KR20150024305A - Coloring material dispersed liquid and photosensitive coloring resin composition - Google Patents

Abstract

A colored material dispersion and a photosensitive colored resin composition having excellent storage stability are provided, and a colored material dispersion liquid exhibiting excellent plate making characteristics when a colored film is formed using the photosensitive colored resin composition. (B) having a tertiary amino group in the side chain and a structure represented by the formula (A) having at least an ethylenically unsaturated group in the side chain, (D) having a carboxyl group in a side chain and a structure (E) having an aromatic ring, the base having a quaternary ammonium salt in the side chain and / or the quaternary ammonium salt in the side chain, / 100 g, an acid value of 50 to 120 mgKOH / g, and a polystyrene reduced weight average molecular weight of 5,000 to 30,000 by gel permeation chromatography.

Description

TECHNICAL FIELD [0001] The present invention relates to a coloring material dispersion and a photosensitive colored resin composition,

The present invention relates to a colored material dispersion and a photosensitive colored resin composition using the same.

Recently, a color liquid crystal display (LCD) has been rapidly spread as a flat display for personal computers and cellular phones. For example, in a color filter for LCD, generally, a method of forming red, green, and blue colors sequentially on the surface of a transparent substrate such as glass or plastic sheet formed with a black matrix in a color pattern such as a stripe image or a mosaic image And the coloring material dispersion technique of either the coloring layer or the black matrix plays an important role.

In addition, there is an increasing demand for the color characteristics of the color filter for LCD by varying the soybeans of various display devices such as organic EL and display information thereof. Particularly, a demand for a wide color reproducibility range becomes strong, and as a coloring material for a color filter, a technique for stably dispersing a coloring material at a high concentration is important. In general, the coloring material dispersion is formed from a coloring material, a solvent, a dispersing agent, and a binder resin. By adding a large amount of a dispersing agent to the composition, it is possible to stably disperse the coloring material. However, Or the concentration of the alkali-soluble photopolymerizable resin is diluted, causing problems such as lowered sensitivity, poor curing, lowered coating film strength, poor developing property, and the like. In particular, development defects cause serious problems in production. Therefore, it was a problem to secure the stability of the pigment dispersion by imparting high dispersion stability to the binder resin itself in a small amount of the dispersant as possible in the colorant dispersion. In addition, since the demands for color characteristics have diversified recently, development of coloring materials using not only conventional organic pigments but also dyes and inorganic pigments as the coloring materials has been progressing. In the prior art, It becomes difficult to stabilize the dispersion of the particles.

In addition, in the field of touch panel displays in which technological innovation is remarkable, a black matrix is formed as a light-shielding film in the same manner as a color filter, and is generally formed by printing ink on a cover glass or a cover film facing the sensor substrate . On the other hand, there is an increasing demand for lightening the touch panel, and development of technology for simultaneously forming a light shielding film and a touch sensor on a cover glass is underway. In such a case, since it is necessary to form an electrode or the like after the black matrix is formed on the cover glass, a high heat resistance capable of withstanding the step of forming the electrode in a high-temperature vacuum state is required.

As pigments that can be used in the black matrix, titanium black such as carbon black, low-order titanium oxide or titanium oxynitride, metal oxides such as iron oxide, and other organic pigment coloring systems are used, but carbon black and titanium oxynitride are mainstream. In order to obtain a black matrix having high insulating properties, carbon black treated with titanium black or a resin or the like or a mixture of organic pigments is used as a light shielding material (for example, see Patent Document 1). However, in order to obtain a high light shielding property, it is necessary to stably disperse various pigments at a high pigment concentration, and conventional techniques are insufficient in view of long-term storage stability.

As a technique for stabilizing dispersion with a small amount of a dispersant, there is disclosed a technique of using a polymer dispersant having both an acid value and an amine value and a copolymer having an imide group and a photo-curable functional group (see, for example, Patent Document 2) It is insufficient to disperse and stabilize the coloring material made of titanium black or carbon black which is difficult. As a technique for stably dispersing the pigment even at a high pigment concentration, a technique of using an acid dispersant having an acid value and an amine dispersant having an amine value (see, for example, Patent Document 3) or both a basic block and an acidic block (For example, refer to Patent Document 4). Although it is useful as a coloring liquid for inkjet coating, it has been difficult to apply it to a coloring liquid for photolithography in which photosensitivity and developability are required.

On the other hand, as the acrylic resin for pigment dispersion, an acrylic copolymer having a carboxyl group and an acryloyl group or a methacryloyl group on the side chain (for example, see Patent Document 5), an acrylic copolymer having a acid value or an amine value at a specific molecular weight or hydroxyl group (See, for example, Patent Document 6). However, all of them are insufficient in terms of compatibility with all of dispersion stability, photosensitivity and developability.

Japanese Patent Application Laid-Open No. 2010-95716 Japanese Patent No. 4195323 Japanese Patent No. 4544292 Japanese Patent Application Laid-Open No. 2009-167303 Japanese Patent No. 3120476 Japanese Patent Application Laid-Open No. 2003-171605

The present invention has been made in view of such drawbacks of the prior art, and it is an object of the present invention to provide a coloring material dispersion liquid excellent in dispersion stability and alkali development solubility even in a composition containing a coloring material at a high concentration. Further, by using such a coloring material dispersion, a photosensitive colored resin composition excellent in storage stability and plate making characteristics is provided.

DISCLOSURE OF THE INVENTION The inventors of the present invention have made extensive studies in order to solve the problems of the prior art, and as a result, they found that the problem of the present invention can be solved by using an acrylic copolymer having a specific structure as described below in dispersing a coloring material.

That is, the object of the present invention is achieved by the following constitution.

(1) A coloring material dispersion containing at least a coloring material, an acrylic copolymer and an organic solvent, wherein the acrylic copolymer has a structure represented by the following formula (A) having at least an ethylenic unsaturated group in its side chain and a tertiary amino group (B) and / or a structure represented by the following formula (C) having a quaternary ammonium salt in its side chain, a structure (D) having a carboxyl group in its side chain, and a structure (E ), Wherein the base has a weight average molecular weight of 5 to 70 mmol / 100 g, an acid value of 50 to 120 mgKOH / g, and a polystyrene-reduced weight average molecular weight determined by gel permeation chromatography of 5,000 to 30,000.

Wherein R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ represents an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, a divalent aromatic hydrocarbon having 6 to 10 carbon atoms Lt; RTI ID = 0.0 >

Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, Bivalent aromatic hydrocarbon group; R ⁶ and R ⁷ independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms An aromatic hydrocarbon group]

Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, Each of R ¹⁰ , R ¹¹ and R ¹² is independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 8 carbon atoms, And X represents any one of bromine, chlorine, iodine, hydrogen sulfate, and hydroxide;

(2) The colored material dispersion liquid according to (1), wherein the structure (D) having a carboxyl group is represented by the following formula (D1).

Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is any one selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon chain having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon chain having 6 to 10 carbon atoms , And n represents an integer of 0 to 6, and may be a single or a mixture of plural n)

(3) The coloring material dispersion according to (1) or (2), wherein the structure (E) having an aromatic ring is represented by the following formula (E1) or (E2).

Wherein R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms , A halogen atom, an ester group, an acyl group and a nitro group]

Wherein R ¹⁷ is a hydrogen atom or a methyl group, R ¹⁸ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms , A halogen atom, an ester group, an acyl group and a nitro group]

(4) The colorant according to any one of (1), (2) and (3), wherein the acrylic copolymer further has a structure represented by the following formula (F) Re-dispersion.

Wherein R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ²¹ is an alkyl group having 2 to 40 carbon atoms.

(5) The coloring material dispersion according to (4), wherein the total number of carbon atoms of R ²⁰ and R ²¹ is 4 or more.

(6) The colorant dispersion according to any one of (3) to (5), which has a structure represented by the formula (E2).

(7) The colorant dispersion according to any one of (1) to (6), further comprising a polymer dispersant having at least a tertiary amino group in addition to the acrylic copolymer.

(8) A photosensitive colored resin composition comprising at least the colorant dispersion according to any one of (1) to (7), a polyfunctional acrylic monomer and a photo radical polymerization initiator.

(Effects of the Invention)

The coloring material dispersion liquid of the present invention has characteristics of excellent dispersion stability and solubility in alkaline development even when a colorant is contained at a high concentration. By using this coloring material dispersion liquid, a photosensitive colored resin composition excellent in storage stability and plate making property can be obtained.

Hereinafter, the present invention will be described in more detail.

The colored material dispersion of the present invention is characterized by comprising at least a coloring material, an acrylic copolymer having a specific structure, and an organic solvent.

The acrylic copolymer used in the present invention is characterized in that it has a tertiary amino group and / or a quaternary ammonium salt, a carboxyl group and an aromatic ring in the side chain and also contains an ethylenic unsaturated bond in the side chain of the acrylic copolymer.

When the acrylic copolymer used in the present invention has photosensitivity characteristics, that is, when an initiator that generates radicals, anions or cations is used together with an active energy ray such as ultraviolet (UV), the acrylic copolymer itself is subjected to a crosslinking reaction (A) having an ethylenic unsaturated group in its side chain in order to exhibit a function to be incorporated.

