 -Diamino-2-naphthol-4-sulfonic acid (molecular weight 254), 1-amino-2-naphthol-6,8-disulfonic acid (molecular weight 319), 1-amino-2-naphtho 3,6-disulfonic acid (molecular weight 319), 2,8-diamino-1-naphthol-5,7-disulfonic acid (molecular weight 334), 2,7-diamino-1-naphthol-3-sulfonic acid (molecular weight) 254), 2,6-diamino-1-naphthol-3-sulfonic acid (molecular weight 254), 2,8-diamino-1-naphthol-3,6-disulfonic acid (molecular weight 334), 2-amino-7-phenyl And amino-1-naphthol-3-sulfonic acid (molecular weight 330).

  It is also preferable to use anthracenesulfonic acid (molecular weight 258), anthraquinone-2-sulfonic acid, anthraquinone-1-sulfonic acid (molecular weight 288).

2-amino-1-naphthalenesulfonic acid (tobias acid molecular weight 223), 4-amino-1-naphthalenesulfonic acid (naphthoic acid molecular weight 223), 8-amino-1-naphthalenesulfonic acid (peric acid molecular weight 223), 2-amino-6-naphthalenesulfonic acid (brenanoic acid, molecular weight 223), 1-amino-5-naphthalenesulfonic acid (lorentzic acid, molecular weight 223), 5-amino-2-naphthalenesulfonic acid (molecular weight 223), 1-amino- One amino group and one sulfonic acid group such as 6-naphthalenesulfonic acid (molecular weight 223), 6-amino-1-naphthalenesulfonic acid (molecular weight 223), 3-amino-1-naphthalenesulfonic acid (molecular weight 223), etc. It is preferable to use naphthylamine sulfonic acid having high heat resistance and light resistance. Shii is intended. Among these, 2-amino-1-naphthalenesulfonic acid (tobias acid) is particularly preferable.
Furthermore, 2-hydroxy-6-naphthalenesulfonic acid (shefic acid molecular weight 224), 1-hydroxy-4-naphthalenesulfonic acid (nevir-winter acid: NW acid molecular weight 224), 1-hydroxy-5-naphthalenesulfonic acid (L It is also preferable to use hydroxynaphthalenesulfonic acid having one hydroxyl group and one sulfonic acid group, such as acid molecular weight 224) and 2-hydroxy-8-naphthalenesulfonic acid (croseinic acid molecular weight 224).

  Among them, an organic sulfonic acid having 2 to 3 sulfone groups is preferable in that the color developability is good and high brightness can be achieved. When there are 4 or more sulfonic acids, environmental stability deteriorates and changes with time are likely to occur. With one sulfonic acid, the basic dye and the counter compound react in a 1: 1 ratio, and color is generated when the main color is used. May be worse.

  In the case of an organic sulfonic acid having a molecular weight in the range of 200 to 250, even if there is one sulfonic acid group per molecule, the color development is not impaired because the molecular weight of the counter compound itself is small. .

  Examples of organic carboxylic acids include tetrachlorophthalic acid (molecular weight 304), palmitic acid (molecular weight 257), stearic acid (molecular weight 285), arachidic acid (molecular weight 313), behenic acid (molecular weight 341), lignoceric acid (molecular weight 369). Oleic acid (molecular weight 282), elaidic acid (molecular weight 282), erucic acid (molecular weight 339), nervonic acid (molecular weight 367), linoleic acid (molecular weight 280), gamolenic acid (molecular weight 278), arachidonic acid (molecular weight 305), Examples include α-linolenic acid (molecular weight 278), stearidonic acid (molecular weight 276), eicosapentaenoic acid (molecular weight 302), and docosahexaenoic acid (molecular weight 328).

<Acid dye>
Further, the hue can be controlled by using a counter compound as an acid dye. Examples of the acid dye include anthraquinone acid dyes, monoazo acid dyes, disazo acid dyes, oxazine acid dyes, amino ketone acid dyes, quinoline acid dyes, and triarylmethane acid dyes.

  More specifically, examples of the acid dye include C.I. I. Acid Yellow 11, C.I. I. Acid Yellow 23, C.I. I. Acid Green 3 (edible green No. 1), C.I. I. Acid Green 5 (edible green No. 2), C.I. I. Acid Green 9, C.I. I. Acid Green 16, C.I. I. Acid Green 19, C.I. I. Acid Green 25 etc.

  In the case of an acid dye, a more preferable molecular weight range is 300 to 750. More preferably, it is the range of 350-700. By setting the molecular weight within this range, a colorant having a good balance between weather resistance and coloring power can be obtained, which is preferable.

In the case of a red pixel, a red pixel can be obtained by salt formation with a safranin basic dye or a phloxine basic dye. At this time, preferred acid dyes are C.I. I. Acid Yellow 11 (molecular weight 380), C.I. I. Acid Yellow 23 (molecular weight 534), and the like.
In the case of a blue pixel, a blue pixel can be obtained by salt formation with the triarylmethane basic dye or methylene blue basic dye.

  In the case of a green pixel, the C.I. Green pixels can be obtained by salt formation with triarylmethane basic dyes such as I. Basic Green 1 (Brilliant Green GX) and 4 (Malachite Green). Preferred acid dyes at this time include C.I. I. Acid Green 3 (edible green No. 1) (molecular weight 690), C.I. I. Acid Green 5 (edible green No. 2) (molecular weight 761), C.I. I. Acid Green 9 (molecular weight 724), C.I. I. Acid Green 16 (molecular weight 560), C.I. I. Acid Green 19 (molecular weight 625), C.I. And I. Acid Green 25 (molecular weight 622).

(Salt making)
These salt-forming compounds of a basic dye and a counter compound can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
An example of a triarylmethane-based basic dye is that a triarylmethane-based basic dye is dissolved in water, then an organic sulfonic acid or (organic sodium sulfonate) solution is added, and the chlorination treatment can be performed while stirring. That's fine. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane-based basic dye and the sulfonic acid group (—SO ₃ H) portion of the organic sulfonic acid are bonded is obtained.
Here, the organic sulfonic acid can be dissolved in an alkali solution such as sodium hydroxide before the salt-forming treatment and used as a form of sodium sulfonate (—SO ₃ Na). In the present invention, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) which is sodium sulfonate are also synonymous.

