KR102041833B1 - Coloring material dispersed liquid and photosensitive coloring resin composition - Google Patents

Abstract

It provides the coloring material dispersion liquid and the photosensitive colored resin composition which have the outstanding storage stability, and provides the coloring material dispersion liquid which shows the outstanding plate making characteristic when a colored film is formed using the said photosensitive colored resin composition. At least a coloring material, an acrylic copolymer and an organic solvent, wherein the acrylic copolymer is represented by a structure represented by formula (A) having at least an ethylenically unsaturated group in the side chain and a formula (B) having a tertiary amino group in the side chain. It has a structure represented by Formula (C) which has a quaternary ammonium salt in a losing structure and / or a side chain, the structure (D) which has a carboxyl group in a side chain, and the structure (E) which has an aromatic ring, and has a base value of 5-70 mmol / 100g, and the acid value is 50 to 120mgKOH / g, characterized in that the polystyrene reduced weight average molecular weight of 5,000 to 30,000 by gel permeation chromatography.

Description

Colorant dispersion and photosensitive colored resin composition {COLORING MATERIAL DISPERSED LIQUID AND PHOTOSENSITIVE COLORING RESIN COMPOSITION}

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

In recent years, color liquid crystal display (LCD) is rapidly spreading as a flat display such as a personal computer or a mobile phone. For example, in LCD color filters, different colors of red, green, and blue are sequentially formed in a color pattern such as a stripe pattern or a mosaic pattern on the surface of a transparent substrate such as a glass or a plastic sheet on which a black matrix is formed. The colorant dispersion technique of any one of a colored layer and a black matrix is playing an important role.

In addition, the demand for color characteristics of the above-described color filter for LCDs is increasing due to the rise of various display devices such as organic EL and various display information. In particular, the demand for a wider color reproducibility range is intensifying, and as a color filter coloring material, a technique of stably dispersing the coloring material at a high concentration is important. Generally, a coloring material dispersion liquid is formed from a coloring material, a solvent, a dispersing agent, and binder resin, and it becomes possible to disperse | distribute a coloring material stably by adding a large amount of a dispersing agent in a composition, but a dispersing agent in the heating process for manufacturing a color filter There was a case that yellowing caused a decrease in brightness, or the concentration of alkali-soluble photocurable resin was diluted, resulting in problems such as lowering of sensitivity, poor curing, poor coating film strength, poor developability, and the like. In particular, developing defects cause serious problems in production. Therefore, the colorant dispersion liquid has been a challenge to ensure the stability of the pigment dispersion liquid by giving high dispersion stability to the binder resin itself with as little dispersant as possible. In addition, in recent years, since the demand for color characteristics is diversified, development of coloring materials using dyes and inorganic pigments, as well as conventional organic pigments, is progressing. It has become a difficult situation to stabilize dispersion.

In addition, in the field of touch panel displays with remarkable technological innovations, black matrices are formed as light shielding films similarly to color filters, and they are generally formed by printing inks on cover glass or cover film facing the sensor substrate. . On the other hand, the demand for weight reduction of touch panels is increasing, and the development of the technology which simultaneously forms a light shielding film and a touch sensor on a cover glass is advanced. In such a case, since it is necessary to form an electrode or the like after forming the black matrix on the cover glass, high heat resistance that can withstand the process of forming the electrode in a high temperature vacuum state is required.

As pigments that can be used in the black matrix, carbon black, titanium oxide such as lower titanium oxide or titanium oxynitride, metal oxides such as iron oxide, and other organic pigment blends are used, but carbon black and titanium oxynitride are the mainstream. In order to obtain the black matrix which has high insulation, the thing which mixed the carbon black surface-treated with titanium black, resin, etc. or organic pigment as a light-shielding material is used (for example, refer patent document 1). However, in order to obtain high light-shielding property, it is necessary to stably disperse | distribute various pigments at high pigment concentration, and it was insufficient in the viewpoint of long-term storage stability in the prior art.

As a technique for stabilizing dispersion with a small amount of dispersant, a technique using a polymer dispersant having both an acid value and an amine value and a copolymer having an imide group and a photocurable functional group is disclosed (see Patent Document 2, for example). In order to disperse | distribute and stabilize this difficult titanium black and carbon black coloring material, it was insufficient. In addition, even at a high pigment concentration, as a technique for stably dispersing a pigment, a technique using an acid value dispersant having an acid value and an amine value dispersant having an amine number (see, for example, Patent Document 3), and both a basic block and an acid block The technique (for example, refer patent document 4) using the resin type dispersing agent which has the block structure to have is mentioned. Although it is useful as a coloring liquid for inkjet coating, application to the coloring liquid for photolithography which requires photosensitive property and developability was difficult.

On the other hand, as an acrylic resin for pigment dispersion, an acrylic copolymer having a carboxyl group and an acryloyl group or a methacryloyl group in its side chain (see Patent Document 5, for example), or an acrylic having an acid value or an amine value in a specific molecular weight or hydroxyl group. Although resin (for example, refer patent document 6) is mentioned, all were inadequate from the viewpoint of making all dispersion stability, photosensitive, and developability compatible.

Japanese Patent Publication No. 2010-95716 Japanese Patent No. 4195323 Japanese Patent Publication No. 4452252 Japanese Patent Publication No. 2009-167303 Japanese Patent No. 3120476 Japanese Patent Publication No. 2003-171605

The present invention has been devised in view of such drawbacks of the prior art, and its object is to provide a colorant dispersion having excellent dispersion stability and alkali development solubility even in a composition containing a coloring agent at a high concentration. Moreover, by using such a coloring material dispersion liquid, the photosensitive coloring resin composition excellent in storage stability and plate making characteristic is provided.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the prior art subject, it discovered that the subject of this invention can be solved by using the acrylic copolymer which has a specific structure as follows when disperse | distributing a coloring material.

That is, this object of this invention is achieved by the following structures.

(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 ethylenically unsaturated group in the side chain, and a tertiary amino group in the side chain. A structure represented by the following formula (B) having a structure and / or a structure represented by the following formula (C) having a quaternary ammonium salt in the side chain, a structure having a carboxyl group in the side chain (D), and a structure having an aromatic ring (E And a polyhydric equivalent weight average molecular weight of 5,000 to 30,000, having a base value of 5 to 70 mmol / 100 g, an acid value of 50 to 120 mg KOH / g, and gel permeation chromatography.

[In formula, R <^1> , R <^2> is a hydrogen atom or a methyl group independently of each other, R <^3> is a C1-C4 alkylene group, a C3-C6 bivalent alicyclic hydrocarbon group, a C6-C10 divalent aromatic hydrocarbon Any one selected from the group]

[In formula, R <^4> is a hydrogen atom or a methyl group, R <^5> is a C1-C4 alkylene group, a C1-C4 divalent alkoxy group, a C3-C6 bivalent alicyclic hydrocarbon group, C6-C10 Any one selected from a divalent aromatic hydrocarbon group, R ⁶ and R ⁷ independently of each other, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, 6 to 10 carbon atoms Any one selected from aromatic hydrocarbon groups]

[In formula, R <^8> is a hydrogen atom or a methyl group, R <^9> is a C1-C4 alkylene group, a C1-C4 divalent alkoxy group, a C3-C6 bivalent alicyclic hydrocarbon group, a C6-C10 Any one selected from a divalent aromatic hydrocarbon group, R ¹⁰ , R ¹¹ , and R ¹² independently of one another are an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, and carbon 6 Any one selected from -10 aromatic hydrocarbon groups, X represents any one of bromine, chlorine, iodine, hydrogen sulfate and hydroxide]

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

[In formula, R <^13> is a hydrogen atom or a methyl group, R <^14> is a C1-C4 alkylene group, a C3-C6 bivalent alicyclic hydrocarbon chain, a C6-C10 divalent aromatic hydrocarbon chain is any one selected. N represents an integer of 0 to 6, and may be a single type or a mixture of a plurality of n.]

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

[In formula, R <^15> is a hydrogen atom or a methyl group, R <^16> is hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 alicyclic hydrocarbon group, a C6-C10 aromatic hydrocarbon group , Halogen atom, ester group, acyl group, and nitro group.