Wherein R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ represents an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, a divalent aromatic hydrocarbon having 6 to 10 carbon atoms Lt; RTI ID = 0.0 >

In the formula (A), R ¹ and R ² are each independently a hydrogen atom or a methyl group, and when R ¹ is hydrogen, it is an acrylic unit, and when it is a methyl group, it is a methacryl unit. R ³ is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, To 6 divalent alicyclic hydrocarbon groups and 6 to 8 divalent aromatic hydrocarbon groups.

The method of introducing the (meth) acrylic unit represented by the above formula (A) is not particularly limited and may be introduced by a usual method. For example, a method in which a (meth) acrylic copolymer in which a carboxyl group-containing unsaturated monomer is copolymerized is subjected to addition reaction with a glycidyl group-containing polymerizable unsaturated monomer. In this case, examples of the carboxyl group-containing unsaturated monomer to be copolymerized include acrylic acid and methacrylic acid, and examples of the glycidyl-containing unsaturated monomer include glycidyl acrylate and glycidyl methacrylate. In the present invention, these acrylic monomers may be used singly or as a mixture of two or more kinds.

The acrylic copolymer used in the present invention is a copolymer having a (meth) acrylic unit represented by the following formula (B) having a tertiary amino group in the side chain and / or a quaternary ammonium salt in the side chain, in order to exhibit high dispersion stability. (Meth) acrylic unit represented by the following general formula (C).

The (meth) acrylic unit represented by the formula (C) having a (meth) acrylic unit represented by the formula (B) having a tertiary amino group and a quaternary ammonium salt in the side chain has a high affinity with all the coloring materials, So that either or both of them may be introduced. In the case of application to applications requiring developability as in the present invention, it is preferable to introduce a (meth) acrylic unit of the formula (B) having a tertiary amino group from the viewpoint of easily achieving balance between development and dispersion stability.

Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, Bivalent aromatic hydrocarbon group; R ⁶ and R ⁷ independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms An aromatic hydrocarbon group]

In the formula (B), R ⁴ is a hydrogen atom or a methyl group, and when R ⁴ is hydrogen, it is an acrylic unit, and when it is a methyl group, it is a methacryl unit. R ⁵ is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, An alkylene group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

R ⁶ and R ⁷ may be the same or different from each other and are selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms , Preferably an alkylene group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

Examples of the unsaturated monomer constituting the (meth) acrylic unit having a tertiary amino group represented by the formula (B) include 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2-dipropylaminoethyl acrylate, 2-diphenylaminoethyl acrylate, 2-dibenzylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-diethylaminoethyl methacrylate, 2- 2-diphenylaminoethyl methacrylate, 2-benzylaminoethyl methacrylate, and the like, but there is no particular limitation. These (meth) acrylic monomers may be used singly or as a mixture of two or more kinds.

The (meth) acrylic unit having a tertiary amino group represented by the formula (B) can be introduced by copolymerizing an unsaturated monomer containing an amino group.

Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, Each of R ¹⁰ , R ¹¹ and R ¹² is independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 8 carbon atoms, And X represents any one of bromine, chlorine, iodine, hydrogen sulfate, and hydroxide;

In the above formula (C), R ⁸ is a hydrogen atom or a methyl group, and when R ⁸ is hydrogen, it is an acrylic unit, and when it is a methyl group, it is a methacryl unit. R ⁹ is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, An alkylene group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

R ¹⁰ , R ¹¹ and R ¹² may be the same or different from each other, and may be an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms And preferably an alkylene group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

X is selected from bromine, chlorine, iodine, hydrogen sulfate, and hydroxides, preferably bromine or chlorine.

Examples of the unsaturated monomer constituting the (meth) acrylic unit having a quaternary ammonium salt represented by the formula (C) include acrylic acid-dimethylaminoethyl methyl chloride salt, acrylic acid dimethylaminoethyl benzyl chloride salt, methacrylic acid-dimethylaminoethyl methyl chloride salt , Dimethylaminoethylbenzyl chloride salt of methacrylic acid, and the like, but there is no particular limitation. These (meth) acrylic monomers may be used singly or as a mixture of two or more kinds.

The (meth) acrylic unit having a quaternary ammonium salt represented by the formula (C) can be introduced by copolymerizing an unsaturated monomer containing a quaternary ammonium salt.

From the viewpoint of industrial use, tertiary amines such as methacrylic acid-2-dimethylaminoethyl are preferable. In the present invention, the acrylic monomer represented by the formula (B) and / or (C) may be used alone or as a mixture of two or more kinds.

The acrylic copolymer used in the present invention is required to have an acidic group such as a carboxyl group, a sulfonic acid group and a phosphoric acid group in its side chain in order to impart alkali developing property, and the present invention necessarily has a structure (D) having a carboxyl group in a molecular side chain .

The structure (D) having such a carboxyl group can be introduced by copolymerizing a carboxyl group-containing unsaturated monomer. Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid and the like. Considering that a (meth) acrylic unit having an ethylenically unsaturated group is introduced into the molecular side chain represented by the above formula (A) as a carboxyl group-containing structure (D), a carboxyl group-containing unsaturated monomer represented by the following formula From the viewpoint of control of the reaction and stability.

Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is any one selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon chain having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon chain having 6 to 10 carbon atoms , And n represents an integer of 0 to 6, and may be a single or a mixture of plural n)

In the formula (D1), R ¹³ is a hydrogen atom or a methyl group, and when R ¹³ is hydrogen, it is acrylic acid, and when it is a methyl group, it is methacrylic acid. R ¹⁴ is selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms, To 6 divalent alicyclic hydrocarbon groups and 6 to 8 divalent aromatic hydrocarbon groups. n is an integer of 0 to 6, preferably 0. n may be an integer or a plurality of integers between 0 and 6.

Examples of the unsaturated monomer (D1) having a carboxyl group represented by the above structure include acrylic acid, methacrylic acid, 2-carboxyethyl acrylate oligomer, 2-carboxyethyl methacrylate oligomer and the like. These (meth) acrylic monomers may be used singly or as a mixture of two or more kinds.

The acrylic copolymer of the present invention necessarily has a structure (E) having an aromatic ring in its side chain in order to exhibit high heat resistance. The structure (E) having an aromatic ring in the side chain can be introduced by copolymerization of an unsaturated monomer having an aromatic ring. A structure of the benzyl group and the benzyl group such as the following formula (E1) A derivative is particularly preferable, and the effect of improving the heat resistance is further improved.

Wherein R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms , A halogen atom, an ester group, an acyl group and a nitro group]

In the above formula (E1), R ¹⁵ is a hydrogen atom or a methyl group, and when R ¹⁵ is hydrogen, it is an acrylic unit, and when it is a methyl group, it is a methacryl unit. R ¹⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, Preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alicyclic hydrocarbon group having 5 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.

Examples of the (meth) acrylic monomer containing an aromatic ring represented by the formula (E1) include benzyl acrylate and benzyl methacrylate, but are not limited thereto. In the present invention, these (meth) acrylic monomers may be used singly or as a mixture of two or more kinds.

Wherein R ¹⁷ is a hydrogen atom or a methyl group, R ¹⁸ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, An aromatic hydrocarbon group, a halogen atom, an ester group, an acyl group and a nitro group]

In the formula (E2), R ¹⁷ is a hydrogen atom or a methyl group, and when R ¹⁷ is hydrogen, it is an acrylic unit, and when it is a methyl group, it is a methacryl unit. R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, Preferably an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alicyclic hydrocarbon group having 5 to 6 carbon atoms, or an aromatic hydrocarbon group having 6 to 8 carbon atoms.

Examples of the unsaturated monomer containing an aromatic ring represented by the formula (E2) include styrene,? -Methylstyrene, 4-vinyltoluene and its structural isomers, 4-methoxystyrene and its structural isomers, Styrene and its structural isomers, 4-tert-butoxystyrene and its structural isomers, 4-vinylbiphenyl, 2-vinylnaphthalene and its structural isomers, 9-vinyl anthracene and 9- . In the present invention, these acrylic monomers may be used singly or as a mixture of two or more kinds.

The acrylic copolymer is characterized by comprising a structural unit containing a polymerizable unsaturated bond, a tertiary amino group and / or a quaternary ammonium salt, a carboxyl group and an aromatic ring in the side chain. Among them, it is preferable to include a (meth) acrylic unit having a tertiary amino group in the side chain. A particularly preferable acrylic copolymer is an acrylic copolymer containing a structural unit represented by the following formula (1) May contain another main chain constituent unit.

Wherein R ¹ , R ² , R ⁴ , R ¹³ and R ¹⁷ are independently a hydrogen atom or a methyl group, R ³ is an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, R ⁶ and R ⁷ are independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, An aromatic hydrocarbon group having 6 to 10 carbon atoms, R ¹⁸ is selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, A hydrocarbon group, a halogen atom, an ester group, an acyl group and a nitro group;

In order to achieve high dispersion stability, the acrylic copolymer used in the present invention is more preferably copolymerized with a (meth) acrylic monomer having a long-chain alkyl group on the side chain represented by the following formula (F).

Wherein R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ²¹ is an alkyl group having 2 to 40 carbon atoms.