<Photopolymerizable monomer (D)>
Examples of the photopolymerizable monomer (D) used in the present invention include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl succinic acid. , 2-acryloyloxypropyl succinic acid, 2-methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol Acrylate, methoxypropylene glycol methacrylate, methoxydi Propylene glycol acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and commercially available products such as 2-acryloyloxyethyl succinic acid (trade name M-5300) And monofunctional monomers.
These monofunctional monomers can be used singly or as a mixture of two or more at any ratio as required.

  The photopolymerizable monomer (D) used in the present invention includes ethylene glycol di (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, 1,4-butanediol di ( Examples thereof include bifunctional monomers such as (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and epoxy acrylate.

  The photopolymerizable monomer (D) used in the present invention includes trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentane. Examples thereof include tri- or higher functional monomers such as monohydroxy oligoacrylates such as methacrylate or monohydroxy oligomethacrylates.

The photopolymerizable monomer (D) used in the present invention may include a polyfunctional monomer having an acidic group. For example, a free hydroxyl group-containing poly (meth) of polyhydric alcohol and (meth) acrylic acid. Examples include esterified products of acrylates and dicarboxylic acids; esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth) acrylates, and the like.
Specific examples include monomethyl oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

  These photopolymerizable monomers (D) can be used alone or in combination of two or more.

  The photopolymerizable monomer (D) used in the present invention is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the pigment in the color filter coloring composition, and is photocurable and developable. From the viewpoint, it is more preferably 10 to 200 parts by weight.

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) of the present invention is a compound that initiates polymerization of a photopolymerizable functional group by generating radicals, cations, and anions upon irradiation with light.

As a thing generating a radical among photoinitiators (E),
For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)- Acetophenone compounds such as butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin compounds such as ether, benzyl dimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. Thioxanthone compounds, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro) Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4 Triazine compounds such as' -methoxystyryl) -6-triazine, 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime) ], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine, an electron-withdrawing substitution on the phenyl group described in Japanese Patent Application No. 2010-054456 Oxime ester compounds such as N-phenylcarbazole skeleton oxime ester having a group, phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide 2,2′-bis (o-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p Examples include imidazole compounds such as -methylphenyl) biimidazole, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, and titanocene compounds.

As a thing generating a cation among photoinitiators (E),
Examples include onium salt compounds. Examples of onium salt compounds include sulfonium salt compounds, iodonium salt compounds, phosphonium salt compounds, diazonium salt compounds, pyridinium salt compounds, benzothiazolium salt compounds, sulfoxonium salt compounds, and ferrocene compounds. These structures are not particularly limited, and may have a polyvalent cation structure such as a dication, and known counter anions can be appropriately selected and used.
Acid generators other than onium salts include nitrobenzyl sulfonates, alkyl or aryl-N-sulfonyloxyimides, optionally halogenated alkyl sulfonate esters, 1,2-disulfones, oxime sulfonates Benzoin tosylates, β-ketosulfones, β-sulfonylsulfones, bis (alkylsulfonyl) diazomethanes, iminosulfonates, imidosulfonates, trihaloalkyltriazines and other compounds having a trihaloalkyl group, etc. It can be mentioned, but is not limited to these.

  Specific examples include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium, p-toluenesulfonate, N, N-dimethyl-N-benzylanilinium. Antimony hexafluoride, N, N-dimethyl-N-benzylanilinium tetrafluoride, N, N-dimethyl-N-benzylpyridinium antimony hexafluoride, N, N-diethyl-N-benzyltrifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoride antimony, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony, Tiltriphenylphosphonium antimony hexafluoride, antimony tetrabutylphosphonium hexafluoride, boron triphenylsulfonium tetrafluoride, antimony triphenylsulfonium hexafluoride, arsenic triphenylsulfonium hexafluoride, tri (4-methoxyphenyl) sulfonium hexa Arsenic fluoride, diphenyl (4-phenylthiophenyl) sulfonium arsenic hexafluoride, Adeka optomer SP-150 (manufactured by ADEKA), Adeka optomer SP-170 (manufactured by ADEKA), Adeka optomer CP -66 (manufactured by ADEKA Corporation), Adekaoptomer CP-77 (manufactured by ADEKA Corporation), Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun-Aid SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd.) ), Sun Aid S -100L (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun-Aid SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), CYRACURE UVI-6974 (manufactured by Union Carbide), CYRACURE UVI-6990 (manufactured by Union Carbide), UVI-508 (manufactured by General Electric), UVI-509 (manufactured by General Electric), FC-508 (manufactured by Minnesota Mining & Manufacturing), FC-509 (Minnesota Mining & Manufacturing) ), CD-1010 (manufactured by Sartomer), CD-1011 (manufactured by Sartomer) and CI series (manufactured by Nippon Soda Co., Ltd.), diphenyliodonium hexafluoroarsenide, di-4-chlorophenyliodonium hexafluoroarsenide, Di-4-Bromofu Nyliodonium arsenic hexafluoride, phenyl (4-methoxyphenyl) iodonium arsenic hexafluoride, UVE series manufactured by General Electric, FC series manufactured by Minnesota Mining & Manufacturing, UV- manufactured by Toshiba Silicone 9310C and Photoinitiator 2074 manufactured by Rhodia, etc. can be mentioned, but are not limited thereto.

  Examples of the photopolymerization initiator (E) that generate anions include o-nitrobenzoin carbamate, benzoin carbamate, α, α-dimethylbenzyloxycarbamoylamine, o-acyloxime, formanilide derivatives, α-ammonium acetophenone. Etc.

  As these photopolymerization initiators (E), those that generate radicals, cations and anions can be used alone or in combination. Moreover, it can be used 1 type or in mixture of 2 or more types by arbitrary ratios as needed. The photopolymerization initiator (E) is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 7 parts by weight in 100 parts by weight of the solid content in the color filter coloring composition. If the amount is less than 0.01 part by weight, the photocuring reactivity may be poor and polymerization may not proceed. If the amount exceeds 10 parts by weight, transparency may deteriorate due to the yellowing of the initiator.

<Sensitizer (H)>
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer (H). Content of a sensitizer (H) can be used in the quantity of 1-100 weight part with respect to 100 weight part of photoinitiators (E) in the coloring composition for color filters.

  Sensitizers (H) include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, Examples include spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler ketone derivatives, and the like.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained. The sensitizer (G) may contain two or more sensitizers in any ratio.