[In formula, R <^17> is a hydrogen atom or a methyl group, R <^18> is hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 alicyclic hydrocarbon group, a C6-C10 aromatic hydrocarbon group , Halogen atom, ester group, acyl group, and nitro group.

(4) The coloring according to any one of (1), (2) or (3), wherein the acrylic copolymer further has a structure represented by the following formula (F) having a carboxylic acid ester in the side chain. Redispersion.

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

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

(6) The coloring material dispersion liquid in any one of (3)-(5) which has a structure represented by said Formula (E2).

(7) The coloring material dispersion liquid in any one of (1)-(6) containing the polymeric dispersing agent which has an at least tertiary amino group in addition to the said acrylic copolymer.

(8) The photosensitive colored resin composition containing at least the coloring material dispersion liquid as described in any one of (1)-(7), a polyfunctional acrylic monomer, and an optical radical polymerization initiator.

(Effects of the Invention)

Even if the coloring material dispersion liquid of this invention contains a coloring material in high concentration, the characteristic excellent in dispersion stability and alkali image development solubility is acquired. By using this coloring material dispersion liquid, the photosensitive colored resin composition excellent in storage stability and plate making characteristic is obtained.

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

The coloring material dispersion liquid of this invention consists of at least a coloring material, the acrylic copolymer which has a specific structure, and the organic solvent. It is characterized by the above-mentioned.

The acrylic copolymer used in the present invention is characterized by having a tertiary amino group and / or quaternary ammonium salt, carboxyl group and aromatic ring in the side chain, and containing an ethylenically unsaturated bond in the acrylic copolymer side chain.

When the acrylic copolymer used in the present invention has photosensitive properties, that is, when an initiator which generates radicals, anions or cations by an active energy ray such as ultraviolet (UV) is used in combination, the acrylic copolymer itself is subjected to crosslinking reaction. In order to express the function blown in, the side chain necessarily has an acryl unit or methacryl unit represented by following formula (A) which has an ethylenically unsaturated group.

[In formula, R <^1> , R <^2> is a hydrogen atom or a methyl group independently of each other, R <^3> is a C1-C4 alkylene group, a C3-C6 bivalent alicyclic hydrocarbon group, a C6-C10 divalent aromatic hydrocarbon Any one selected from the group]

In said Formula (A), R <^1> , R <^2> is a hydrogen atom or a methyl group independently of each other, and when R <^1> is hydrogen, it becomes an acryl unit, and when it is a methyl group, it becomes a methacryl unit. R ³ is selected from an alkylene group of 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group of 3 to 6 carbon atoms, a divalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and preferably an alkylene group of 1 to 3 carbon atoms, or 5 carbon atoms. It may be a -6 divalent alicyclic hydrocarbon group or a C6-C8 divalent aromatic hydrocarbon group.

It does not specifically limit as a introduction method of the (meth) acryl unit represented by said formula (A), It can flow in by a conventional method. For example, the method of addition-reacting glycidyl-group containing polymerizable unsaturated monomer to the (meth) acryl copolymer which copolymerized the carboxyl group-containing unsaturated monomer, etc. are mentioned. In this case, acrylic acid, methacrylic acid, etc. can be mentioned as a carboxyl group-containing unsaturated monomer to copolymerize, glycidyl acrylate, glycidyl methacrylate, etc. can be illustrated as a glycidyl-containing unsaturated monomer. In this invention, these acrylic monomers may be used individually or in mixture of 2 or more types.

In order to express high dispersion stability, the acrylic copolymer used by this invention has the following formula which has a (meth) acryl unit represented by following formula (B) which has a tertiary amino group in a side chain, and / or a quaternary ammonium salt in a side chain. It is essential to contain the (meth) acryl unit represented by (C).

The (meth) acrylic unit represented by the formula (B) having a tertiary amino group and the (meth) acrylic unit represented by the formula (C) having a quaternary ammonium salt in the side chain have high affinity with all the coloring materials and dispersion stability. In order to improve the efficiency, either or both of them may be introduced. In the case of application to the use which needs developability like this invention, it is preferable to introduce the (meth) acryl unit of Formula (B) which has a tertiary amino group from a viewpoint of obtaining a balance of developability and dispersion stability easily.

[In formula, R <^4> is a hydrogen atom or a methyl group, R <^5> is a C1-C4 alkylene group, a C1-C4 divalent alkoxy group, a C3-C6 bivalent alicyclic hydrocarbon group, C6-C10 Any one selected from a divalent aromatic hydrocarbon group, R ⁶ and R ⁷ independently of each other, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, 6 to 10 carbon atoms Any one selected from aromatic hydrocarbon groups]

In said Formula (B), R <^4> is a hydrogen atom or a methyl group, and when R <^4> is hydrogen, it becomes an acryl unit and when it is a methyl group, it becomes a methacryl unit. R ⁵ is selected from an alkylene group of 1 to 4 carbon atoms, a divalent alkoxy group of 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group of 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group of 6 to 10 carbon atoms, preferably A C1-C3 alkylene group, a C5-C6 divalent alicyclic hydrocarbon group, and a C6-C8 bivalent aromatic hydrocarbon group may be sufficient.

R ⁶ and R ⁷ may be the same as or different from each other independently and are selected from an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, and an aromatic hydrocarbon group of 6 to 10 carbon atoms, Preferably, a C1-C3 alkylene group, a C1-C3 alkoxy group, a C5-C6 bivalent alicyclic hydrocarbon group, and a C6-C8 divalent aromatic hydrocarbon group may be sufficient.

As an unsaturated monomer which comprises the (meth) acryl unit which has a tertiary amino group represented by Formula (B), 2-dimethylaminoethyl acrylate, 2-diethylaminoethyl acrylate, 2-dipropylaminoethyl acrylate, and acrylic acid 2-diphenylaminoethyl, acrylic acid-2-dibenzylaminoethyl, methacrylic acid-2-dimethylaminoethyl, methacrylic acid-2-diethylaminoethyl, methacrylic acid-2-dipropylaminoethyl, meta Although methacrylic acid-2-diphenylaminoethyl, methacrylic acid-2-benzylaminoethyl, etc. can be illustrated, It is not specifically limited. These (meth) acryl monomers may be used independently or may be used in two or more types of mixtures.

The (meth) acryl unit which has a tertiary amino group represented by Formula (B) can flow in by copolymerizing the unsaturated monomer containing an amino group.

[In formula, R <^8> is a hydrogen atom or a methyl group, R <^9> is a C1-C4 alkylene group, a C1-C4 divalent alkoxy group, a C3-C6 bivalent alicyclic hydrocarbon group, a C6-C10 Any one selected from a divalent aromatic hydrocarbon group, R ¹⁰ , R ¹¹ , and R ¹² independently of one another are an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, and carbon 6 Any one selected from -10 aromatic hydrocarbon groups, X represents any one of bromine, chlorine, iodine, hydrogen sulfate and hydroxide]

In said Formula (C), R <^8> is a hydrogen atom or a methyl group, and when R <^8> is hydrogen, it becomes an acryl unit, and when it is a methyl group, it becomes a methacryl unit. R ⁹ is selected from an alkylene group of 1 to 4 carbon atoms, a divalent alkoxy group of 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group of 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group of 6 to 10 carbon atoms, preferably A C1-C3 alkylene group, a C5-C6 divalent alicyclic hydrocarbon group, and a C6-C8 bivalent aromatic hydrocarbon group may be sufficient.

R ¹⁰ , R ¹¹ , and R ¹² may be the same as or different from each other, and each may have 1 to 4 alkyl groups, 1 to 4 alkoxy groups, 3 to 6 alicyclic hydrocarbon groups, and 6 to 10 aromatic hydrocarbon groups. It is selected from, Preferably it may be a C1-C3 alkylene group, a C1-C3 alkoxy group, a C5-C6 bivalent alicyclic hydrocarbon group, a C6-C8 divalent aromatic hydrocarbon group.

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

As an unsaturated monomer which comprises the (meth) acryl unit which has a quaternary ammonium salt represented by Formula (C), acrylic acid dimethyl amino ethyl methyl chloride salt, dimethyl amino ethyl benzyl chloride salt, methacrylic acid dimethyl amino ethyl methyl chloride salt Although the methacrylate dimethylaminoethylbenzyl chloride salt etc. are illustrated, it is not specifically limited. These (meth) acryl monomers may be used independently or may be used in two or more types of mixtures.