In the formula (F), R ¹⁹ is a hydrogen atom or a methyl group, and when R ¹⁹ is hydrogen, it is an acrylic unit, and when it is a methyl group, it is a methacryl unit. R ²⁰ is hydrogen or an alkyl group having 1 to ²⁰ carbon atoms, preferably hydrogen or an alkyl group having 2 to 6 carbon atoms. R ²¹ is an alkyl group having 2 to 40 carbon atoms, preferably an alkyl group having 2 to 18 carbon atoms. In the present invention, this acrylic monomer is defined as a structure having a carboxylic acid ester on the side chain.

The unsaturated monomer containing a carboxylic acid ester represented by the formula (F) has preferably 4 or more carbon atoms, more preferably 4 to 24 carbon atoms, of the total number of carbon atoms of R ²⁰ and R ²¹ . When R ²⁰ is hydrogen, R ²¹ may be an alkyl group having 4 or more carbon atoms. When the total number of carbon atoms of R ²⁰ and R ²¹ is 4 or more, the dispersion stability of the coloring material can be further improved.

Examples of the unsaturated monomer containing a carboxylic acid ester represented by the formula (F) include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and the like, but there is no particular limitation. These acrylic monomers may be used singly or as a mixture of two or more kinds.

In the present invention, the structure having a carboxylic acid ester in the side chain can be introduced by copolymerizing an unsaturated monomer containing a long-chain alkyl group. Examples of the long chain alkyl group-containing unsaturated monomer include octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, dodecyl acrylate, and dodecyl methacrylate. Among them, the unsaturated monomer having a carboxylic acid ester in the side chain having the structure represented by the formula (F) tends to exhibit higher dispersion stability, and therefore is particularly preferable.

In the acrylic copolymer of the present invention, any (meth) acrylic acid ester may be copolymerized as a monomer in addition to the above structural units, if necessary. Specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, Acrylic acid esters such as propyl acrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate, or methacrylic esters Or their (fluoro) alkyl ester monomers.

In the acrylic copolymer used in the present invention, it is important to set the acid value and the base value in an appropriate range. The amount of the base is preferably 5 to 70 mmol / 100 g, and preferably 10 to 30 mmol / 100 g. If the base is lower than this range, the pigment dispersion stability becomes poor, and if the base is high, the developability becomes poor. It is possible to set the composition ratio of the basic acrylic copolymer to a predetermined range by adjusting the composition ratio of the constituent units of the formulas (B) and (C). Further, the base value of the acrylic copolymer is defined as the number of moles of perchloric acid, which is important for neutralizing 100 g of the acrylic copolymer (unit: mmol / 100 g).

The acid value of the acrylic copolymer is required to be 50 to 120 mgKOH / g, preferably to be 50 to 100 mgKOH / g. When the upper limit is exceeded, the dispersion stability tends to deteriorate. When the lower limit is exceeded, the alkali development tends to become difficult. The acid value can be set within a predetermined range by adjusting the composition ratio of the constituent units of the acrylic copolymer. Further, the acid value of the acrylic copolymer is defined as the number of mg of potassium hydroxide which is important for neutralizing 1 g of the acrylic copolymer (unit: mgKOH / g).

In the present invention, the weight average molecular weight (Mw) of the acrylic copolymer is 5,000 to 30,000, preferably 5,000 to 20,000. If the weight average molecular weight is less than 5,000, sufficient steric hindrance can not be formed, and the dispersion becomes unstable due to the interaction of the coloring materials. On the other hand, if the weight-average molecular weight is more than 30,000, the resin adsorption probability per unit of the coloring material decreases to cause unstable dispersion or deteriorate developability. In addition, the weight average molecular weight (Mw) of the acrylic copolymer is determined by measuring the tetrahydrofuran as a carrier by gel permeation chromatography and using a standard polystyrene calibration curve.

In the acrylic copolymer used in the present invention, the structural units represented by the above formulas (B), (C), (D1), (E1) and (E2) Can be obtained in the form of random copolymer or block copolymer by general radical polymerization reaction such as solution polymerization, emulsion polymerization, bulk polymerization and the like. Particularly preferred is a random copolymer. The (meth) acrylic unit represented by the formula (A) can be introduced by a general method in which the side chain functional group of the acrylic copolymer obtained above is introduced by the addition reaction of a monomer having a functional group capable of reacting with the side chain functional group .

The organic solvent used in the coloring material dispersion of the present invention is not particularly limited, but specifically includes at least one selected from aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers and alcohols. Among them, at least one selected from carboxylic acid esters, ketones, and ethers can be used. Examples of the carboxylic acid ester preferably used include esters of saturated aliphatic carboxylic acids and saturated alcohols.

Specific examples of the esters include benzyl acetate, ethyl benzoate,? -Butyrolactone, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxy ethyl acetate, 3-methoxy- , Diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol mono Methyl ether propionate, propylene glycol monoethyl ether acetate, pentyl acetate, propylene glycol monomethyl ether acetate, and the like, but are not limited thereto.

Among these organic solvents, it is preferable to use 3-methoxy-3-methyl-butylacetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, 3-methoxy-butyl acetate , And propylene glycol monomethyl ether acetate are particularly preferable.

Examples of the organic solvent other than the above include aliphatic ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tertiary butyl ether and dipropylene glycol monomethyl ether, and aliphatic esters other than the above For example, ethyl acetate, butyl acetate, isopentyl acetate, or aliphatic alcohols such as butanol, 3-methyl-2-butanol and 3-methyl-3-methoxybutanol, ketones such as cyclopentanone and cyclohexanone, It is also possible to use an organic solvent such as xylene, ethylbenzene or solvent naphtha in combination.

As the coloring material in the coloring material dispersion of the present invention, any one of organic pigment, inorganic pigment and dye can be suitably used.

Examples of the organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, and polyazo pigments, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or nonmetal phthalocyanine, aminoanthraquinone, diaminoanthraquinone, Anthraquinone type pigments such as anthraquinone type pigments such as anthraquinone type pigments, anthraquinone type pigments, dioxazine type pigments, perinone type pigments, perylene type pigments, thioindigo type pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threne pigments, and metal complex pigments.

Examples of the inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, zinc white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, red iron oxide, molybdate red, Cobalt blue, cerulean blue, cobalt silica blue, cobalt blue, cobalt green, cobalt green, cobalt green, cobalt green, cobalt yellow, yellow iron oxide, titanium yellow, chromium oxide, Zinc silicate blue, manganese violet, or cobalt violet.

Examples of the dye include azo dyes, anthraquinone dyes, condensed polycyclic aromatic carbonyl dyes, indigoid dyes, carbonium dyes, phthalocyanine dyes, methine and polymethine dyes.

Specific examples of typical pigments and dyes are represented by color index (CI) numbers, the following are preferably used, but not all of them are limited thereto.

Examples of the red pigment include Pigment Red (hereinafter referred to as PR) 9, PR48, PR97, PR122, PR123, PR144, PR149, PR166, PR168, PR177, PR179, PR180, PR192, PR209, PR215, PR216, PR217, PR220 , PR223, PR224, PR226, PR227, PR228, PR240, PR254, and the like are used.

Examples of the orange pigment include pigment orange (hereinafter referred to simply as PO) 13, PO36, PO38, PO43, PO51, PO55, PO59, PO61, PO64, PO65 and PO71.

Examples of the yellow pigments include Pigment Yellow (hereinafter simply referred to as PY) PY12, PY13, PY17, PY20, PY24, PY83, PY86, PY93, PY95, PY109, PY110, PY117, PY125, PY129, PY137, PY138, PY139, PY147 , PY148, PY150, PY153, PY154, PY166, PY168, PY185 and the like are used.

Examples of purple pigments include pigment violet (hereinafter simply referred to as PV) 19, PV23, PV29, PV30, PV32, PV37, PV40 and PV50.

Examples of blue pigments include Pigment Blue (hereinafter abbreviated as PB) 15, PB15: 3, PB15: 4, PB15: 6, PB22, PB60, PB64 and the like.

Examples of the green pigment include pigment greens (hereinafter simply referred to as PG) 7, PG10, PG36, PG58, and the like.

Examples of the black pigments include black organic pigments, mixed color organic pigments, and inorganic pigments. Examples of the black organic pigments include carbon black, perylene black and aniline black. As the color organic pigments, at least two kinds of pigments selected from red, blue, green, yellow, magenta, A metal oxide, a composite oxide, a metal sulfide, a metal nitride, a metal oxynitride, or the like as the inorganic pigments, and graphite, and metal fine particles such as titanium, copper, iron, manganese, cobalt, chrome, nickel, . These may be used alone or in combination of two or more. In particular, carbon black and titanium nitride are preferably used by having high light shielding properties.

Examples of white pigments include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, silicon dioxide and the like.