<Organic solvent>
The solvent sufficiently disperses the colorant in the resin, and the filter composition is formed by applying the colored composition of the present invention on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Used to make things easier.

Examples of the organic solvent that can be used in the present invention include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, Examples include butyl acetate, benzene, toluene, ethylbenzene, xylene, cyclohexane, hexane, octane, cyclomethane, chloroform, dimethylformamide, dimethylacetamide, acetonitrile, dimethyl sulfoxide, and the like. These can be used alone or in combination of two or more. In particular, it is preferable to use a ketone-based, ester-based, or ether-based solvent because the solubility of other components is good.

  Other usable organic solvents include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2- Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1 , 3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene , M-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N- Tylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene Glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol Cole monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate , Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl Pill ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, Propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate , Isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters and the like are preferably used. These can be used alone or in combination.

In consideration of the drying property of the organic solvent, it is preferable to include a high boiling point solvent of 160 ° C. or higher in the die coating method, screen printing method, offset printing method, gravure printing method, etc., for example, 3-methoxy-3-methyl- 1-butanol (bp 174 ° C.), 1,3-butanediol (bp 203 ° C.), 3-methyl-1,3-butanediol (bp 203 ° C.), 2-methyl-1,3-propanediol (bp 213 ° C.), diisobutyl Ketone (bp 168.1 ° C.), ethylene glycol monobutyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203. 3 ° C), diethyleneglyco Rumonomethyl ether (bp 194.0 ° C.), diethylene glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2) ° C), propylene glycol diacetate (bp 190.0 ° C), dipropylene glycol monomethyl ether (bp 187.2 ° C), dipropylene glycol monoethyl ether (bp 197.8 ° C), dipropylene glycol monopropyl ether (bp 212.0 ° C) ), Dipropylene glycol dimethyl ether (bp 175 ° C.), tripropylene glycol monomethyl ether (bp 206.3 ° C.), 3-ethoxypro Ethyl on acid (bp1
69.7 ° C.), 3-methoxybutyl acetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1) C), N-methylpyrrolidone (bp 202 ° C.), p-chlorotoluene (bp 162.0 ° C.), o-diethylbenzene (bp 183.4 ° C.), m-diethylbenzene (bp 181.1 ° C.), p-diethylbenzene (bp 183.8). ° C), o-dichlorobenzene (bp180.5 ° C), m-dichlorobenzene (bp173.0 ° C), n-butylbenzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butyl Benzene (bp 169.1 ° C.), cyclohexanol (bp 161.1 ° C.), Black hexyl acetate (bp173 ℃), include such methylcyclohexanol (bp174 ℃), preferably high-boiling solvent or 160 ° C. 5 to 50 wt% based on the total amount of solvent.

  Among the above organic solvents, when considering the dispersion characteristics / solubility / dryability of the coloring material, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. It is preferable to use aromatic alcohols such as glycol acetates and benzyl alcohol, and ketones such as cyclohexanone.

  The amount of the organic solvent used is preferably such that the solid content concentration of the color filter coloring composition is 5 to 50% by weight. By setting the solid content concentration of the coloring composition for a color filter in such a range, it is possible to provide a highly smooth film or fine pattern having a more uniform thickness. That is, if the solid content concentration exceeds 50% by weight, the leveling property when applying the color filter coloring composition, the smoothness of the resulting film or fine pattern, and the transparency may be lowered. On the other hand, if the solid content concentration is less than 5% by weight, a film and a pattern having a predetermined thickness may not be obtained.

<Pigment (F)>
As a pigment contained in the coloring composition for a color filter of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, a pigment having high color developability and high heat resistance is preferable, and an organic pigment (F) is usually used.
Below, the specific example of the organic pigment which can be used for the coloring composition for color filters of this invention is shown with a color index number.

  Examples of the coloring composition for blue color filter for forming the blue filter segment include CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, Blue pigments such as 64 and 80 can be used. Purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination with the coloring composition for the blue color filter.

  From the viewpoint of obtaining sufficient color reproducibility, the preferable concentration of the pigment component is 10% by weight or more, more preferably 15% by weight based on the total nonvolatile components (100% by weight) of the coloring composition for color filter of the present invention. % Or more, and most preferably 20% by weight or more. Moreover, since the stability of the coloring composition for color filters is improved, the concentration of the preferred pigment component is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.

<Multifunctional thiol (I)>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups.
When the polyfunctional thiol is used together with a radical polymerizable compound among the above-mentioned photopolymerization initiators (E), a thiyl radical that acts as a chain transfer agent in the radical polymerization process after light irradiation and is not easily inhibited by polymerization by oxygen. Since it generate | occur | produces, the coloring composition for color filters obtained becomes high sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

  For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaeryth Tallhexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- ( N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types.

The content of the polyfunctional thiol is preferably 0.05 to 100 parts by weight, more preferably 1.0 to 50.0 parts by weight with respect to 100 parts by weight of the pigment.
By using 0.05 part by weight or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Epoxy resin (J)>
As the epoxy resin, known ones can be used. Among the photopolymerizable monomers (D), compounds having an epoxy group, compounds having an alicyclic epoxy group, aliphatic compounds described as those that undergo cationic polymerization. An epoxy resin, a compound having an oxetanyl group, a compound described as a compound having an epoxy group among the compounds (a3) containing one or more functional groups capable of reacting with the hydroxy group, and the like can be used. Examples of products that are preferably used when used as a color filter coloring composition include the following.

Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (the above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256, JER 1032H60, JER 157S65, JER 157S70 , JER152, JER154 (above are trade names; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (trade names; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H, EPPN-501H, EPPN-201, EOCN-102S , EOCN-103S, EOCN-104S, EOCN-1020, XD-1000, NC-3000, (trade name; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150, EHPE-3150CE (trade name; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-901, EX-810, EX-830, EX-851, EX-611, EX-512, EX-421, EX-411, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation).

  In that case, the total amount of the β-hydroxyalkylamide (A), the polymer (B) containing a carboxyl group, the thermoplastic resin not containing a carboxyl group and the thermosetting resin is 100 weights of the pigment in the color filter coloring composition. It can be used in an amount of 1 to 400 parts by weight, preferably 1 to 250 parts by weight with respect to parts.

<Storage stabilizer (K)>
The coloring composition for a color filter of the present invention can contain a storage stabilizer. By containing a storage stabilizer, the viscosity with time of the composition can be stabilized. Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and their methyl ethers such as oxalic acid. Used alone or in combination.