The (meth) acryl unit having a quaternary ammonium salt represented by 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 2-dimethylaminoethyl methacrylate are preferred. In the present invention, the acrylic monomers represented by the formulas (B) and / or (C) may be used alone or in a mixture of two or more kinds.

In order to provide alkali developability, the acrylic copolymer used by this invention must have acidic groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, in a side chain, and in this invention, it must necessarily have a structure (D) which has a carboxyl group in a molecular side chain. .

The structure (D) which has such a carboxyl group can flow in by copolymerizing a carboxyl group-containing unsaturated monomer. Acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid, etc. can be illustrated as a carboxyl group-containing unsaturated monomer. Considering the inflow of the (meth) acryl unit having an ethylenically unsaturated group into the molecular side chain represented by the above formula (A) as the structure (D) having a carboxyl group, the carboxyl group-containing unsaturated monomer represented by the following formula (D1) is It is preferable from the viewpoint of control and stability of the reaction.

[In formula, R <^13> is a hydrogen atom or a methyl group, R <^14> is a C1-C4 alkylene group, a C3-C6 bivalent alicyclic hydrocarbon chain, a C6-C10 divalent aromatic hydrocarbon chain is any one selected. N represents an integer of 0 to 6, and may be a single type or a mixture of a plurality of n.]

In said Formula (D1), R <^13> is a hydrogen atom or a methyl group, and when R <^13> is hydrogen, it is acrylic acid and methacrylic acid when it is a methyl group. R ¹⁴ is selected from an alkylene group of 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group of 3 to 6 carbon atoms, a divalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and preferably an alkylene group of 1 to 3 carbon atoms, or 5 carbon atoms. It may be a -6 divalent alicyclic hydrocarbon group or a C6-C8 divalent aromatic hydrocarbon group. n is an integer of 0-6, Preferably it is 0. n may be one integer or multiple integers between 0-6.

As an unsaturated monomer (D1) containing the carboxyl group represented by the said structure, acrylic acid, methacrylic acid, 2-carboxyethyl acrylate oligomer, 2-carboxyethyl methacrylate oligomer, etc. can be illustrated. These (meth) acryl monomers may be used independently or may be used in two or more types of mixtures.

In order to express high heat resistance, the acrylic copolymer of this invention necessarily has the structure (E) which has an aromatic ring in a side chain. The structure (E) having an aromatic ring in the side chain can be introduced by copolymerizing an unsaturated monomer having an aromatic ring, and a derivative of a benzyl group and a benzyl group such as the following formula (E1), or a phenyl group and a phenyl group such as (E2) Derivatives are particularly preferable, and the effect of improving the higher heat resistance is obtained.

[In formula, R <^15> is a hydrogen atom or a methyl group, R <^16> is hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 alicyclic hydrocarbon group, a C6-C10 aromatic hydrocarbon group , Halogen atom, ester group, acyl group, and nitro group.

In said Formula (E1), R <^15> is a hydrogen atom or a methyl group, and when R <^15> is hydrogen, it becomes an acryl unit, and when it is a methyl group, it becomes a methacryl unit. R ¹⁶ is hydrogen, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, an aromatic hydrocarbon group of 6 to 10 carbon atoms, a halogen atom, an ester group, an acyl group and a nitro group Any one selected from hydrogen, preferably hydrogen, an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, an alicyclic hydrocarbon group of 5 to 6 carbon atoms, and an aromatic hydrocarbon group of 6 to 8 carbon atoms.

As a (meth) acryl monomer containing the aromatic ring represented by said formula (E1), although benzyl acrylate, benzyl methacrylate, etc. are illustrated, for example, It is not limited to these. In this invention, these (meth) acryl monomers may be used individually or in mixture of 2 or more types.

[In formula, R <^17> is a hydrogen atom or a methyl group, In formula, R <^18> is hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 alicyclic hydrocarbon group, C6-C10 Aromatic hydrocarbon group, halogen atom, ester group, acyl group and nitro group.

In said Formula (E2), R <^17> is a hydrogen atom or a methyl group, and when R <^17> is hydrogen, it becomes an acryl unit, and when it is a methyl group, it becomes a methacryl unit. R ¹⁸ is hydrogen, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, an aromatic hydrocarbon group of 6 to 10 carbon atoms, a halogen atom, an ester group, an acyl group and a nitro group Any one selected from hydrogen, preferably hydrogen, an alkyl group of 1 to 3 carbon atoms, an alkoxy group of 1 to 3 carbon atoms, an alicyclic hydrocarbon group of 5 to 6 carbon atoms, and an aromatic hydrocarbon group of 6 to 8 carbon atoms.

As an unsaturated monomer containing the aromatic ring represented by said Formula (E2), for example, styrene, (alpha) -methylstyrene, 4-vinyltoluene, its structural isomer, 4-methoxystyrene, its structural isomer, 4-butoxy Styrene and its structural isomers, 4-tert-butoxystyrene and its structural isomers, 4-vinylbiphenyl, 2-vinylnaphthalene and its structural isomers, 9-vinylanthracene, 9-vinylcarbazole, etc. It is not limited to. In this invention, these acrylic monomers may be used individually or in mixture of 2 or more types.

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. Especially, it is preferable to include the (meth) acryl unit which contains a tertiary amino group in a side chain, As an especially preferable acrylic copolymer, the acrylic copolymer containing the structural unit represented by following formula (1) is illustrated, and it is necessary In accordance with this, other main chain structural units may be contained.

[In formula, R <^1> , R <^2> , R <^4> , R <^13> , R <^17> is a hydrogen atom or a methyl group independently of each other, R <^3> is a C1-C4 alkylene group, a C3-C6 bivalent alicyclic hydrocarbon group, Any one selected from a C6-C10 divalent aromatic hydrocarbon group, R ⁶ , R ⁷ independently of each other, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, 6 to 10 carbon atoms of any one selected from an aromatic hydrocarbon group, R ¹⁸ is hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, 3 to 6 carbon atoms of the alicyclic hydrocarbon group, 6 to 10 carbon atoms of the aromatic A hydrocarbon group, a halogen atom, an ester group, an acyl group, and a nitro group.

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

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

In said Formula (F), R <^19> is a hydrogen atom or a methyl group, and when R <^19> is hydrogen, it becomes an acryl unit, and when it is a methyl group, it becomes 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 this invention, this acrylic monomer is defined as the structure which has a carboxylic acid ester in a side chain.

As for the unsaturated monomer containing the carboxylic acid ester represented by Formula (F), the sum total of the number of carbon atoms of R <^20> and R <^21> becomes like this. Preferably it is four or more, More preferably, it may be 4-24 pieces. In addition, when R <^20> is hydrogen, R <^21> should just be a C4 or more alkyl group. Dispersion stability of a coloring material can be improved further by making the sum total of carbon number of R <^20> and R <^21> four or more.

Although the unsaturated monomer containing the carboxylic acid ester represented by Formula (F) can be illustrated, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, etc. are not specifically limited. These acrylic monomers may be used independently or may be used in two or more types of mixtures.

In the present invention, the structure having a carboxylic acid ester in the side chain can be introduced by copolymerizing a long chain alkyl group-containing unsaturated monomer. Examples of the long-chain alkyl group-containing unsaturated monomers include octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, dodecyl acrylate and dodecyl methacrylate. Especially, since the unsaturated monomer which has a carboxylic acid ester in the side chain which has a structure represented by said Formula (F) tends to express higher dispersion stability, it is especially preferable.

The acrylic copolymer of this invention can copolymerize arbitrary (meth) acrylic acid ester as a monomer other than the structural unit mentioned above as needed. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methyl methacrylate, ethyl methacrylate, meta Acrylic esters or methacrylic acid esters such as propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, and isobornyl methacrylate Or their (fluor) alkyl ester monomers, but not limited thereto.

In the acrylic copolymer used in the present invention, it is important to make the acid value and the base value within an appropriate range. As a basic value, it is essential to set it as 5-70 mmol / 100 g, and it is preferable to copolymerize so that it may become 10-30 mmol / 100 g preferably. When the base value is lower than this range, the pigment dispersion stability is poor, and when the base value is high, developability is poor. A base value can be in a predetermined range by preparing the composition ratio of the structural unit of an acrylic copolymer, especially the composition ratio of the structural unit of Formula (B) and (C). In addition, the base value of the acrylic copolymer is defined as the number of mol of perchloric acid which is important for neutralizing 100 g of the acrylic copolymer (unit: mmol / 100 g).