Examples of the dye include CI Direct Red 2, 4, 9, 23, 26, 28, 31, 39, 62, 63, 72, 75, 76, 79, 80, 81, 83, 84, 89, 92, 95, 111, 173, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233, 240, 241, 242, 243, 247, CI Acid Red 35, 42 , 51, 52, 57, 62, 80, 82, 111, 114, 118, 119, 127, 128, 131, 143, 145, 151, 154, 157, 158, 211, 249, 254, 257, 261, 263 , 266, 289, 299, 301, 305, 319, 336, 337, 361, 396, 397, CI Reactive Red 3,13,17,19,21,22,23,24,29,35,37,40 , 41, 43, 45, 49, 55, CI Basic Red 12,13,14,15,18,22,23,24,25,27,29,35,36,38,39,45,46, CI Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101, CI Acid Violet 5,9,11,34,43,47,48, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34, CI Basic Violet 1, 2, 3 , 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48, 58, 59, 68, 87, 93, 95, 96, 98, 100, 106, CI Acid Yellow 17, 19, 23, 25, 39, 40, 42, 44, 49, 50, 61, 64, 76, 79, 110, 127 , 135, 143, 151, 159, 169, 174, 190, 195, 196, 197, 199, 218, 219, 222, 227, CI Reactive Yellow 2, 3, 13, 14, 15, 17, 18, 23 , 24, 25, 26, 27, 29, 35, 37, 41, 42, CI Basic Yellow 1,2,4,11,13,14,15,19,21,23,24,25,28,29, 32,36,39, 40, CI Acid Green 16, CI Acid Blue 9,45,80,83,90,185, CI Basic Orange 21,23, and the like.

In the coloring material dispersion of the present invention, it is more preferable to add a polymeric dispersing agent in order to uniformly or stably disperse the coloring material in the resin solution. Examples of the polymer dispersant include a polyester-based polymer dispersant, an acrylic polymer dispersant, a polyurethane-based polymer dispersant, a polyarylamine-based polymer dispersant, and a carbodiimide-based dispersant. These polymer dispersants are appropriately selected and used depending on the type of the colorant.

There are various kinds of dispersing agents such as a dispersant having an amine chelate, a dispersant having an acid chelate, an amine value and an acid value, and a dispersant having no amine trivalent acid. However, in order to remarkably exert the effect of the present invention, Is more preferably used, and more preferably, a polymer dispersant having amine amines is preferable.

Specific examples of the dispersant having amine amines include Disperbyk 102, Disperbyk 160, Disperbyk 161, Disperbyk 162, Disperbyk 2163, Disperbyk 2164, Disperbyk 166, Disperbyk 167, Disperbyk 168, Disperbyk 2000, Disperbyk 2050, Disperbyk 2150, Disperbyk 2155, Disperbyk LPN 6919 , Disperbyk LPN 21116, Disperbyk LPN 21234, Disperbyk 9075, Disperbyk 9077 (manufactured by BYK-Chemie); EFKA 4402, EFKA 4403, EFKA 4800 (or more), EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4401, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4403, EFKA 4403, EFKA 4403, Manufactured by BASF); Ajisper PB711 (manufactured by Ajinomoto Fine-Techno Co., Inc.), and the like.

It is more preferable to use a polymeric dispersant having at least a tertiary amino group even in the case of a dispersant having an amine chelate. Specific examples thereof include Disperbyk LPN 6919, Disperbyk LPN 21116 and the like.

Disperbyk 142, Disperbyk 145, Disperbyk 2001, Disperbyk 2010, Disperbyk 2020, Disperbyk 2025, Disperbyk 9076, and Anti-Terra-205 (all manufactured by BYK-Chemie) as the polymer dispersant having an amine value and an acid value; Solsperse 24000 (manufactured by The Lubrizol Corporation); Ajisper PB821, Ajisper PB880 and Ajisper PB881 (manufactured by Ajinomoto Fine-Techno Co., Inc.).

These polymer dispersants may be used alone or in combination of two or more. These polymer dispersants do not have photosensitivity. Therefore, when added in a large amount, there is a risk of deteriorating the photosensitive performance of the intended photosensitive colored resin composition, and it is preferable that the added amount is appropriately added in consideration of dispersion stability and photosensitive performance. The addition of 1 to 50 (mass%), more preferably 3 to 30 (mass%), to the coloring material has the effect of stabilizing the dispersion at a high level without deteriorating the photosensitive performance.

In the coloring material dispersion of the present invention, the weight composition ratio of the coloring material component / the resin component is preferably in the range of 90/10 to 20/80, more preferably 90/10 to 40/60. Here, the resin component means the sum of additives such as a polymer dispersant in addition to the acrylic copolymer. If the amount of the resin component is too small, the dispersion stability of the coloring material becomes poor. On the contrary, if the amount of the coloring material component is very small, it is difficult to form a coating film having a high coloring power when the colored coating film is formed using the coloring material dispersion Which is undesirable.

The solid content concentration of the resin component and the coloring material component in the coloring material dispersion of the present invention is preferably 2 mass% or more and 60 mass% or less, more preferably 5 mass% or more and 30 mass% or less from the viewpoints of dispersion stability and productivity .

The method for producing the coloring material dispersion of the present invention is not particularly limited, but a method of dispersing the coloring material in the acrylic copolymer solution using a dispersing machine is generally performed.

As the dispersing device for dispersing the coloring material, various methods such as a ball mill, a sand grinder, a three-roll mill, and a high-speed impact mill can be used, but a bead mill is preferable from the dispersion efficiency and the fine particle oxidation. As the bead mill, a cow ball mill, a basket mill, a pin mill, a dynomill, and the like can be used. As the bead of the bead mill, it is preferable to use titania beads, zirconium oxide beads, zircon beads and the like.

The bead diameter used for dispersion is preferably 0.01 mm or more and 5.0 mm or less, and more preferably 0.03 mm or more and 1.0 mm or less. It is preferable to use a minute dispersion bead in which the diameter of the primary particle of the coloring material and the diameter of the secondary particle formed by agglomeration of the primary particle are small, to 0.03 mm or more and 0.10 mm or less. In this case, it is preferable to use a bead mill having a separator by a centrifugal separation method capable of separating the minute dispersion beads and the dispersion liquid. On the other hand, when dispersing a coloring material containing coarse and coarse particles of the order of sub-micron, it is preferable to use a dispersion bead of 0.10 mm or more to obtain a sufficient crushing power to finely disperse the pigment.

Examples of the photosensitive colored resin composition using the colorant dispersion of the present invention are illustrated below, but the present invention is not limited thereto.

The photosensitive colored resin composition of the present invention comprises at least an alkali-soluble polymer, a reactive monomer, and a photopolymerization initiator added to the colored material dispersion of the present invention. The amount ratio thereof is generally 10/90 to 90/10 in terms of the weight composition ratio of the alkali-soluble polymer and the reactive monomer, and the addition amount of the photopolymerization initiator is about 1 to 20% by weight based on the total weight of the polymer and the monomer. Here, as the weight of the alkali-soluble polymer, the total weight of the acrylic copolymer contained in the coloring material dispersion is added by adding the weight of the newly added alkali-soluble polymer.

As the alkali-soluble polymer of the photosensitive colored resin composition of the present invention, a novel alkali-soluble polymer may be used, even if the acrylic copolymer used for the colorant dispersion is used. The alkali-soluble polymer to be newly used will be described in detail below.

As the alkali-soluble polymer, an alkali-soluble polymer having a carboxyl group is preferable, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferably used. Examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid, acid anhydrides thereof, phthalic acid mono (2- (Meth) acryloyloxyethyl), and the like. Particularly, an acrylic polymer comprising a constituent unit derived from (meth) acrylic acid is preferable, and an acrylic polymer obtained by reacting a compound containing an ethylenic unsaturated group and an epoxy group in a carboxylic acid contained in the constituent unit is used , Sensitivity at the time of exposure and development is improved, and therefore, it can be preferably used. The ethylenic unsaturated group is preferably an acryl group or a methacryl group.

These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. Specific examples of the copolymerizable ethylenically unsaturated compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, propyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-butyl methacrylate, n-butyl methacrylate, sec-butyl acrylate, sec- Unsaturated carboxylic acid alkyl esters such as pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate and benzyl methacrylate, aromatic vinyl compounds such as o-methylstyrene, m-methylstyrene and? -methylstyrene, (bridged) cyclic hydrocarbon groups such as tricyclodecanyl (meth) acrylate, Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate, carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate, acrylonitrile, methacrylic acid, Acrylonitrile and? -Chloroacrylonitrile; aliphatic conjugated dienes such as 1,3-butadiene and isopropyl; polystyrenes each having an acryloyl group or methacryloyl group at the ends; polymethylacrylate; poly Methyl methacrylate, polybutyl acrylate, polybutyl methacrylate, and the like, but are not limited thereto.

Particularly, an acrylic polymer comprising (meth) acrylic acid and benzyl (meth) acrylate is particularly preferable from the standpoints of dispersion stability and pattern processability.

In addition to the acrylic polymer obtained by reacting the (meth) acrylic acid contained in the constituent unit of the substrate with a compound containing an ethylenic unsaturated group and an epoxy group, an acrylic polymer having an ethylenic unsaturated group in its side chain can be preferably used. Specific examples thereof include copolymers described in Japanese Patent No. 3120476 and Japanese Patent Application Laid-open No. Hei 8-262221, or a commercially available acrylic polymer "Cyclomer (registered trademark) P" (manufactured by Daicel Chemical Industries, Ltd. ), An alkali-soluble cardo resin, and the like.