The storage stabilizer can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the pigment in the color filter coloring composition.
By using 0.01 parts by weight or more of the storage stabilizer, the temporal stability of the color filter coloring composition is improved.

<Ultraviolet absorber (L) / polymerization inhibitor (M)>
The coloring composition for a color filter of the present invention can contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled. Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, etc. Hydroxyphenyltriazine, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, Benzotriazoles such as 2- (3-tbutyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4- Benzophenone series such as hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, salicylate series such as phenyl salicylate, p-tert-butylphenyl salicylate, Cyanoacrylates such as ethyl-2-cyano-3,3′-diphenylacrylate, 2,2,6,6, -tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis (2, 2,6,6-tetramethyl-4-piperidyl) -sebacate, poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] And hindered amines such as [(2,2,6,6-tetramethyl-4-piperidinyl) imino] and the like. Or in a mixture used. Examples of the polymerization inhibitor include methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, t-butylcatechol and the like. Hydroquinone derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxyl Min such nitroso compounds and their ammonium salts or aluminum salts and the like, and used alone or in combination.

  The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the pigment in the color filter coloring composition. By using 0.01 part by weight or more of the ultraviolet absorber or the polymerization inhibitor, better resolution can be obtained.

<Leveling agent (N)>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in 100% by weight of the total weight of the coloring composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

  The coloring composition for a color filter of the present invention can contain an amine compound having a function of reducing dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Pigment dispersion (G)>
The coloring composition for a color filter of the present invention finely disperses a pigment in a dye carrier such as a resin and / or a solvent using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor. To produce a pigment dispersion, β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, a dye (C), and, if necessary, a photopolymerizable monomer (D). , A photopolymerization initiator (E), an organic solvent, and in some cases, a sensitizer, a polyfunctional thiol, an ultraviolet absorber, a polymerization inhibitor, a storage stabilizer, and other components can be mixed and stirred. Moreover, the coloring composition for color filters containing 2 or more types of pigments mixes each pigment dispersion separately finely in a pigment | dye carrier and / or a solvent, Furthermore, (beta) -hydroxyalkylamide (A) , A polymer (B) containing a carboxyl group, a dye (C), and if necessary, a photopolymerizable monomer (D), a photopolymerization initiator (E), an organic solvent and the like can be produced by mixing and stirring. it can.
You may use the polymer (B) containing a carboxyl group as a pigment | dye carrier at the time of manufacturing a pigment dispersion.

When the pigment is dispersed in a dye carrier such as a resin and / or a solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. The dispersion aid is excellent in dispersion of the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, the color composition for a color filter is obtained by dispersing the pigment in a resin and / or solvent using the dispersion aid. When an object is used, a color filter excellent in transparency can be obtained.
The dispersing aid can be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment.

[Resin type pigment dispersant]
The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkylene imines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

[Surfactant]
Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxy Ethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as nolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline These can be used alone or in admixture of two or more.

[Pigment derivatives]
The pigment derivative is a compound in which a substituent is introduced into an organic pigment, and the organic pigment also includes light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone that are not generally called pigments. Examples of the pigment derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

<Coloring composition for photosensitive color filter>
The coloring composition for photosensitive color filter of the present invention can be prepared in the form of a solvent developing type or alkali developing type colored resist material.
The colored resist material includes β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, a photopolymerization initiator (E), and, if necessary, a photopolymerizable monomer (D), A composition containing an organic solvent contains a salt-forming compound [C1] composed of a triarylmethane basic dye and a counter compound having a molecular weight in the range of 200 to 3,500.

  The photosensitive coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

<Color filter manufacturing method>
Next, a method for producing a color filter using the coloring composition for photosensitive color filter of the present invention will be described.
The color filter of the present invention is provided with a filter segment or a black matrix formed from the coloring composition for photosensitive color filter of the present invention on a transparent substrate, and a general color filter is at least one red filter. A segment, at least one green filter segment, and at least one blue filter segment, or at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

[substrate]
As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used. Although the heating conditions can also be changed depending on the types of components used in the coloring composition for photosensitive color filters, the addition amount (blending amount), etc., the temperature is usually in the range of 50 to 300 ° C. Heat curing is preferably performed under conditions of 1 to 10 hours, and more preferably, the temperature is in the range of 100 to 250 ° C. and the heat curing conditions are 0.5 to 5.0 hours.

[Photolithography]
Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the coloring composition for photosensitive color filter prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by a coating method such as spray coating, spin coating, slit coating, roll coating, etc. Is applied so as to be 0.2 to 10 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than printing methods such as a screen printing method, an offset printing method, and a gravure printing method.

[Developer]
In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, after applying and drying the photosensitive color filter coloring composition of the present invention, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried, followed by polymerization with oxygen. Ultraviolet exposure can also be performed after forming a film that prevents inhibition.

[Printing method]
The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  The use of the coloring composition for a color filter of the present invention is not particularly limited. In addition to a color filter and a black matrix, a color filter protective film, a photo spacer, a protrusion for liquid crystal alignment, a microlens, an optical hard coat, UV It can be used to produce inks, photosensitive lithographic printing plates, various coatings and the like. In addition, adhesives and adhesive sheets for electronic materials, including the periphery of flexible printed wiring boards, coating agents, solder resists for circuit coating, coverlay films, electromagnetic wave shielding adhesives, plating resists, and interlayer electrical insulation materials for printed wiring boards It can also be used for optical waveguides, photothermal dual-curing potting agents and the like.

  The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

(Molecular weight of resin)
The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

(NMR measurement method)
All NMR measurements in the examples were performed in DMSO-d6 using 1H-NMR measurement using JNM-ECX400P manufactured by JEOL. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values in terms of polystyrene measured by GPC-8020 manufactured by Tosoh Corporation.

(IR measurement method)
All IR measurements in the examples were performed using Spectrum One manufactured by PerkinElmer.