As an acid value of an acryl copolymer, it is essential to set it as 50-120 mgKOH / g, It is preferable to copolymerize so that it may become 50-100 mgKOH / g preferably. When the upper limit is exceeded, dispersion stability tends to be deteriorated, and when the upper limit is exceeded, alkali development tends to be difficult. An acid value can be made into a predetermined range by preparing the composition ratio of the structural unit of an acrylic copolymer. In addition, the acid value of an acrylic copolymer is defined as the mg number of potassium hydroxide which is important for neutralizing 1g of acrylic copolymers (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 cannot be formed and dispersion becomes unstable due to the interaction between the coloring materials. On the other hand, when the weight average molecular weight is greater than 30,000, there is a problem that the resin adsorption probability per colorant unit is lowered, resulting in unstable dispersion or deterioration in developability. In addition, the weight average molecular weight (Mw) of an acryl copolymer shall be measured by gel permeation chromatography using tetrahydrofuran as a carrier, and shall be converted using the analytical curve by standard polystyrene.

In the acrylic copolymer used in the present invention, the structural units represented by the above formulas (B) (C) (D1) (E1) (E2) and (F), and other arbitrary (meth) acrylic acid ester units It can be obtained in the form of a random copolymer, a block copolymer, etc. by general radical polymerization reactions, such as solution polymerization, emulsion polymerization, and block polymerization. Especially the form of a random copolymer is preferable. In addition, the (meth) acryl unit represented by Formula (A) can be introduced by the general method introduced by addition-reacting the monomer which has a functional group which can react with the side chain functional group of the acryl copolymer obtained above. .

Although it does not specifically limit as an organic solvent used for the coloring matter dispersion liquid of this invention, Specifically, 1 or more types chosen from aliphatic hydrocarbon, carboxylic acid ester, ketone, ether, alcohol are mentioned. Especially, 1 or more types chosen from carboxylic acid ester, ketone, and ether can be used. Preferred carboxylic acid esters include esters composed of saturated aliphatic carboxylic acids and saturated alcohols.

Specific esters include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonic acid, 2-ethylhexyl acetate, 2-butoxyethyl acetate, 3-methoxy-3-methyl-butyl acetate , Diethyl oxalate, ethyl acetoacetate, cyclohexyl acetate, 3-methoxy-butyl acetate, methyl acetoacetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isopentyl propionate, propylene glycol mono Although methyl ether propionate, propylene glycol monoethyl ether acetate, a pentyl acetate, a propylene glycol monomethyl ether acetate, etc. are mentioned, It is not limited to these.

Among these organic solvents, 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate and 3-methoxy-butyl acetate in a solvent of acetic acid ester or propionic acid ester And propylene glycol monomethyl ether acetate are particularly preferred.

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

In the coloring material dispersion of the present invention, any of organic pigments, inorganic pigments and dyes can be suitably used as the coloring material.

Examples of the organic pigments include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine, or metal phthalocyanine, aminoanthraquinone, diaminoanthraquinone, Anthraquinone pigments such as anthrapyrimidine, flavanthrone, ananthrone, indanthrone, pyrantrone, or bioanthrone, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, and thioindigo pigments And isoindolin-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, styrene-based pigments, or metal complex-based pigments.

Inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, cadmium red, bengalla, molybdenum red, molybdate orange, chromium Vermilion, sulfur lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, victorian green, ultramarine, wire, cobalt blue, cerulean blue, cobalt silica blue, cobalt Zinc silica blue, manganese violet, cobalt violet, etc. are mentioned.

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

When the specific example of a typical pigment and dye is shown by a color index (CI) number, the following are used preferably, but all are not limited to these.

Examples of red pigments include Pigment Red (hereinafter simply 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.

As examples of the orange pigment, Pigment Orange (hereinafter simply referred to as PO) 13, PO36, PO38, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71 and the like are used.

Examples of yellow pigments are Pigment Yellow (hereinafter referred to simply 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.

As examples of the purple pigment, pigment violet (hereinafter simply referred to as PV) 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50 and the like are used.

As examples of the blue pigment, Pigment Blue (hereinafter, simply referred to as PB) 15, PB15: 3, PB15: 4, PB15: 6, PB22, PB60, PB64 and the like are used.

As examples of the green pigment, Pigment Green (hereinafter simply referred to as PG) 7, PG10, PG36, PG58 and the like are used.

As an example of a black pigment, it can use from black organic pigment, mixed organic pigment, inorganic pigment, etc. As black organic pigments, carbon black, perylene black, aniline black, etc. are mixed and at least two or more kinds of pigments selected from red, blue, green, purple, yellow, magenta, cyan and the like are mixed and blackened. Examples of inorganic pigments include graphite, metal fine particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, metal oxides, complex oxides, metal sulfides, metal nitrides, and metal oxynitrides. Can be. These may be used individually by 1 type, or may mix and use 2 or more types. In particular, carbon black and titanium nitride are preferably used because they have high light shielding properties.

In addition, examples of the white pigment include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, silicon dioxide and the like.

Examples of the dye include, for example, 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, 51, 75, 90, 103, 126, CI Reactive Violet 1, 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, CI direct Yellow 8, 9, 11, 12, 27, 28, 29, 33, 35, 39, 41, 44, 50, 53, 58, 59, 68, 87, 93, 95, 96, 98, 100, 106, 108, 109, 110, 130, 142, 144, 161, 163, 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, etc. are mentioned.

In the coloring material dispersion liquid of this invention, it is more preferable to add a polymeric dispersing agent in order to disperse | distribute a coloring material uniformly or stably in a resin solution. Examples of the polymer dispersant include polyester polymer dispersants, acrylic polymer dispersants, polyurethane polymer dispersants, polyarylamine polymer dispersants, and carbodiimide dispersants. These polymeric dispersants are suitably selected and used according to the kind of coloring material.

Polymeric dispersants include a dispersant having only an amine value, a dispersant having only an acid value, a dispersant having an amine value and an acid value, and various dispersants having neither an amine value nor an acid value, but in order to make the effect of the present invention remarkable, It is more preferable to use, more preferably a polymer dispersant having only an amine number.

Specific examples of the dispersant having an amine value only 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 2150, Disperbyk 2150N , Disperbyk LPN 21116, Disperbyk LPN 21234, Disperbyk 9075, Disperbyk 9077 (above, produced by BYK-Chemie); EFKA 4015, EFKA 4020, EFKA 4046, EFKA 4047, EFKA 4050, EFKA 4055, EFKA 4060, EFKA 4080, EFKA 4300, EFKA 4330, EFKA 4340, EFKA 4400, EFKA 4401, EFKA 4402, EFKA 4403, EFKA 4800 Manufactured by BASF); Ajisper PB711 (manufactured by Ajinomoto Fine-Techno Co., Inc.) and the like, but are not limited to these.

Also in the dispersing agent having only an amine number, it is particularly preferable to use a polymer dispersing agent having at least a tertiary amino group, and specific examples thereof include Disperbyk LPN 6919 and Disperbyk LPN 21116.

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

These polymer dispersants may be used alone or in combination of two or more thereof. Since these polymeric dispersing agents do not have photosensitivity, when added in large quantities, there exists a possibility that the photosensitive performance of the target photosensitive colored resin composition may deteriorate, and it is preferable to set it as the appropriate addition amount which added dispersion stability and photosensitive performance. When it adds 1-50 (mass%) with respect to a coloring material, More preferably, it adds 3-30 (mass%), there exists an effect which stabilizes dispersion | distribution highly without degrading photosensitive performance, and still more preferable.

In the coloring material dispersion liquid of this invention, it is preferable that the weight composition ratio of a coloring material component / resin component is the range of 90/10-20/80, More preferably, it is 90/10-40/60. Here, a resin component is taken as the sum total of additives, such as a polymer dispersing agent, in addition to an acryl copolymer. If the amount of the resin component is very small, the dispersion stability of the coloring material is poor, on the contrary, if the amount of the coloring material component is very small, it is difficult to form a coating film having high coloring power when the colored coating film is formed using the coloring material dispersion. It is not desirable to do so.