The weight average molecular weight (Mw) of the alkali-soluble polymer is preferably 5000 to 40000 (in terms of tetrahydrofuran as a carrier measured by gel permeation chromatography and converted using a calibration curve by standard polystyrene) A polymer having an acid value of 60 to 150 (mgKOH / g) is most preferable from the viewpoints of photosensitivity, solubility in an ester solvent, solubility in an alkaline developer, and restraint of residues.

As the reactive monomer of the photosensitive colored resin composition of the present invention, a polyfunctional, monofunctional acrylic monomer or oligomer can be used. Among them, it is preferable to contain a polyfunctional monomer. Examples of the polyfunctional monomer include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (Meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylate, rosin-modified epoxy di (meth) acrylate, adipic acid 1,6-hexanediol (Meth) acrylate, fluorene diacrylate oligomers such as those described in Japanese Patent No. 3621533 or Japanese Patent Application Laid-Open No. 8-278630, tripropylene glycol di (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, dipentaerythritol hexa (meth) acrylate and acid modified products thereof, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (Meth) acrylate and its acid modified product, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4, 5-dihydroxyphenyl) methane, bis [4- Phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene , 9,9-bis [3-chloro-4- (3-acryloxy-2-hydroxypropoxy) - hydroxypropoxy) phenyl] fluorene, bisphenoxyethanol flu Norbornene diacrylate, norbornene diacrylate, neodiacrylate, bisphenoxyethanol fluorene dimethacrylate, biscraclefluroene diacrylate, and biscraclefluorene dimethacrylate. These may be used alone or in combination.

By selecting and combining these multifunctional monomers and oligomers, it is possible to control the sensitivity and processability characteristics of the resist. Particularly, in order to raise the sensitivity, it is preferable to use a compound having three or more functional groups and more preferably five or more functional groups. Particularly, it is preferable to use a compound having dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) Body is preferable. An unsaturated group-containing alkali-soluble monomer obtained by reacting a reaction product of an epoxy compound having two glycidyl ether groups and methacrylic acid with a polybasic carboxylic acid or an acid anhydride thereof is also preferably used from the viewpoints of developability and processability. Further, the combined use of (meth) acrylate having a fluorine ring having a high water repellency and containing a large number of aromatic rings in the molecule is preferable because the pattern can be controlled in a desirable shape at the time of development.

The photopolymerization initiator of the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably a photoradical polymerization initiator, more preferably an alkylphenone-based and / or oxime ester-based photopolymerization initiator.

Examples of the alkylphenon-based photopolymerization initiator include an? -Aminoalkylphenone-based,? -Hydroxyalkylphenone-based, and the like. Of these, the? -Aminoalkylphenone-based is particularly preferable from the viewpoint of high sensitivity. 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, Ciba Specialty Chemicals "Irgacure (registered trademark)" 2-dimethylamino-1- (4-morpholinophenyl) -butanone, Ciba Specialty Chemicals "Irgacure & Methylphenyl) -1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1-on.

Specific examples of the oxime ester photopolymerization initiator include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] which is Ciba Specialty Chemicals "Irgacure (registered trademark) -9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O- N-1819, "Adeka Cruise" NCI-831 from Asahi Denka Kogyo KK.

In addition to these photopolymerization initiators, it is also possible to use a photopolymerization initiator such as a benzophenone compound, an oxytron compound, an imidazole compound, a benzothiazole compound, a benzoxazole compound, a carbazole compound, a triazine compound, A known photopolymerization initiator such as a photopolymerization initiator may be used in combination. Examples thereof include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzoin, benzoin methyl ether, Butyl anthraquinone, 1-chloro anthraquinone, 2,3-dichloroanthraquinone, 3-chloro- anthraquinone, 3-chloro- anthraquinone, 2-methyl anthraquinone, 2-ethyl anthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethyl anthraquinone, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 4- (p-methoxyphenyl) -2,6- -Di- (trichloromethyl) -s-triazine, and the like.

The organic solvent that can be preferably used in the photosensitive colored resin composition of the present invention is not particularly limited, and esters, aliphatic alcohols, ketones and the like can be used.

Specific examples of the esters include benzyl acetate (boiling point 214 占 폚), ethyl benzoate (boiling point 213 占 폚),? -Butyrolactone (boiling point 204 占 폚), methylbenzoate (boiling point 200 占 폚), diethyl malonate Butyl acetate (boiling point: 188 占 폚), diethyl oxalate (boiling point: 185 占 폚), 2-ethylhexyl acetate (boiling point: 199 占 폚), 2-butoxy ethyl acetate (Boiling point 171 ° C), 3-methoxy-butyl acetate (boiling point 173 ° C), acetoacetic acid methyl ester (boiling point 172 ° C), ethyl 3-ethoxypropionate Propylene glycol monomethyl ether propionate (boiling point: 160 占 폚), propylene glycol monoethyl ether acetate (boiling point: 158 占 폚), 2-ethylbutyl acetate (boiling point: 162 占 폚), isopentylpropionate ° C.), pentyl acetate (boiling point: 150 ° C.), propylene glycol monomethyl ether acetate Boiling point 146 DEG C), and the like, but are not limited thereto.

Among these solvents, it is preferred to use 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, 3-methoxy- Propylene glycol monomethyl ether acetate is particularly preferred.

Propylene glycol monomethyl ether (boiling point: 120 占 폚), propylene glycol monoethyl ether (boiling point: 133 占 폚), propylene glycol tertiary butyl ether (boiling point: 153 占 폚), dipropylene glycol monomethyl ether (Bp 77 ° C), butyl acetate (boiling point 126 ° C), isopentyl acetate (boiling point 142 ° C), or butanol (butyl alcohol) Aliphatic alcohols such as 3-methyl-2-butanol (boiling point 112 ° C) and 3-methyl-3-methoxybutanol (boiling point 174 ° C), ketones such as cyclopentanone and cyclohexanone, (Boiling point: 144 占 폚), ethylbenzene (boiling point: 136 占 폚), and solvent naphtha (petroleum oil: boiling point: 165 to 178 占 폚).

In addition, since the application by the die coating apparatus becomes mainstream as the substrate becomes larger, it is preferable to use a mixed solvent of two or more components in order to realize appropriate volatility and dryness. If the boiling points of all the solvents constituting the mixed solvent are 150 DEG C or lower, uniformity of the film thickness can not be obtained, the film thickness of the coated portion becomes thick, aggregation of the pigment occurs in the claw portion for discharging the coating liquid from the slit, Causing many problems that lines are formed in the coating film. On the other hand, when the mixed solvent contains a large amount of a solvent having a boiling point of 200 ° C or higher, the surface of the coating film becomes sticky to cause sticking. Therefore, a mixed solvent containing 30 to 75% by mass of a solvent having a boiling point of 150 ° C to 200 ° C is preferable.

In the photosensitive colored resin composition of the present invention, it is preferable to add an adhesion improver to the colored resin composition in order to improve the adhesion between the coating film and the undercoated substrate, and a silane coupling agent is preferably used. The silane coupling agent is not particularly limited, and silane coupling agents having functional groups such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group and an amino group can be exemplified, but are not limited thereto. Specific examples thereof include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methacryloxypropyltrimethoxysilane, (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butyrylidene) ) Propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanate propyl tri Ethoxysilane, p-trimethyltrimethoxysilane and the like are preferable.

The addition amount of the adhesion improver is preferably from 1 to 15 mass%, more preferably from 2 to 10 mass%, based on the total amount of the solid components of the colored resin composition, that is, the total amount of the colorant and the acrylic copolymer, alkali- Do. If it is less than 1% by mass, the effect of improving the adhesiveness is not sufficient. If it is more than 15% by mass, the fine pattern is lost in the alkali development and the resolution is lowered.

In addition, a surfactant may be added to the photosensitive colored resin composition of the present invention for the purpose of preventing spreadability, smoothness of a colored film, and Benard Cells. The amount of the surfactant to be added is usually 0.001 to 10 mass%, preferably 0.01 to 1 mass%, of the pigment. If the addition amount is too small, the coatability, the smoothness of the colored film and the effect of preventing the vanadic cell are not exhibited, and if it is too much, the physical properties of the coating film may be inferior.

Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; cationic surfactants such as lauryldimethylamine oxide, An amphoteric surfactant such as methylhydroxy ethyl imidazolium betaine, a nonionic surfactant such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and sorbitan monostearate, and polydimethylsiloxane, , A fluorine-based surfactant, and the like. But the present invention is not limited thereto, and one or more surfactants may be used.

In the photosensitive colored resin composition of the present invention, the weight composition ratio of the coloring material component / the resin component is preferably in the range of 80/20 to 10/90 in order to obtain a coating having sufficient tinting strength. Here, the resin component is the sum of additives such as a reactive monomer, an oligomer, a photopolymerization initiator, and a polymer dispersant in addition to the alkali-soluble polymer added to the acrylic copolymer or the colored resin composition used for the colorant dispersion.

In the photosensitive colored resin composition of the present invention, the solid content concentration of the resin component and the coloring agent component is preferably 2% or more and 60% or less, more preferably 5% or more and 30% or less from the viewpoint of coatability and drying property.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

<Evaluation method>

"Mountain"

The amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic copolymer was referred to as acid (unit: mgKOH / g).