(Measuring method of average primary particle size of pigment)
The average primary particle diameter of the pigment was measured (calculated) by the following method.
A sample for measurement was prepared by adding propylene glycol monomethyl ether acetate to the pigment powder, adding a small amount of dispersant Disper BYK-161 (BIC Chemie's dispersant), and treating with ultrasonic waves for 1 minute. Using a transmission (TEM) electron microscope, three photographs (for 3 fields of view) in which primary particles of 100 or more pigments could be confirmed were prepared, and the size of 100 primary particles was measured sequentially from the upper left. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment are measured in nm units, the average is the primary particle diameter of the pigment particles, and a total of 300 distributions are created in increments of 5 nm. The median value in increments of 5 nm (for example, 8 nm in the case of 6 nm or more and 10 nm or less) was approximated as the particle diameter of those particles, and the number average particle diameter was calculated by calculating based on each particle diameter and the number thereof.

<Synthesis of β-hydroxyalkylamide (A)>
(Synthesis Example 1: β-hydroxyalkylamide solution (A-1))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was carried out, and the integration ratio of the methylene group of the ester bond (near δ = 4.1) and the methyl group derived from 2-ethylhexanoic acid (near δ = 0.85) was 2: 6. From this, it was confirmed that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-1 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 2: β-hydroxyalkylamide solution (A-2))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-2 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 3: β-hydroxyalkylamide solution (A-3))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 216 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-3 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 4: β-hydroxyalkylamide solution (A-4))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 288 parts of 2-ethylhexanoic acid was dripped in this over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-4 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 5: β-hydroxyalkylamide solution (A-5))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. While blowing dry air, a mixture of 144 parts of 2-ethylhexanoic acid, 270 parts of 2-acryloyloxyethyl hexahydrophthalate (light acrylate HOAHH manufactured by Kyoeisha Chemical Co., Ltd.), and 0.4 part of methoquinone was added from the dropping device. It was added dropwise over time. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-5 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 6: β-hydroxyalkylamide solution (A-6))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 119 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic-N), 2-acryloyloxyethyl succinic acid (HO-MS, Kyoeisha Chemical Co., Ltd.) A mixture of 173 parts and methoquinone 0.3 part was added dropwise from a dropping device over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-6 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 7: β-hydroxyalkylamide solution (A-7))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. While blowing dry air, 133 parts of Ricacid DDSA (manufactured by Shin Nippon Chemical Co., Ltd.) was added dropwise from the dropping device over 1 hour. After the dropping, a mixture of 78 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was added dropwise over 1 hour from the dropping device. After dropping, the mixture was stirred at 150 ° C. for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-7 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 8: β-hydroxyalkylamide solution (A-8))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 361 parts of n-octanoic acid was dripped over 1 hour from the dripping apparatus. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. A mixture of 636 parts of this liquid product, 49 parts of maleic anhydride, 4 parts of dimethylbenzylamine and 0.4 part of methoquinone was heated again to 100 ° C. while blowing dry air and stirred for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-8 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 9: β-hydroxyalkylamide solution (A-9))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. To 447 parts of this liquid product, a mixture of 141 parts of 2-acryloyloxyethyl isocyanate (Karenz AOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was dropped from a dropping device over 1 hour. It stirred at 100 degreeC after dripping for 1 hour. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, the temperature was lowered to 60 ° C., and propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-9 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 10: β-hydroxyalkylamide solution (A-10))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. 158 parts of 3,5,5-methylhexanoic acid (Kyowa Hakko Chemical Co., Ltd. Kyowanoic-N) was added dropwise from the dropping device over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. In a second reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, gas introduction tube, 222 parts of isophorone diisocyanate, 116 parts of 2-hydroxyethyl acrylate, 0.1 part of tetrabutyl titanate The reaction was carried out at 60 ° C. for 8 hours while blowing dry air. 461 parts of the above slurry product was added to the second reaction vessel and reacted at 60 ° C. for 8 hours. 1H-NMR measurement was performed to confirm that the target product was produced. Further, the structure was confirmed by IR. Thereafter, propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-10 containing a uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 11: β-Hydroxyalkylamide Solution (A-11))
225 parts of dimethyl suberate, 234 parts of diethanolamine, 10 parts of potassium hydroxide, and 300 parts of toluene are placed in a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube. The tube was filled with toluene and heated to reflux while blowing nitrogen to remove water produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-11 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 12: β-hydroxyalkylamide solution (A-12))
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, dimethyl sebacate 256 parts, diethanolamine 234 parts, potassium hydroxide 10 parts, toluene 300 parts, and Dean Stark The tube was filled with toluene and heated to reflux while blowing nitrogen to remove water produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-12 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

(Synthesis Example 13: β-hydroxyalkylamide solution (A-13))
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 287 parts of dimethyl dodecanedioate, 234 parts of diethanolamine, 10 parts of potassium hydroxide and 300 parts of toluene were added. The Stark tube was filled with toluene and heated to reflux while blowing nitrogen to remove water produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., propylene glycol monomethyl ether acetate was added to adjust the solid content to 20%. The obtained β-hydroxyalkylamide solution A-13 containing no uniform yellowish brown transparent photopolymerizable functional group was taken out.

<Synthesis of polymer (B) containing carboxyl group>
(Synthesis Example 14: Polymer solution containing carboxyl group (B-1))
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 20 parts of methacrylic acid at the same temperature, A mixture of 10 parts of methyl methacrylate, 55 parts of n-butyl methacrylate, 15 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of dropping, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. Got. After cooling to room temperature, a polymer solution B-1 containing a carboxyl group not containing a photopolymerizable functional group having a solid content of 20% was obtained by diluting with cyclohexanone. The weight average molecular weight was 40,000.

(Synthesis Example 15: Polymer solution containing carboxyl group (B-2))
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 25 parts of methacrylic acid at the same temperature, A mixture of 20 parts of 2-hydroxyethyl methacrylate, 30 parts of methyl methacrylate, 25 parts of styrene and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, the temperature of the reaction vessel was cooled to 70 ° C., and dry air was further introduced into the reaction vessel, and 24 parts of 2-methacryloyloxyethyl isocyanate, 36 parts of cyclohexanone, 0.1 part of dibutyltin dilaurate, 0.1 part of methoquinone 0.1 Then, stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the solution was diluted with cyclohexanone to obtain a polymer solution B-2 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group. The weight average molecular weight was 42,000.