As solid content concentration which combined the resin component and the coloring material component in the coloring material dispersion liquid of this invention, 2 mass% or more and 60 mass% or less are preferable from a viewpoint of dispersion stability and productivity, and also it is preferable that they are 5 mass% or more and 30 mass% or less. .

Although it does not specifically limit as a manufacturing method of the coloring material dispersion liquid of this invention, The method of disperse | distributing a coloring material in the acrylic copolymer solution using a disperser is generally performed.

As a disperser which disperse | distributes a coloring material, various methods, such as a ball mill, a sand grinder, three roll mills, a high speed impact mill, are mentioned, A bead mill is preferable from dispersion efficiency and microdispersion. As a bead mill, a coball mill, a basket mill, a pin mill, a dyno mill, etc. can be used. As beads of bead mills, it is preferable to use titania beads, zirconium oxide beads, zircon beads and the like.

As a bead diameter used for dispersion, 0.01 mm or more and 5.0 mm or less are preferable, More preferably, they are 0.03 mm or more and 1.0 mm or less. When the primary particle diameter of a coloring material and the particle diameter of the secondary particle formed by aggregation of a primary particle are small, it is preferable to use the fine dispersion beads which made 0.03 mm or more and 0.10 mm or less. In this case, it is preferable to disperse | distribute using the bead mill which has a separator by the centrifugal separation system which can isolate | separate minute dispersion beads and a dispersion liquid. On the other hand, when disperse | distributing the coloring material containing the coarse particle | grains of submicron grade, since a sufficient grinding force can be obtained by using a dispersion bead of 0.10 mm or more, it is preferable to disperse a pigment finely.

Although the photosensitive colored resin composition using the coloring material dispersion liquid of this invention is illustrated below, it is not limited to these.

The photosensitive colored resin composition of this invention is comprised by adding at least alkali-soluble polymer, a reactive monomer, and a photoinitiator to the coloring material dispersion liquid of this invention. These amount ratios are usually 10/90 to 90/10 as the weight composition ratio of the alkali-soluble polymer and the reactive monomer, and are about 1 to 20% by weight based on the total weight of the polymer and the monomer as the added amount of the photopolymerization initiator. Here, as the weight of the alkali-soluble polymer, the total weight of the acrylic copolymer contained in the coloring material dispersion liquid by adding the weight of the newly added alkali-soluble polymer is used.

As an alkali-soluble polymer of the photosensitive coloring resin composition of this invention, the acrylic copolymer used for the coloring material dispersion liquid may be used, or a new alkali-soluble polymer may be used. The alkali-soluble polymer used newly is demonstrated in detail below.

As an alkali-soluble polymer, the alkali-soluble polymer which has a carboxyl group is preferable, and the copolymer of unsaturated carboxylic acid and an ethylenically unsaturated compound can be used preferably. Examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid, dicarboxylic acids such as itaconic acid, maleic acid and fumaric acid or acid anhydrides thereof, and phthalic acid mono (2- And polyhydric carboxylic acid mono esters such as (meth) acryloyloxyethyl). In particular, an acrylic polymer comprising a structural unit derived from (meth) acrylic acid is preferable, and an acrylic polymer obtained by reacting a carboxylic acid contained in the structural unit with a compound containing an ethylenically unsaturated group and an epoxy group is used. Since the sensitivity at the time of exposure and image development becomes good, it can use preferably. As an ethylenically unsaturated group, an acryl group and methacryl group are preferable.

These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. As an ethylenically unsaturated compound copolymerizable, specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, n-propyl methacrylate, isopropyl methacrylate, acrylic acid n-butyl, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, tert-butyl methacrylate, n-acrylate Unsaturated carboxylic acid alkyl esters such as pentyl, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, p-methyl styrene, Aromatic vinyl compounds, such as o-methylstyrene, m-methylstyrene, (alpha) -methylstyrene, (crosslinked) cyclic hydrocarbon groups, such as tricyclo decanyl (meth) acrylate, and fires, such as amino ethyl acrylate Carboxylic acid vinyl esters such as unsaturated carboxylic acid glycidyl esters such as carboxylic acid amino alkyl esters, glycidyl acrylate and glycidyl methacrylate, vinyl acetate and vinyl propionate, acrylonitrile and methacryl Aliphatic conjugated dienes such as vinyl cyanide compounds such as ronitrile and α-chloroacrylonitrile, and 1,3-butadiene and isopropyl; polystyrenes having acryloyl group or methacryloyl group, respectively, polymethylacrylate and poly Although methyl methacrylate, polybutyl acrylate, polybutyl methacrylate, etc. are mentioned, It is not limited to these.

In particular, an acrylic polymer comprising (meth) acrylic acid and benzyl (meth) acrylate is particularly preferable from the viewpoints of dispersion stability and pattern workability.

Moreover, in addition to the acryl-type polymer obtained by making the compound which contains an ethylenically unsaturated group and an epoxy group react with the (meth) acrylic acid contained in the structural unit of the said base material, the acryl-type polymer which has an ethylenically unsaturated group in a side chain can be used preferably. As a specific example, the photopolymerizable resin "Cyclomer (trademark) P" which is a copolymer described in Japanese Patent No. 3120476, Japanese Patent Application Laid-Open No. 8-262221, or a commercial acrylic polymer (manufactured by Daicel Chemical Industries, Ltd.) ), Alkali-soluble cardo resins, and the like.

As weight average molecular weight (Mw) of alkali-soluble polymer, the thing of 5000-400000 (the thing which measured the tetrahydrofuran by the gel permeation chromatography as a carrier and converted using the calibration curve with standard polystyrene), and also has an average molecular weight A polymer having an acid value of 60 to 15000 (mgKOH / g) is most preferred from the viewpoints of photosensitive characteristics, solubility in an ester solvent, solubility in an alkaline developer, and residue suppression.

As a reactive monomer of the photosensitive coloring resin composition of this invention, a polyfunctional, monofunctional acryl-type monomer or oligomer can be used. Especially, it is preferable to contain a polyfunctional monomer, As a polyfunctional monomer, Bisphenol A diglycidyl ether (meth) acrylate, a poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth), for example ) Acrylic acid, adipic acid 1,6-hexanediol (meth) acrylic acid ester, phthalic anhydride propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylic acid Latex, alkyd-modified (meth) acrylates, fluorene diacrylate oligomers such as those described in Japanese Patent No. 3621533 or Japanese Patent Application Laid-open No. Hei 8-278630, or tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimetholpropane tri (meth) a Relate, pentaerythritol tri (meth) acrylate, triacyl formal, pentaerythritol tetra (meth) acrylate and acid-modified compounds thereof, dipentaerythritol hexa (meth) acrylate and acid-modified compounds thereof, dipentaerythritol penta ( Meta) acrylate and its acid modified substance, 2,2-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] propane, bis [4- (3-acryloxy-2-hydroxyprop Foxy) phenyl] methane, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] sulfone, bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] ether, 4, 4'-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] cyclohexane, 9,9-bis [4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene , 9,9-bis [3-methyl-4- (3-acryloxy-2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [3-chloro-4- (3-acryloxy-2 -Hydroxypropoxy) phenyl] fluorene, bisphenoxy ethanol flu Orene diacrylate, bisphenoxyethanol fluorene dimethacrylate, biscresol fluorene diacrylate, biscresol fluorene dimethacrylate, and the like. These can be used individually or in mixture.

By selection and combination of these polyfunctional monomers and oligomers, it is possible to control the sensitivity and processability of the resist. In order to raise a sensitivity especially, the use of the compound which has 3 or more functional groups, more preferably 5 or more is preferable, and especially dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and its acid modification Sieve is preferred. Moreover, the unsaturated group containing alkali-soluble monomer obtained by making polybasic acid carboxylic acid or its acid anhydride react with the reaction compound of the epoxy compound which has two glycidyl ether groups, and methacrylic acid is also used preferably from a viewpoint of developability and workability. Moreover, since the use of the (meth) acrylate which has many aromatic rings in a molecule | numerator, and has a fluorene ring with high water repellency can control a pattern to a preferable shape at the time of image development, it is preferable.