"Base"

The number of moles of perchloric acid needed to neutralize 100 g of the acrylic copolymer was referred to as the base (unit: mmol / 100 g).

"Molecular Weight"

(GPC) "HLC-8220 GPC" (Tosoh Corporation's testing apparatus), and the weight average molecular weight (Mw) of the carrier was measured using tetrahydrofuran and polystyrene as a molecular weight standard.

"Viscosity"

A viscometer (RE105L, manufactured by Toki Sangyo Co., Ltd.) was set at 25.0 占 폚 to 0.2 占 폚, and the value at 100 rpm was set to a viscosity value.

"Dispersion stability"

The dispersion state was evaluated comprehensively based on the initial viscosity of the coloring material dispersion, the viscosity change after one week, that is, the percentage of increase (viscosity, unit%) of viscosity after one week with respect to the initial viscosity. Although the smaller the viscosity at the time of aging, it is preferable that the smaller the viscosity is, the larger the viscosity is due to the interaction between the finely dispersed pigments. The tolerance standard is evaluated as follows.

○ Dispersion is very good (within 50% of the week of production)

△ Good dispersing condition (the point of increase in the week of production exceeds 50% and within 100%)

× dispersed state is unstable (the increase in the week of production is greater than 100%)

"Developability"

From the viewpoint of industrial use, the dissolution time of the non-photosensitive portion of the coating film developed with 0.045% potassium hydroxide aqueous solution was evaluated as DELTA as follows.

○ Developability is very good (dissolution of resist coating unexposed area within 50 seconds)

? Developability is good (dissolution of the resist film unexposed area within 50 seconds and over within 100 seconds)

× poor developing property (it takes more than 100 seconds to complete the dissolution of the resist film unexposed area)

"Heat resistance"

After heat-baking at 150 占 폚 for 30 minutes with a thermogravimetric analyzer (Q50 manufactured by TA Instruments), post-baking was performed in the order of 280 占 폚 for 60 minutes, and heat resistance was evaluated by changing the weight of the sample before and after post- From the viewpoint of the enemy use, the permissible standard was evaluated as? As follows.

○ Heat resistance is very good (weight change of 1.5% or less)

△ Good heat resistance (weight change of more than 1.5% and 2.0% or less)

× poor heat resistance (weight change exceeding 2.0%)

&Lt; Synthesis of acrylic copolymer >

An example of the synthesis of the acrylic copolymer in the present invention is shown below. Further, the present invention is not limited to the following method. Table 1 shows the production method and characteristic values of the acrylic copolymer in this Synthesis Example. The notation of &quot; part &quot; in each of the synthesis examples represents parts by weight.

The abbreviations of (meth) acrylic monomers and other monomers shown in Table 1 are as follows.

Methyl methacrylate (MMA)

· Methacrylic acid dodecyl (DOMA)

Stearyl methacrylate (SLMA)

a structure represented by formula (D1) wherein n is 0;

· Methacrylic acid (MAA)

· Acrylic acid (AA)

A structure represented by formula (E2);

Styrene (St)

4-methylstyrene (4MSt)

A structure represented by formula (E1);

· Benzyl methacrylate (Bz-MA)

A structure represented by formula (B);

- 2-Dimethylaminoethyl methacrylate (MLDA)

- Acrylic acid-2-dimethylaminoethyl (ALDA)

A structure represented by formula (C);

Methacrylic acid-2-dimethylaminoethyl hydrochloride (MLDA-Cl)

A structure represented by the formula (F);

· 2-ethylhexyl acrylate (2EHA),

- 2-ethylhexyl methacrylate (2EHMA)

A structure represented by formula (D1);

· Acidic functional group-containing monomer mixture (produced by Rhone-Poulenc) (β-CEA)

An addition reaction monomer for introducing the structure (A) having an ethylenically unsaturated group;

Glycidyl methacrylate (GMA)

A polymerization initiator;

Azobisisobutyronitrile (AIBN)

Normal dodecyl mercaptan (MDM)

Adjustment of the base shown in Table 1 was carried out by adjusting the acid value by increasing or decreasing the amount of the carboxyl group-containing monomers (AA, MAA, or? -CEA) by increasing or decreasing the amount of the amino group-containing monomers (MLDA, ALDA or MLDA- Respectively.

The adjustment of the weight average molecular weight shown in Table 1 was carried out by increasing or decreasing the amount of the polymerization initiator (AIBN) and / or normal dodecyl mercaptan (MDM).

[Synthesis Example 1]

200 parts of propylene glycol monoethyl ether acetate solvent was charged into a pressure-resistant container equipped with a stirrer, a thermometer, a reflux condenser and a dropping pump, the inside of the reaction vessel was filled with nitrogen and the temperature was raised to 90 ° C to obtain methacrylic acid- 1 part of dimethylaminoethyl (MLDA), 32 parts of methyl methacrylate (MMA), 20 parts of 2-ethylhexyl methacrylate (2EHMA), 30 parts of styrene (St), 17 parts of methacrylic acid (MAA) 2.0 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator, and 3.0 parts of normal dodecyl mercaptan (MDM) were added dropwise over 3 hours with a dropping pump to carry out copolymerization. Subsequently, 10 parts of glycidyl methacrylate (GMA) was added dropwise with dropping pump for 1 hour by replacing air in the inside of the reaction vessel with air, followed by further reaction, and the inside of the vessel was further stirred for 2 hours. As a result, an acrylic copolymer (P-1) having a characteristic value of 5 mmol / 100 g of base, 75 mgKOH / g of acid value and 7000 of weight average molecular weight was obtained.

[Synthesis Example 2]

Except that the amounts of MMA and MLDA were changed to 31 parts and 2 parts, respectively. As a result, an acrylic copolymer (P-2) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 3]

MMA and MLDA were respectively changed to 30 parts and 3 parts, respectively. As a result, an acrylic copolymer (P-3) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 4]

MMA and MLDA were respectively changed to 29 parts and 4 parts, respectively. As a result, an acrylic copolymer (P-4) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 5]

MMA and MLDA were respectively changed to 26 parts and 7 parts, respectively. As a result, an acrylic copolymer (P-5) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 6]

The procedure of Synthesis Example 1 was repeated except that the amount of MMA was changed to 33 parts without using MLDA. As a result, an acrylic copolymer (P-6) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 7]

MMA and MLDA were changed to 17 parts and 16 parts, respectively. As a result, an acrylic copolymer (P-7) having the characteristic values shown in Table 1 was obtained

[Synthesis Example 8]

The procedure of Synthesis Example 3 was repeated except that MLDA was changed to ALDA. As a result, an acrylic copolymer (P-8) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 9]

The procedure of Synthesis Example 3 was repeated except that MLDA was replaced with MLDA-Cl. As a result, an acrylic copolymer (P-9) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 10]

The same procedure as in Synthesis Example 3 was carried out except that the amounts of MMA and MAA were changed to 37 parts and 10 parts, respectively. As a result, an acrylic copolymer (P-10) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 11]

And the amounts of MMA and MAA were changed to 27 parts and 20 parts, respectively. As a result, an acrylic copolymer (P-11) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 12]

And the amounts of MMA and MAA were changed to 23 parts and 24 parts, respectively. As a result, an acrylic copolymer (P-12) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 13]

The same procedure as in Synthesis Example 3 was carried out except that MAA was not used and the amount of MMA was changed to 47 parts. As a result, an acrylic copolymer (P-13) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 14]

Except that the amounts of MMA and MAA were changed to 40 parts and 7 parts, respectively. As a result, an acrylic copolymer (P-14) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 15]

Except that the amounts of MMA and MAA were changed to 15 parts and 32 parts, respectively. As a result, an acrylic copolymer (P-15) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 16]

The procedure of Synthesis Example 3 was repeated except that MAA was changed to AA. As a result, an acrylic copolymer (P-16) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 17]

MMA was added in an amount of 14 parts, and 17 parts of MAA was changed to 33 parts of? -CEA. As a result, an acrylic copolymer (P-17) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 18]

2 EHMA was changed to 2 EHA. As a result, an acrylic copolymer (P-18) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 19]

2EHMA was replaced with methacrylic acid dodecyl (DOMA). As a result, an acrylic copolymer (P-19) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 20]

2EHMA was changed to stearyl methacrylate (SLMA). As a result, an acrylic copolymer (P-20) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 21]

Except that 2EHMA was not used and the amount of MMA was changed to 50 parts. As a result, an acrylic copolymer (P-21) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 22]

MDM was added in an amount of 5.0 parts. As a result, an acrylic copolymer (P-22) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 23]

MDM was used in an amount of 2.0 parts. As a result, an acrylic copolymer (P-23) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 24]

MDM was used in an amount of 1.0 part. As a result, an acrylic copolymer (P-24) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 25]

Except that MDM was not used. As a result, an acrylic copolymer (P-25) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 26]

AIBN was added in an amount of 6.0 parts. As a result, an acrylic copolymer (P-26) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 27]

Except that MDM was not used and the amount of AIBN was changed to 0.8 parts. As a result, an acrylic copolymer (P-27) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 28]

St was prepared in the same manner as in Synthesis Example 3 except that 4 MSt was used. As a result, an acrylic copolymer (P-28) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 29]

St was prepared in the same manner as in Synthesis Example 3 except that BzMA was used. As a result, an acrylic copolymer (P-29) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 30]

St was not used and the amount of MMA was changed to 60 parts. As a result, an acrylic copolymer (P-30) having the characteristic values shown in Table 1 was obtained.