(Synthesis Example 16: Polymer solution containing carboxyl group (B-3))
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and 40 parts of methacrylic acid at the same temperature, A mixture of 25 parts of methyl methacrylate, 12.5 parts of styrene, 17.5 parts of n-butyl methacrylate, 5 parts of 2-methoxyethyl acrylate, and 4 parts of 2,2′-azobisisobutyronitrile is added dropwise over 1 hour. The polymerization reaction was carried out. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 25 parts of glycidyl methacrylate, 37 parts of cyclohexanone, 1 part of dimethylbenzylamine, and 0.1 part of methoquinone were charged, and stirring was continued at the same temperature for 10 hours. After cooling to room temperature, the polymer solution B-3 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group was obtained by diluting with cyclohexanone. The weight average molecular weight was 41000.

(Synthesis example 17: Polymer solution (B-4) containing a carboxyl group)
Into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, 100 parts of cyclohexanone was heated to 80 ° C. while injecting nitrogen gas into the vessel, and 68 parts of glycidyl methacrylate at the same temperature, A mixture of 17 parts of methyl methacrylate, 7.5 parts of n-butyl methacrylate, 7.5 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and then the mixture was stirred at the same temperature for 3 hours. Obtained. Subsequently, dry air was introduced into the reaction vessel, and 55 parts of acrylic acid, 83 parts of cyclohexanone, 1 part of dimethylbenzylamine and 0.1 part of methoquinone were charged, and stirring was continued for 10 hours at the same temperature. Further, 117 parts of tetrahydrophthalic anhydride was charged and stirring was continued for 10 hours at the same temperature. After cooling to room temperature, the polymer solution B-4 containing a photopolymerizable functional group having a solid content of 20% and a carboxyl group was obtained by diluting with cyclohexanone. The weight average molecular weight was 44,000.

<Synthesis of polymer having no carboxyl group>
(Comparative Synthesis Example 1: Polymer solution having no carboxyl group (B-5))
Put 100 parts of cyclohexanone into a reaction vessel equipped with a stirrer, thermometer, dripping device, reflux condenser, and gas introduction tube, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature 2-hydroxyethyl methacrylate A mixture of 55.5 parts, 10 parts of methyl methacrylate, 19.5 parts of n-butyl methacrylate, 15 parts of benzyl methacrylate and 4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. went. After completion of dropping, the mixture was further reacted at 80 ° C. for 3 hours, and then 1 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain an acrylic resin solution. Got. After cooling to room temperature, the solution was diluted with cyclohexanone to obtain a polymer solution B-5 containing a hydroxyl group without having a carboxyl group with a solid content of 20%. The weight average molecular weight was 38000.

  The produced β-hydroxyalkylamide (A), the polymer (B) containing a carboxyl group, and the polymer having no carboxyl group are shown together in Table 1.

<Production method of fine pigment (F)>
[Blue refined pigment (F-1): PB15: 6]
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor "Lionol Blue ES") 100 parts, ground salt 800 parts, and diethylene glycol 100 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C for 12 hours. did. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (F-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

[Purple refined pigment (F-5): PV23]
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts of purple refinement | purification pigments (F-5). The average primary particle diameter of the obtained pigment was 26.4 nm.

<Method for Producing Triarylmethane Salt Formation Compound>
(Preparation of Triarylmethane Salt Formation Compound (C1-1))
Victoria Pure Blue Dye (CI Basic Blue 7) 5 g (9.73 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 30 mL of methanol and stirred with sodium naphthalenedisulfonate (Tokyo Chemical Industry Co., Ltd.) 1 .62 g (4.87 mmol) is added, and the mixture is stirred at room temperature for 1 hour to sufficiently react. Thereafter, the solution was concentrated by removing methanol with an evaporator, and then 100 mL of water was added, and the precipitate was collected by filtration and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and a salt-forming compound of Victoria pure blue dye and naphthalenedisulfonic acid, a triarylmethane-based salt-forming compound (C1-1) )

(Preparation of triarylmethane salt-forming compound (C1-2))
Victoria Pure Blue Dye (CI Basic Blue 7) 5 g (9.73 mmol) manufactured by Tokyo Chemical Industry Co., Ltd. was dissolved in 30 mL of methanol and stirred with sodium naphthalene trisulfonate (Tokyo Chemical Industry Co., Ltd.) 1.41 Add g (3.24 mmol) and stir at room temperature for 1 hour to allow sufficient reaction. Thereafter, the solution was concentrated by removing methanol with an evaporator, and then 100 mL of water was added, and the precipitate was collected by filtration and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and a salt-forming compound of Victoria pure blue dye and naphthalenetrisulfonic acid, a triarylmethane-based salt-forming compound (C1- 2) was obtained.

(Preparation of Triarylmethane Salt Formation Compound (C1-3))
2-Amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) is dissolved in a 9 mol% sodium hydroxide solution and sufficiently mixed and stirred to obtain its sodium salt. This 2-amino-1-naphthalenesulfonic acid (tobias acid) (molecular weight 223) sodium salt aqueous solution is heated to 85 ° C., and then Victoria Pure Blue dye (CI Basic Blue 7) is added dropwise little by little. The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After the Victoria pure blue dye is added dropwise, the mixture is stirred at 85 ° C. for 55 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and a salt-forming compound of Victoria pure blue dye and 2-amino-1-naphthalenesulfonic acid (tobias acid), tria A reel methane salt forming compound (C1-3) was obtained.

(Preparation of triarylmethane salt-forming compound (C1-4))
1-Amino-5-naphthalenesulfonic acid (Lorentzic acid) (molecular weight 223) is dissolved in 9 mol% sodium hydroxide solution and sufficiently mixed and stirred to obtain its sodium salt. This 1-amino-5-naphthalenesulfonic acid (Lorentzic acid) (molecular weight 223) sodium salt aqueous solution is heated to 85 ° C., and then Victoria Pure Blue dye (CI Basic Blue 7) is added dropwise little by little. The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After the Victoria pure blue dye is added dropwise, the mixture is stirred at 85 ° C. for 55 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and a salt-forming compound of Victoria pure blue dye and 1-amino-5-naphthalenesulfonic acid (Lorentzic acid), tria A reel methane salt forming compound (C1-4) was obtained.

(Preparation of Triarylmethane Salt Formation Compound (C1-5))
1-Hydroxy-4-naphthalenesulfonic acid (NW acid) (molecular weight 224) is dissolved in a 9 mol% sodium hydroxide solution and sufficiently mixed and stirred to obtain its sodium salt. This 1-hydroxy-4-naphthalenesulfonic acid (NW acid) (molecular weight 224) sodium salt aqueous solution is heated to 85 ° C., and then Victoria Pure Blue dye (CI Basic Blue 7) is added dropwise little by little. The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After the Victoria pure blue dye is added dropwise, the mixture is stirred at 85 ° C. for 55 minutes to sufficiently react. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a drier, and a salt-forming compound of Victoria pure blue dye and 1-hydroxy-4-naphthalenesulfonic acid (NW acid), tria A reel methane salt forming compound (C1-5) was obtained.