Although it does not specifically limit as a photoinitiator of the photosensitive coloring resin composition of this invention, Preferably, a radical photopolymerization initiator is preferable, Especially, it is more preferable to contain an alkyl phenone system and / or an oxime ester system photoinitiator.

As an alkylphenone type photoinitiator, (alpha)-aminoalkyl phenone system or the (alpha)-hydroxyalkyl phenone system etc. are mentioned, Especially, the (alpha)-aminoalkyl phenone system is preferable from a viewpoint of high sensitivity. For example, 2, 2- diethoxy acetophenone, 2-methyl- 1- (4-methylthiophenyl) -2-morpholino propane- 1-one, Ciba Specialty Chemicals "Irgacure (trademark)" 369 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, Ciba Specialty Chemicals "Irgacure®" 379 2- (dimethylamino) -2-[( 4-methylphenyl) methyl] -1- [4- (4-morphonyl) phenyl] -1-butanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one etc. are mentioned.

Specific examples of oxime ester photopolymerization initiators include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime), which is Ciba Specialty Chemicals "Irgacure®" OXE01. , Ciba Specialty Chemicals "Irgacure®" ethanone, OXE02, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O- Acetyl oxime), "Adeka® Optomer" N-1818, N-1919, "Adeka Cruise" NCI-831 by Asahi Denka Kogyo KK, and the like.

In addition to these photoinitiators, inorganic compounds such as benzophenone compounds, oxanthone compounds, imidazole compounds, benzothiazole compounds, benzoxazole compounds, carbazole compounds, triazine compounds, phosphorus compounds or titanates You may use together well-known photoinitiators, such as a photoinitiator. For example, benzophenone, N, N'- tetraethyl-4,4'- diamino benzophenone, 4-methoxy-4'- dimethylamino benzophenone, bebenzoin, benzoin methyl ether, benzoin iso Butyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro- 2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 1,2-benzoanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-mercaptobenzothiazole, 2-mercaptobenzooxazole, 4- (p-methoxyphenyl) -2,6 -Di- (trichloromethyl) -s-triazine and the like.

It does not specifically limit as an organic solvent which can be preferably used for the photosensitive coloring resin composition of this invention, Ester, aliphatic alcohol, ketone, etc. can be used.

Specific esters include benzyl acetate (boiling point 214 ° C), ethyl benzoate (boiling point 213 ° C), γ-butyrolactone (boiling point 204 ° C), methylbenzoate (boiling point 200 ° C), diethyl malonic acid (boiling point 199 ° C) 2-ethylhexyl acetate (boiling point 199 ° C), 2-butoxyethyl acetate (boiling point 192 ° C), 3-methoxy-3-methyl-butyl acetate (boiling point 188 ° C), diethyl oxalate (boiling point 185 ° C), Ethyl acetoacetic acid (boiling point 181 ° C), cyclohexyl acetate (boiling point 174 ° C), 3-methoxy-butyl acetate (boiling point 173 ° C), methyl acetoacetate (boiling point 172 ° C), ethyl-3-ethoxypropionate ( Boiling point 170 ° C.), 2-ethylbutyl acetate (boiling point 162 ° C.), isopentyl propionate (boiling point 160 ° C.), propylene glycol monomethyl ether propionate (boiling point 160 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ℃, pentyl acetate (boiling point 150 ℃), propylene glycol monomethyl ether acetate ( Boiling point 146 ° C.) and the like, but are not limited to these.

Among these solvents, 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether propionate, 3-methoxy-butyl acetate in a solvent of acetic acid ester or propionic acid ester, Propylene glycol monomethyl ether acetate is particularly preferred.

Moreover, propylene glycol monomethyl ether (boiling point of 120 degreeC), propylene glycol monoethyl ether (boiling point of 133 degreeC), propylene glycol tertiary butyl ether (boiling point of 153 degreeC), dipropylene glycol monomethyl ether (boiling point of 188) as a solvent of that excepting the above. Aliphatic ethers, such as propylene glycol derivatives, such as propylene glycol, aliphatic esters other than the above, for example, ethyl acetate (boiling point 77 ° C), butyl acetate (boiling point 126 ° C), isopentyl acetate (boiling point 142 ° C), or butanol Aliphatic alcohols, such as (boiling point 118 degreeC), 3-methyl- 2-butanol (boiling point 112 degreeC), and 3-methyl-3- methoxybutanol (boiling point 174 degreeC), ketones, such as cyclopentanone and cyclohexanone, and xylene It is also possible to use together solvents, such as (boiling point of 144 degreeC), ethylbenzene (boiling point of 136 degreeC), and solvent naphtha (petroleum oil: boiling point of 165-178 degreeC).

Moreover, since application | coating by a die coating apparatus becomes mainstream with the enlargement of a board | substrate, it is preferable to comprise with the mixed solvent of two or more components in order to implement suitable volatility and dryness. When the boiling point of all the solvents constituting the mixed solvent is 150 ° C. or less, the uniformity of the film thickness cannot be obtained, the film thickness of the coated portion becomes thick, and agglomerates of pigments are formed in the metal parts to discharge the coating liquid from the slit, Many problems arise that lines are generated in the coating film. On the other hand, when the boiling point of the said mixed solvent contains many solvents 200 degreeC or more, the coating film surface will become adhesive and will generate sticking. Therefore, the mixed solvent containing 30-75 mass% of solvents whose boiling point is 150 degreeC or more and 200 degreeC is preferable.

In order to improve the adhesiveness of a coating film and an undercoat board | substrate, it is preferable to add an adhesive improving agent to a colored resin composition, and a silane coupling agent is used suitably for the photosensitive colored resin composition of this invention. There is no restriction | limiting in particular as a silane coupling agent, Although the silane coupling agent which has functional groups, such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, is mentioned, It is not limited to these. Specifically, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxy Methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-methacryloxypropyltrimeth Methoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy sisilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene ) Propylamine, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-isocyanate propyltri Preference is given to ethoxysilane, p-thryltrimethoxysilane, and the like.

As addition amount of an adhesion | attachment improving agent, 1-15 mass% is preferable with respect to the total amount of solid components of a colored resin composition, ie, the total sum of a coloring material, an acrylic copolymer, an alkali-soluble polymer, and a reactive monomer, and 2-10 mass% is more preferable. Do. When less than 1 mass%, the adhesive improvement effect is not enough, and when more than 15 mass%, a fine pattern will fall in alkali image development, and resolution will fall.

Moreover, surfactant can also be added to the photosensitive colored resin composition of this invention for the purpose of preventing applicability | paintability, the smoothness of a colored film, and Benard Cells. The addition amount of surfactant is normally 0.001-10 mass% of a pigment, Preferably it is 0.01-1 mass%. If the addition amount is very small, the coating property, the smoothness of the colored film and the prevention of Benad cell is not effective, and if the addition amount is very large, the coating film properties may be inferior.

Specific examples of the surfactant include anionic surfactants such as lauryl ammonium sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryl trimethylammonium chloride, lauryldimethylamine oxide and laurylcarb. Amphoteric skeleton such as methyl methyl hydroxyethyl imidazolium betaine, nonionic surfactant such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, polydimethylsiloxane and the like Silicone surfactant, a fluorine-type surfactant, etc. which are made are mentioned. In this invention, it is not limited to these, One type or two types or more can be used for surfactant.

In the photosensitive colored resin composition of the present invention, the weight composition ratio of the colorant component / resin component is preferably in the range of 80/20 to 10/90, in order to obtain a film having sufficient coloring power. Here, a resin component is taken as the sum total of additives, such as a reactive monomer, an oligomer, a photoinitiator, a polymer dispersing agent, in addition to the acrylic copolymer used for the coloring material dispersion, and the alkali-soluble polymer added with the coloring resin composition.

As solid content concentration which combined the resin component and the coloring material component in the photosensitive colored resin composition of this invention, 2% or more and 60% or less are preferable from a viewpoint of coating property and dryness, and it is more preferable that they are 5% or more and 30% or less.

(Example)

Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example.

<Evaluation method>

`` Sanga ''

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

`` Base ''

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

"Molecular Weight"

The gel permeation chromatography (GPC) "HLC-8220 GPC" (test apparatus of Tosoh Corporation) was used, and the carrier was made into the value of the weight average molecular weight (Mw) measured using polystyrene as tetrahydrofuran and a molecular weight standard.