&Lt; Preparation of coloring material dispersion and photosensitive colored resin composition >

[Example 1]

200 g of the titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) produced by the thermal plasma method, 114 g of the 35 wt% solution of the acrylic copolymer (P-1) in propylene glycol monoethyl ether acetate, 3 g of the polymer dispersant 25 g of Disperbyk LPN-21116 (DP-1, manufactured by BYK-Chemie, a 40 wt% solution of propylene glycol monoethyl ether acetate) having a quaternary ammonium group and quaternary ammonium salt and 661 g of propylene glycol monoethyl ether acetate (PMA) And the mixture was stirred with a homomixer (manufactured by PRIMIX Corporation) for 20 minutes to obtain a preliminary dispersion. Thereafter, the preliminary dispersion liquid was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 75% of zirconium oxide beads (YTZ ball, manufactured by Neturen Co., Ltd.) , And dispersed for 3 hours at a rotation speed of 8 m / s to obtain a colored material dispersion 1 having a solid content concentration of 25% by weight and a coloring material / resin (weight ratio) = 80/20. The colorant dispersion liquid 1 obtained had a viscosity of 3.4 mPa · s immediately after preparation and a viscosity of 5.5 mPa · s after a lapse of one week.

33.00 g of this colored material dispersion 1 and 7.53 g of a 35% by weight solution of the acrylic copolymer (P-1) in propylene glycol monoethyl ether acetate, 55.36 g of propylene glycol monoethyl ether acetate, "Adeka (TM) (Manufactured by Asahi Denka Kogyo KK), 2.64 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DHPA), 0.45 g of 3-acryloxypropyltrimethoxysilane, 0.45 g of BYK-331 0.04 g) were mixed to prepare a photosensitive colored resin composition.

The obtained photosensitive colored resin composition was applied on a substrate of non-alkali glass (Corning Incorporated, produced by "1737 material") using a spin coater and prebaked at 90 캜 for 10 minutes. After that, Dainippon Screen Mfg. Co., Ltd. Exposure through a gray-tone mask was performed using an exposure apparatus "XG-5000 ", and a negative resist was developed using 0.045% potassium hydroxide aqueous solution. The development time was 33 seconds.

The dissolution time of the non-photosensitive portion of the developed coating film was measured and evaluated by the above-described test method. The results are shown in Table 2.

In Table 2, the kinds of the coloring material, the acrylic copolymer, the polymer dispersing agent and the solvent constituting the coloring material dispersion liquid are given in abbreviated form, and the blending amounts (% by weight) of each are described.

[Examples 2 to 22 and Comparative Examples 1 to 8]

(P-2 to P-30) obtained by changing the acid value, the base, and the characteristic value of the weight average molecular weight and some unsaturated monomers in place of the acrylic copolymer (P-1) Table 2 shows the results of Examples 2 to 22 and Comparative Examples 1 to 8, in which the coloring material dispersion and the photosensitive colored resin composition were prepared and evaluated.

The heat-sensitive coloring resin compositions obtained in Examples 3, 21 and 22 and Comparative Example 8 were evaluated for heat resistance before and after post-baking by the above-mentioned method. The results are shown in Table 2.

It was found that the dispersion stability of the coloring material dispersion prepared in the examples and the developability of the black matrix can be both satisfied and that the acrylic copolymer should have a specific range of base, acid value, and weight average molecular weight. Further, it was found that it is necessary to introduce an aromatic ring into the side chain in order to obtain sufficient heat resistance.

It has also been found that the stability of the pigment dispersion becomes higher by introducing an acrylic group having a long chain to the side chain.

[Example 23]

175 g of the titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) produced by the thermal plasma method, 214 g of a 35 wt% solution of the acrylic copolymer (P-3) in propylene glycol monoethyl ether acetate, Table 3 shows the dispersion stability of the colorant dispersion prepared in the same manner as in Example 3 and the evaluation results of the developability of the photosensitive colored resin composition, except that 611 g of propylene glycol monoethyl ether acetate (PMA) was used.

In Table 3, the kinds of the coloring materials, the acrylic copolymer, the polymer dispersing agent and the solvent constituting the coloring material dispersion are denoted by the abbreviations, and the respective blending amounts (% by weight) are described.

[Comparative Example 9]

The dispersion stability of the colorant dispersion prepared by the same method as in Example 23 and the evaluation results of the developability of the photosensitive colored resin composition were evaluated in the same manner as in Example 23 except that the acrylic copolymer (P-6) was used in place of the acrylic copolymer (P-3) 3.

[Example 24]

Disperbyk LPN-6919 (DP-2, manufactured by BYK-Chemie) having tertiary amino group was used as a polymer dispersant instead of Disperbyk LPN-21116 (DP-1 manufactured by BYK-Chemie and a 40 wt% solution of propylene glycol monoethyl ether acetate) Table 3 shows the dispersion stability of the colorant dispersion liquid prepared in the same manner as in Example 3 and the evaluation results of the developability of the photosensitive colored resin composition, except that a 40 wt% solution of propylene glycol monoethyl ether acetate was used.

[Example 25]

Disperbyk 2001 (DP-3, produced by BYK-Chemie) having a quaternary ammonium salt and a carboxyl group was used as a polymer dispersant instead of Disperbyk LPN-21116 (DP-1, produced by BYK-Chemie and a 40 wt.% Solution of propylene glycol monoethyl ether acetate) Table 3 shows the dispersion stability of the colorant dispersion liquid prepared in the same manner as in Example 3 and the evaluation results of the developability of the photosensitive colored resin composition, except that a 40 wt% solution of propylene glycol monoethyl ether acetate was used.

From the results of Examples 23 to 25 and Comparative Example 9, it is possible to stabilize the dispersion without adding the polymer dispersant by using the acrylic copolymer of the present invention, but it is preferable to add the polymer dispersant to stabilize the dispersion more, It is more preferable to use a polymer dispersant having a tertiary amino group.

[Example 26]

220 g of the titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) produced by the thermal plasma method, 57 g of a 35 wt% solution of the acrylic copolymer (P-3) in propylene glycol monoethyl ether acetate as a dispersant, Except that 25 g of LPN-21116 (DP-1, produced by BYK-Chemie, a 40 wt% solution of propylene glycol monoethyl ether acetate) and 698 g of propylene glycol monoethyl ether acetate (PMA) Table 3 shows the dispersion stability of one coloring material dispersion and the evaluation results of the developability of the photosensitive colored resin composition.

[Example 27]

175 g of the titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) prepared by the thermal plasma method, 186 g of a 35 wt% solution of the acrylic copolymer (P-3) in propylene glycol monoethyl ether acetate as a dispersant, Except that 25 g of LPN-21116 (DP-1, produced by BYK-Chemie, a 40 wt% solution of propylene glycol monoethyl ether acetate) and 614 g of propylene glycol monoethyl ether acetate (PMA) Table 3 shows the dispersion stability of one coloring material dispersion and the evaluation results of the developability of the photosensitive colored resin composition.

From the results of Example 3 and Examples 26 to 27, it was found that the acrylic copolymer of the present invention was used, and that the resin composition was more preferable as the weight composition ratio of the coloring material component / resin component than that of 90/10.

[Example 28]

175 g of a high-resistance carbon black (Bk-2, produced by Cabot Corporation), 171 g of a 35 wt% solution of propylene glycol monoethyl ether acetate in an acrylic copolymer (P-3), 10 g of Disperbyk LPN- 38 g of propylene glycol monoethyl ether acetate (manufactured by BYK-Chemie, 40 wt% solution of propylene glycol monoethyl ether acetate) and 616 g of propylene glycol monoethyl ether acetate (PMA) were charged into a tank and stirred with a homomixer (PRIMIX Corporation) for 20 minutes to prepare a preliminary dispersion . Thereafter, the preliminary dispersion liquid was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 75% of zirconium oxide beads (YTZ ball, manufactured by Neturen Co., Ltd.) And dispersed for 3 hours at a rotation speed of 8 m / s to obtain a colored material dispersion 37 having a solid content concentration of 25% by weight and a colorant / resin (weight ratio) = 70/30.

37.71 g of the colorant dispersion liquid 37 and 4.48 g of a 35 wt% solution of the acrylic copolymer (P-1) in propylene glycol monoethyl ether acetate, 53.80 g of propylene glycol monoethyl ether acetate, "Adeka (TM) (Manufactured by Asahi Denka Kogyo KK), 2.55 g of dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.), 0.45 g of 3-acryloxypropyltrimethoxysilane, 0.45 g of BYK-331 Ltd.) were mixed to prepare a photosensitive colored resin composition, and the developing performance was evaluated in the same manner as in Example 1. [ Table 3 shows the dispersion stability of the colorant dispersion and the evaluation results of the developability of the photosensitive resin composition.

[Comparative Example 10]

Table 3 shows the dispersion stability of the colorant dispersion prepared by the same method as in Example 28 except that P-6 was used in place of P-3 as the acrylic copolymer, and the evaluation results of the developability of the photosensitive resin composition.