(Preparation of Triarylmethane Salt Formation Compound (C1-6))
Phosphotungstic acid (molecular weight 2880) is dissolved in a 7-15 mol% sodium hydroxide solution and sufficiently mixed and stirred to obtain its sodium salt. After heating this sodium phosphotungstate aqueous solution to 70-90 ° C., Victoria Pure Blue dye (CI Basic Blue 7) is added dropwise little by little. The Victoria Pure Blue dye may be dissolved in water and used as an aqueous solution. After dripping Victoria pure blue dye, it stirs at 70-90 degreeC for 40-60 minutes, and fully reacts. In order to confirm the end point of the reaction, it can be judged that the salt-forming compound was obtained with the reaction solution dropped on the filter paper and the point where the bleeding disappeared as the end point. The mixture is allowed to cool to room temperature with stirring, and then suction filtered and washed with water. After washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and a salt-forming compound of Victoria pure blue dye and phosphotungstic acid, a triarylmethane-based salt-forming compound (C1-6) )

<Method for Producing Triarylmethane Salt-Forming Compound-Containing Solution>
(Preparation of triarylmethane salt-forming compound-containing solution (CS-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (CS-1).
Triarylmethane salt-forming compound (C1-1): 5.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 95.0 parts

(Preparation of triarylmethane salt-forming compound-containing solution (CS-2 to 7))
Hereinafter, the salt formation compound described above except that the salt formation compound is changed to a triarylmethane salt formation compound (C1-1 to 6) or a triarylmethane dye (Victoria Pure Blue Dye; CI Basic Blue 7). In the same manner as the compound-containing solution (CS-1), salt-forming compound-containing solutions (CS-2 to 7) were prepared.

  The prepared triarylmethane colorant-containing solutions are summarized in Table 2.

・樹脂型顔料分散剤 ： ８．０部
（ビックケミー・ジャパン社製 ＢＹＫ−１１１）
・ポリマー溶液（Ｂ−１） ：６０．０部
・シクロヘキサノン ：１２．０部 <Method for producing pigment dispersion>
[Blue pigment dispersion (GB)]
The mixture having the composition shown below was uniformly stirred and mixed, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then with a 5 μm filter. Filtration gave a blue pigment dispersion (GB).
Blue refined pigment (F-1): 18.0 parts Copper phthalocyanine derivative: 2.0 parts

-Resin type pigment dispersant: 8.0 parts (BYK-111 manufactured by Big Chemie Japan)
Polymer solution (B-1): 60.0 parts Cyclohexanone: 12.0 parts

[Purple pigment dispersion (G-V)]
A purple pigment dispersion (GV) was obtained in the same manner as the blue pigment dispersion (GB) using a mixture having the following composition.
-Purple refined pigment (F-5): 20.0 parts-Resin-type pigment dispersant: 8.0 parts (BYK-111 manufactured by BYK Japan)
Polymer solution (B-1): 60.0 parts Cyclohexanone: 12.0 parts

<Preparation of photosensitive coloring composition>
[Example 1]
(Preparation of colored composition 1)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a colored composition 1.
Triarylmethane salt-forming compound-containing solution (CS-1): 42.7 parts β-hydroxyalkylamide (A-9): 2.8 parts Polymer containing carboxyl group (B-2): 26.4 parts Photopolymerization initiator: 0.8 part (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1-
[4- (4-morpholinyl) phenyl] -1-butanone (“Irgacure 379” manufactured by Ciba Japan)
Sensitizer: 0.2 part (2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.))
Photopolymerizable monomer: 5.0 parts (dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.))
Solvent: 22.095 parts (propylene glycol monomethyl ether acetate (PGMAc))
Leveling agent ("BYK-330" manufactured by Big Chemie): 0.005 part

[Examples 2 to 22, Comparative Examples 1 to 4]
(Preparation of colored compositions 2 to 27)
Hereinafter, the colored composition of Example 1 except that the triarylmethane salt-forming compound-containing solution, β-hydroxyalkylamide, polymer solution, and pigment dispersion were changed to the types and blending amounts (parts by weight) shown in Table 3. In the same manner as Product 1, Colored Compositions 2 to 26 were produced.

<Evaluation of photosensitive coloring composition>
The resulting colored composition was evaluated for brightness, heat resistance, and solvent resistance by the following methods. The results are shown in Table 4.

(Brightness evaluation)
The obtained colored composition was applied onto a glass substrate in a film thickness such that x = 0.1396 and y = 0.0943 using a C light source, and was subjected to ultraviolet exposure through a mask having a predetermined pattern. Thereafter, an alkali developer was sprayed by spraying to remove the uncured portion and form a desired pattern. About the obtained coating film, the brightness before and behind heat processing at 230 degreeC for 20 minutes was measured with the microspectrophotometer ("OSP-SP200" by Olympus Optical Co., Ltd.).
In the evaluation results, ○ is good, Δ is a level that does not cause a problem in use, × corresponds to a state where it cannot be used, ○: 12.0 or more, Δ: 11.5 or more, but less than 12.0 ×: 11 Less than 5

(Heat resistance evaluation)
The substrate obtained by lightness evaluation was measured with a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.) before and after heat treatment at 230 ° C for 60 minutes in an oven, and the difference from lightness before and after heat treatment at 230 ° C for 20 minutes It was measured. The rank of evaluation is as follows. In the evaluation results, ◯ is good, Δ is a level that does not cause a problem in use, and × corresponds to a state where it cannot be used.
Lightness difference (ΔY) = | (Lightness Y after heat resistance) − (Lightness Y before heat resistance) |
○: Less than 0.4 Δ: 0.4 or more and less than 0.8 ×: 0.8 or more

(Chemical resistance evaluation)
The substrate obtained by the lightness evaluation was measured for chromaticity ([L * (1), a * (1), b * (1)]) with a C light source by a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). ). This substrate was immersed in N-methyl-2-pyrrolidone at room temperature for 5 minutes, washed with running water for 1 minute, and then air-dried. Measure the chromaticity ([L * (2), a * (2), b * (2)]) of the substrate obtained, and set the difference (color difference) from the chromaticity of the substrate before immersion to JIS Z 8729. Calculated in accordance with the above.
The rank of evaluation is as follows. In the evaluation results, ◯ is good, Δ is a level that does not cause a problem in use, and × corresponds to a state where it cannot be used.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
○: ΔEab * is less than 3 Δ: ΔEab * is 3 or more and less than 8 ×: ΔEab * is 8 or more

  As shown in Table 4, all of the photosensitive compositions for color filters of Examples 1 to 7 and Examples 9 to 22 had good brightness, heat resistance, and chemical resistance.