"Viscosity"

The viscosity meter (RE105L manufactured by Toki Sangyo Co., Ltd.) was set at a temperature of 25.0 ± 0.2 ° C., and the value at 100 rpm was used as the value of the viscosity.

`` Dispersion stability ''

The dispersion state was comprehensively evaluated by the percentage (thickness, unit%) in which the initial viscosity in a coloring material dispersion and the viscosity change after 1 week, ie, the viscosity after 1 week, increased with respect to the initial viscosity. Although it is preferable that the thickening with time is small, it may thicken because the interaction of pigments disperse | distributed finely acts, and the acceptance criteria were evaluated as (triangle | delta) as follows.

○ Dispersion is very good (within 50% of thickening in one week of production)

△ The dispersion state is good (the thickening in one week of production exceeds 50% and is within 100%)

× Dispersion is unstable (thickened more than 100% in one week of production)

`` Development ''

The dissolution time of the non-photosensitive portion of the coating film developed with 0.045% aqueous potassium hydroxide solution was evaluated as follows with the acceptance criteria as Δ from the viewpoint of industrial use.

○ Developability is very good (resist coating film unexposed part completed within 50 second)

△ Developability is good (resist coating film unexposed part is completed within 100 seconds exceeding 50 seconds)

X Poor developability (requires 100 seconds or more to complete dissolution of resist coating unexposed part)

`` Heat resistance ''

About the heat resistance which performs prebaking 150 degreeC * 30 minutes with a thermogravimetric analyzer (Q50 by TA Instruments), heats in the order of post-baking 280 degreeC * 60 minutes, and evaluates by the sample weight change before and after postbaking, The acceptance criteria were evaluated as Δ as follows from the viewpoint of the red use.

○ Very good heat resistance (less than 1.5% by weight)

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

X Poor heat resistance (weight change exceeding 2.0%)

Synthesis of Acrylic Copolymer

The synthesis example of the acrylic copolymer in this invention is shown below. In addition, this invention is not limited only to the following methods. It shows in Table 1 about the manufacturing method and characteristic value of the acrylic copolymer in this synthesis example. In addition, the description of "part" in each synthesis example shows a weight part.

The abbreviation of the (meth) acryl monomer and other monomer shown in Table 1 is as follows.

Methyl methacrylate (MMA)

Methacrylic acid dodecyl (DOMA)

Stearyl methacrylate (SLMA)

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

Methacrylic acid (MAA)

Acrylic acid (AA)

The structure represented by formula (E2);

Styrene (St)

4-methylstyrene (4MSt)

The structure represented by formula (E1);

Benzyl methacrylate (Bz-MA)

The structure represented by formula (B);

Methacrylic acid-2-dimethylaminoethyl (MLDA)

2-dimethylaminoethyl acrylate (ALDA)

A structure represented by formula (C);

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

The structure represented by formula (F);

2-ethylhexyl acrylate (2EHA),

2-ethylhexyl methacrylate (2EHMA)

The structure represented by formula (D1);

Acid functional group-containing monomer mixture (manufactured by Rhone-Poulenc) (β-CEA)

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

Glycidyl methacrylate (GMA)

Polymerization initiator;

Azobisisobutyronitrile (AIBN)

Normaldodecyl mercaptan (MDM)

The adjustment of the base value shown in Table 1 by the increase and decrease of the input amount of the amino group-containing monomers (MLDA, ALDA, MLDA-Cl), the adjustment of the acid value by the increase and decrease of the input amount of the carboxyl group-containing monomers (AA, MAA, β-CEA) Each was carried out.

Adjustment of the weight average molecular weight shown in Table 1 was performed by the increase and decrease of the addition amount of a polymerization initiator (AIBN) and / or a normal dodecyl mercaptan (MDM).

Synthesis Example 1

200 parts of propylene glycol monoethyl ether acetate solvents were put into a pressure-resistant vessel equipped with a stirring device, a thermometer, a reflux condenser, and a dropping pump. The reaction vessel was filled with nitrogen, and then the temperature was increased to 90 ° C. 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), As a polymerization initiator, what mixed 2.0 parts of azobisisobutyronitrile (AIBN) and 3.0 parts of normal dodecyl mercaptan (MDM) was dripped over 3 hours with the dropping pump, and copolymerization was performed. Thereafter, the reaction vessel was replaced with air, and 10 parts of glycidyl methacrylate (GMA) was added dropwise over 1 hour with a dropping pump, followed by addition reaction, and further stirred for 2 hours in the vessel. As a result, an acrylic copolymer (P-1) having a base value of 5 mmol / 100 g, an acid value of 75 mg KOH / g, and a weight average molecular weight of 7000 was obtained.

Synthesis Example 2

Production was carried out in the same manner as in Synthesis example 1 except that the amounts of MMA and MLDA were 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

Production was carried out in the same manner as in Synthesis example 1 except that the amounts of MMA and MLDA were 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

Production was carried out in the same manner as in Synthesis example 1 except that the amounts of MMA and MLDA were 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

Production was carried out in the same manner as in Synthesis example 1 except that the amounts of MMA and MLDA were set 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

Production was carried out in the same manner as in Synthesis example 1 except that the amount of MMA used was 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

Production was carried out in the same manner as in Synthesis example 1 except that the amounts of MMA and MLDA were set 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

It produced like the synthesis example 3 except having set MLDA to ALDA. As a result, an acrylic copolymer (P-8) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 9

Production was performed in the same manner as in Synthesis example 3 except that MLDA was used as MLDA-Cl. As a result, an acrylic copolymer (P-9) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 10

Production was carried out in the same manner as in Synthesis example 3 except that the input amounts of MMA and MAA were 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

Production was carried out in the same manner as in Synthesis example 3 except that the amounts of MMA and MAA were set 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

Production was carried out in the same manner as in Synthesis example 3 except that the amounts of MMA and MAA added were 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

Production was carried out in the same manner as in Synthesis example 3 except that the amount of MMA was 47 parts without using MAA. As a result, an acrylic copolymer (P-13) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 14

Production was carried out in the same manner as in Synthesis example 3 except that the input amounts of MMA and MAA were 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

Production was carried out in the same manner as in Synthesis example 3 except that the amounts of MMA and MAA were set 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

It produced like the synthesis example 3 except having set MAA to AA. As a result, an acrylic copolymer (P-16) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 17

The preparation amount of the MMA was 14 parts, and the MAA was prepared in the same manner as in Synthesis example 3 except that 17 parts of MAA were 33 parts of? As a result, an acrylic copolymer (P-17) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 18

Production was carried out in the same manner as in Synthesis example 3 except that 2EHMA was used as 2EHA. As a result, an acrylic copolymer (P-18) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 19

It produced like the synthesis example 3 except having used 2EHMA as dodecyl methacrylate (DOMA). As a result, an acrylic copolymer (P-19) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 20

It produced like the synthesis example 3 except having used 2EHMA as stearyl methacrylate (SLMA). As a result, an acrylic copolymer (P-20) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 21

Production was carried out in the same manner as in Synthesis example 3, except that 2 parts of MMA were charged at 50 parts without using EHMA. As a result, an acrylic copolymer (P-21) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 22

Production was carried out in the same manner as in Synthesis example 3 except that the amount of MDM was changed to 5.0 parts. As a result, an acrylic copolymer (P-22) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 23

Production was carried out in the same manner as in Synthesis example 3 except that the amount of MDM was set to 2.0 parts. As a result, an acrylic copolymer (P-23) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 24

Production was carried out in the same manner as in Synthesis example 3 except that the amount of MDM was 1.0. As a result, an acrylic copolymer (P-24) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 25

Production was performed in the same manner as in Synthesis example 3 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

Production was carried out in the same manner as in Synthesis example 3 except that the amount of AIBN charged was 6.0 parts. As a result, an acrylic copolymer (P-26) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 27

Production was carried out in the same manner as in Synthesis example 3, except that the amount of AIBN added was 0.8 part without using MDM. As a result, an acrylic copolymer (P-27) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 28

It produced like the synthesis example 3 except having set St as 4MSt. As a result, an acrylic copolymer (P-28) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 29

It produced like the synthesis example 3 except having set St to BzMA. As a result, an acrylic copolymer (P-29) having the characteristic values shown in Table 1 was obtained.