[Example 29]

120 g of the organic pigment PR177 (R-1, manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.), 114 g of a 35 wt% solution of the acrylic copolymer (P-3) in propylene glycol monoethyl ether acetate, 100 g of LPN-21116 (DP-1, manufactured by BYK-Chemie, a 40 wt% solution of propylene glycol monoethyl ether acetate) and 666 g of propylene glycol monoethyl ether acetate (PMA) For 20 minutes to obtain a preliminary dispersion. Thereafter, a preliminary dispersion liquid was supplied to an Ultra Apex mill (manufactured by Kotobuki Kogyo Co., Ltd.) equipped with a centrifugal separator filled with 75% of 0.05 mm? Zirconium oxide beads (YTZ ball manufactured by Neturen Co., Ltd.) And dispersed for 3 hours at a rotation speed of 8 m / s to obtain a colored material dispersion 39 having a solid content concentration of 20% by weight and a coloring material / resin (weight ratio) = 60/40. The dispersion stability of the obtained coloring material dispersion was evaluated by the same method as in Example 1. [

37.50 g of this coloring material dispersion 39 and 7.29 g of a 35 wt% solution of propylene glycol monoethyl ether acetate in the acrylic copolymer (P-1), 50.26 g of propylene glycol monoethyl ether acetate, 50 g of "Adeka (TM) (Manufactured by Asahi Denka Kogyo KK), 4.05 g of dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.), 0.45 g of 3-acryloxypropyltrimethoxysilane, 0.45 g of BYK-331 Ltd.) were mixed to prepare a photosensitive colored resin composition, and the developing performance was evaluated in the same manner as in Example 1. [

[Comparative Example 11]

Table 3 shows the dispersion stability of the colorant dispersion prepared in the same manner as in Example 29 except that P-6 was used in place of P-3 as the acrylic copolymer, and the evaluation results of the developability of the photosensitive resin composition.

[Example 30]

50 g of the dye AR289 (R-2, manufactured by Chugai Kasei Co., Ltd.), 357 g of a 35 wt% solution of the acrylic copolymer (P-3) in propylene glycol monoethyl ether acetate and 35 g of Disperbyk LPN-21116 (Manufactured by BYK-Chemie, 40 wt% solution of propylene glycol monoethyl ether acetate) and 530 g of propylene glycol monoethyl ether acetate (PMA) were charged into a tank and stirred with a homomixer (PRIMIX Corporation) for 20 minutes To obtain a preliminary dispersion. Thereafter, the preliminary dispersion liquid was supplied to an Ultra Apex mill (Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 75% of zirconium oxide beads (YNZ Ball made by Neturen Co., Ltd.) And dispersed for 3 hours at a rotation speed of 8 m / s to obtain a coloring material dispersion 41 having a solid content concentration of 20% by weight and a coloring material / resin (weight ratio) = 25/75. The dispersion stability of the obtained coloring material dispersion was evaluated by the same method as in Example 1. [

45.00 g of the colorant dispersion liquid 41 and 1.03 g of a 35 wt% solution of the acrylic copolymer (P-1) in propylene glycol monoethyl ether acetate, 48.33 g of propylene glycol monoethyl ether acetate, "Adeka (TM) Optomer" N -1.919 (manufactured by Asahi Denka Kogyo KK), 4.86 g of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., DHPA), 0.45 g of 3-acryloxypropyltrimethoxysilane, 0.75 g of BYK- Ltd.) were mixed to prepare a photosensitive colored resin composition, and the developing performance was evaluated in the same manner as in Example 1. [

[Comparative Example 12]

The dispersion stability of the colorant dispersion prepared by the same method as in Example 30 and the evaluation results of the developability of the photosensitive resin composition are shown in Table 3, except that P-6 was used in place of P-3 as the acrylic copolymer

[Example 31]

(Ag-1, manufactured by Daiwa Kasei Co., Ltd.), 57 g of a 35 wt% solution of propylene glycol monoethyl ether acetate in an acrylic copolymer (P-3) and 35 g of Disperbyk LPN-21116 -1, manufactured by BYK-Chemie, a 40 wt% solution of propylene glycol monoethyl ether acetate) and 733 g of propylene glycol monoethyl ether acetate (PMA) were charged into a tank and stirred with a homomixer (PRIMIX Corporation) for 20 minutes To obtain a preliminary dispersion. Thereafter, a preliminary dispersion liquid was supplied to an Ultra Apex mill (Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 75% of zirconium oxide beads (YTZ ball, manufactured by Neturen Co., Ltd.) And dispersed for 3 hours at a rotation speed of 8 m / s to obtain a colored material dispersion 43 having a solid content concentration of 20% by weight and a coloring material / resin (weight ratio) = 80/20. The dispersion stability of the obtained coloring material dispersion was evaluated by the same method as in Example 1. [

46.88 g of this Coloring Material Dispersion 43 and 6.37 g of a 35 wt% solution of the propylene glycol monoethyl ether acetate of the acrylic copolymer (P-1), 43.36 g of propylene glycol monoethyl ether acetate, "Adeka (TM) Optomer" N -1919 (manufactured by Asahi Denka Kogyo KK), 2.11 g of dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.), 0.45 g of 3-acryloxypropyltrimethoxysilane, 0.45 g of BYK-331 Ltd.) were mixed to prepare a photosensitive colored resin composition, and the developing performance was evaluated in the same manner as in Example 1. [

[Comparative Example 13]

Table 3 shows the dispersion stability of the colorant dispersion prepared by the same method as in Example 31 except that P-6 was used in place of P-3 as the acrylic copolymer, and the evaluation results of the developability of the photosensitive resin composition.

From the results of Examples 28 to 31 and Comparative Examples 10 to 13, it has been found that the use of the acrylic copolymer of the present invention enables dispersion stabilization of not only inorganic pigments but also organic pigments, dyes and metal fine particles.

(Industrial applicability)

The coloring material dispersion of the present invention is excellent in dispersion stability and viscosity stability with time even in a composition containing a coloring material at a high concentration. In addition, it is possible to form a coating film having excellent alkali solubility and heat resistance by preparing the photosensitive colored resin composition using the colorant dispersion of the present invention. Therefore, a high-performance coloring pattern such as a color filter substrate for a liquid crystal display device or a sensor substrate for a touch panel can be produced efficiently.

Claims (8)

A coloring material dispersion liquid containing at least a coloring material, an acrylic copolymer and an organic solvent,
Wherein the acrylic copolymer has a structure represented by the following formula (A) having at least an ethylenic unsaturated group in its side chain and a structure represented by the following formula (B) having a tertiary amino group in the side chain and / or a quaternary ammonium salt in the side chain (D) having a structure represented by the following formula (C), a structure (D) having a carboxyl group in a side chain and a structure (E) having an aromatic ring and having an acid value of 5-70 mmol / 100 g and an acid value of 50-120 mgKOH / g , And a polystyrene-reduced weight average molecular weight of 5,000 to 30,000 by gel permeation chromatography.

Wherein R ¹ and R ² independently represent a hydrogen atom or a methyl group, R ³ represents an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, a divalent aromatic hydrocarbon having 6 to 10 carbon atoms Lt; RTI ID = 0.0 &gt;

Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, Bivalent aromatic hydrocarbon group; R ⁶ and R ⁷ independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms An aromatic hydrocarbon group]

Wherein R ⁸ is a hydrogen atom or a methyl group, R ⁹ is an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, Each of R ¹⁰ , R ¹¹ and R ¹² is independently selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 8 carbon atoms, And X represents any one of bromine, chlorine, iodine, hydrogen sulfate, and hydroxide; The method according to claim 1,
(D) having a carboxyl group is represented by the following formula (D1).

Wherein R ¹³ is a hydrogen atom or a methyl group, R ¹⁴ is any one selected from an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon chain having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon chain having 6 to 10 carbon atoms , And n represents an integer of 0 to 6, and may be a single or a mixture of plural n) 3. The method according to claim 1 or 2,
Wherein the structure (E) having an aromatic ring is represented by the following formula (E1) or (E2).

Wherein R ¹⁵ is a hydrogen atom or a methyl group, R ¹⁶ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms , A halogen atom, an ester group, an acyl group and a nitro group]

Wherein R ¹⁷ is a hydrogen atom or a methyl group, R ¹⁸ is hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms , A halogen atom, an ester group, an acyl group and a nitro group] 4. The method according to any one of claims 1 to 3,
Wherein the acrylic copolymer further has a structure represented by the following formula (F) having a carboxylic acid ester in a side chain.

Wherein R ¹⁹ is a hydrogen atom or a methyl group, R ²⁰ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ²¹ is an alkyl group having 2 to 40 carbon atoms. 5. The method of claim 4,
^Wherein the total number of carbon atoms of R ²⁰ and R ²¹ is 4 or more. 6. The method according to any one of claims 3 to 5,
A colorant dispersion liquid having a structure represented by the above formula (E2). 7. The method according to any one of claims 1 to 6,
Characterized in that, in addition to the acrylic copolymer, a polymeric dispersant having at least a tertiary amino group is contained. A photosensitive colored resin composition characterized by containing at least the colorant dispersion according to any one of claims 1 to 7, a polyfunctional acrylic monomer and a photo radical polymerization initiator.