  The photosensitive composition of Example 8 was inferior in heat resistance and chemical resistance. It is considered that this is because β-hydroxyalkylamide (A) is too small and the amount of the thermosetting reaction with the polymer (B) containing a carboxyl group is smaller than in Examples 1 and 7.

  The resist materials of Comparative Examples 1 to 4 had poor results in any or all of the lightness, heat resistance, and chemical resistance physical properties, and those that satisfy the practical level were not obtained.

  Comparative Example 1 was a composition containing a pigment dispersion instead of the triarylmethane colorant-containing solution, and although the heat resistance and chemical resistance were excellent, the lightness was inferior.

Comparative Example 2 was a composition that did not contain β-hydroxyalkylamide (A), and resulted in greatly inferior heat resistance and chemical resistance. This is considered to be because when the β-hydroxyalkylamide (A) is not present, the thermosetting reaction with the polymer (B) containing a carboxyl group does not occur.
Comparative Example 3 is a composition in which β-hydroxyalkylamide (A) and a polymer not containing a carboxyl group are combined, and this also resulted in greatly inferior heat resistance and chemical resistance. This is considered to be because the thermosetting reaction does not occur between the β-hydroxyalkylamide (A) and the polymer (B-5) containing no carboxyl group.
Accordingly, the β-hydroxyalkylamide (A) and the polymer (B) containing a carboxyl group are essential elements for maintaining heat resistance and chemical resistance.

  Comparative Example 4 is a composition (CS-7) that does not contain a counter compound having a molecular weight in the range of 200 to 3500 in the triarylmethane salt-forming compound, and has high brightness, particularly heat resistance and chemical resistance. The result was inferior.

  As described above, a coloring composition for a color filter comprising at least a β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, and a colorant comprising a dye (C). By combining the coloring composition for a color filter, the dye (C) is a triarylmethane basic dye and a salt-forming compound [C1] comprising a counter compound having a molecular weight in the range of 200 to 3,500. A high-quality color filter having excellent heat resistance and chemical resistance can be obtained.

Claims (10)

A coloring composition for a color filter comprising a β-hydroxyalkylamide (A), a polymer (B) containing a carboxyl group, and a colorant comprising a dye (C),
A coloring composition for a color filter, wherein the dye (C) is a salt-forming compound [C1] comprising a triarylmethane basic dye and a counter compound having a molecular weight in the range of 200 to 3,500.   The coloring composition for a color filter according to claim 1, wherein at least one of β-hydroxyalkylamide (A) or a polymer (B) containing a carboxyl group contains a photopolymerizable functional group.   Furthermore, the coloring composition for color filters of Claim 1 or 2 containing a photopolymerizable monomer (D) and / or a photoinitiator (E). The colored composition for a color filter according to claim 1, wherein the β-hydroxyalkylamide (A) is a compound represented by the following general formula (1).
General formula (1)

[Wherein X is an n-valent group consisting of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, n is an integer of 2 to 6, and R ¹ and R ² are each independently hydrogen Represents an atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (2), or a group represented by the general formula (3), and one or more nitrogen At least one of the one or more R ¹ and R ² bonded to the atom is a group represented by the general formula (2). ]

General formula (2)

General formula (3)

[Wherein R ^{3 to} R ⁶ each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxyl group, and R ⁷ is a residue of a compound having a functional group capable of reacting with a hydroxyl group. Represents. ]]   In the compound having a functional group capable of reacting with the hydroxyl group, the functional group capable of reacting with the hydroxyl group is a carboxyl group, an isocyanate group, a carboxylic acid anhydride group, an acid halide group, a carboxylic acid tertiary alkyl ester group, The coloring composition for a color filter according to claim 4, wherein the coloring composition is at least one selected from the group consisting of a hydroxymethylamino group, an alkoxysilyl group, and an epoxy group.   The colored composition for a color filter according to claim 4 or 5, wherein the compound having a functional group capable of reacting with a hydroxyl group is a monofunctional isocyanate or a monofunctional carboxylic acid. The compound having a functional group capable of reacting with the hydroxyl group is a compound represented by at least one selected from the group consisting of the following general formula (4), general formula (5) and general formula (6). The coloring composition for color filters according to any one of claims 4 to 6.
General formula (4)

[Wherein, R ⁸ represents a linear, cyclic or branched saturated or unsaturated hydrocarbon group having 2 to 18 carbon atoms. ]

General formula (5)

[Wherein R ⁹ is a hydrogen atom or a methyl group, and R ¹⁰ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic group. R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group. ]

General formula (6)

[In the formula, R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a group represented by the general formula (7) or a group represented by the general formula (8). ]

General formula (7)

Wherein, n ¹ is an integer of 1-2. ]

General formula (8)

[Wherein R ¹⁴ represents a linear or branched alkylene group having 2 to 8 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group, and R ¹⁵ represents the number of carbon atoms. 6-13 linear or branched alkylene groups, divalent alicyclic hydrocarbon groups, or divalent aromatic hydrocarbon groups. ]]   The colored composition for a color filter according to any one of claims 4 to 7, wherein the compound having a functional group capable of reacting with a hydroxyl group has a photopolymerizable functional group.   β-hydroxyalkylamide (A) is (a-1) a divalent or higher carboxylic acid or derivative thereof, and (a-2) a primary or secondary amine having one or more hydroxyl groups at the β-position, (A-3) a compound obtained by reacting a part of the hydroxyl group of (a-3) β-hydroxyalkylamide obtained by amidation with a compound having one or more functional groups capable of reacting with hydroxyl group (a-4) The coloring composition for a color filter according to claim 1, wherein the coloring composition is a coloring composition.   A color filter comprising a filter segment or a black matrix formed from the colored composition according to claim 1 on a transparent substrate.