Synthesis Example 30

Production was carried out in the same manner as in Synthesis example 3 except that the amount of MMA added to 60 parts without using St was used. As a result, an acrylic copolymer (P-30) having the characteristic values shown in Table 1 was obtained.

<Creation of a coloring material dispersion and a photosensitive colored resin composition>

EXAMPLE 1

200 g of titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) prepared by thermal plasma method, 114 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of an acrylic copolymer (P-1) as a polymer dispersant 3 25 g of Disperbyk LPN-21116 (DP-1, manufactured by BYK-Chemie, 40 wt% solution of propylene glycol monoethyl ether acetate) having a quaternary amino group and a quaternary ammonium salt and 661 g of propylene glycol monoethyl ether acetate (PMA) were added to the tank. The mixture was stirred for 20 minutes with a homomixer (manufactured by PRIMIX Corporation) to obtain a preliminary dispersion. Thereafter, a preliminary dispersion was supplied to an ultra apex mill (manufactured by Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 0.05% φ zirconium oxide beads (manufactured by Neturen Co., Ltd., YTZ ball) 75%. The dispersion was carried out at a rotational speed of 8 m / s for 3 hours to obtain a coloring material dispersion 1 having a solid content concentration of 25% by weight and a coloring material / resin (weight ratio) = 80/20. The obtained coloring matter dispersion 1 had a viscosity of 3.4 mPa · s immediately after preparation and a viscosity of 5.5 mPa · s after the passage of time for one week.

33.00 g of this colorant dispersion 1 and 7.53 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of the acrylic copolymer (P-1), 55.36 g of propylene glycol monoethyl ether acetate, "Adeka (TM) Optomer" N -1919 (manufactured by Asahi Denka Kogyo KK) 0.99 g, dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.) 2.64 g, 0.45 g of 3-acrylooxypropyltrimethoxysilane, BYK333 (BYK-Chemie) Production) Photosensitive colored resin composition which mixed 0.04g was prepared.

The obtained photosensitive coloring resin composition was apply | coated with the spin coater on the alkali free glass ("1737 material made by Corning Incorporated") board | substrate, and prebaked at 90 degreeC for 10 minutes. Thereafter, Dainippon Screen Mfg. Co., Ltd. Using the produced exposure machine "XG-5000", it exposed through the gray tone mask and developed the negative resist using 0.045% potassium hydroxide aqueous solution. The developing time was 33 seconds.

In addition, the dissolution time of the non-photosensitive part of the developed coating film was measured and evaluated by the said test method. The results are shown in Table 2.

In addition, in Table 2, while describing the kind of the coloring material, acrylic copolymer, polymer dispersing agent, and solvent which comprise a coloring material dispersion liquid with abbreviation, each compounding quantity (weight)% was described.

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

Instead of the acrylic copolymer (P-1), the acid value and the base value were the same as those in Example 1 except for using the acrylic copolymer (P-2 to P-30) in which the characteristic value of the weight average molecular weight and some unsaturated monomers were used. Table 2 shows the result detail to Examples 2-22 and Comparative Examples 1-8 which produced the coloring material dispersion liquid and the photosensitive coloring resin composition by the method, and evaluated.

Moreover, about the photosensitive colored resin composition obtained in Examples 3, 21, 22, and the comparative example 8, the heat resistance before and after postbaking was evaluated 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 were compatible, and it was necessary to make the acrylic copolymer a characteristic value of a base in a specific range, an acid value, and a weight average molecular weight. Moreover, in order to acquire sufficient heat resistance, it turned out that an aromatic ring should flow into a side chain.

Moreover, it turned out that stability of a pigment dispersion liquid becomes more advanced by introducing a long chain acrylic group into a side chain.

[Example 23]

175 g of titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) prepared by thermal plasma method, 214 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of an acrylic copolymer (P-3), and a polymer dispersant were added. The evaluation results of the dispersion stability of the coloring material dispersion prepared in the same manner as in Example 3 and the developability of the photosensitive colored resin composition are shown in Table 3, except that 611 g of propylene glycol monoethyl ether acetate (PMA) was not used.

In addition, in Table 3, while describing the kind of the coloring material, acrylic copolymer, polymer dispersing agent, and solvent which comprise a coloring material dispersion liquid with the symbol, each compounding quantity (weight)% was described.

(Comparative Example 9)

The evaluation result of the dispersion stability of the coloring material dispersion liquid produced by the method similar to Example 23, and the developability of the photosensitive coloring resin composition except having used the acrylic copolymer (P-6) instead of the acrylic copolymer (P-3) is shown in the table. 3 is shown.

[Example 24]

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

EXAMPLE 25

Disperbyk 2001 (DP-3, manufactured by BYK-Chemie) having a quaternary ammonium salt and carboxyl group instead of Disperbyk LPN-21116 (DP-1, manufactured by BYK-Chemie, 40 wt% solution of propylene glycol monoethyl ether acetate) as a polymer dispersant Table 3 shows the evaluation results of the dispersion stability of the coloring material dispersion prepared in the same manner as in Example 3 and the developability of the photosensitive colored resin composition, except that a 40% by weight 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 dispersion without adding a polymer dispersant by using the acrylic copolymer of the present invention, but to stabilize the dispersion more preferably, a polymer dispersant is preferably added. It was found that it is more preferable to use a polymer dispersant having a tertiary amino group.

EXAMPLE 26

220 g of titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) prepared by thermal plasma method, 57 g of 35% by weight solution of propylene glycol monoethyl ether acetate of acrylic copolymer (P-3), and Disperbyk as polymer dispersant Production was carried out in the same manner as in Example 3, except that 25 g of LPN-21116 (DP-1, manufactured by BYK-Chemie, a 40 wt% solution of propylene glycol monoethyl ether acetate) and 698 g of propylene glycol monoethyl ether acetate (PMA) were used. Table 3 shows the evaluation results of the dispersion stability of the colorant dispersion and the developability of the photosensitive colored resin composition.

[Example 27]

175 g of titanium nitride particles (Bk-1, manufactured by Nisshin Engineering Inc.) prepared by thermal plasma method, 186 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of an acrylic copolymer (P-3), and Disperbyk as a polymer dispersant Production was carried out in the same manner as in Example 3, except that 25 g of LPN-21116 (manufactured by BYK-Chemie, 40 wt% propylene glycol monoethyl ether acetate) and 614 g of propylene glycol monoethyl ether acetate (PMA) were used. Table 3 shows the evaluation results of the dispersion stability of the colorant dispersion and the developability of the photosensitive colored resin composition.

From the result of Example 3 and Examples 26-27, it turned out that using the acrylic copolymer of this invention and having more resin components than 90/10 as a weight composition ratio of a coloring material component / resin component.

EXAMPLE 28

175 g of high-resistance carbon black (Bk-2, manufactured by Cabot Corporation), 171 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of the acrylic copolymer (P-3), and Disperbyk LPN-21116 (DP-1, 38 g of propylene glycol monoethyl ether acetate) made by BYK-Chemie) and 616 g of propylene glycol monoethyl ether acetate (PMA) were added to a tank, and stirred for 20 minutes with a homomixer (manufactured by PRIMIX Corporation) to prepare a preliminary dispersion. Got it. Thereafter, a preliminary dispersion was supplied to an ultra apex mill (manufactured by Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 0.05% φ zirconium oxide beads (manufactured by Neturen Co., Ltd., YTZ ball) 75%. The dispersion was carried out at a rotational speed of 8 m / s for 3 hours to obtain a coloring material dispersion 37 having a solid content concentration of 25% by weight and a coloring material / resin (weight ratio) = 70/30.

37.71 g of this colorant dispersion 37 and 4.48 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of the acrylic copolymer (P-1), 53.80 g of propylene glycol monoethyl ether acetate, "Adeka (R) Optomer" N -1919 (manufactured by Asahi Denka Kogyo KK) 0.96 g, dipentaerythritol hexaacrylate (DHPA made by Nippon Kayaku Co., Ltd.) 2.55 g, 0.45 g of 3-acrylooxypropyltrimethoxysilane, BYK333 (BYK-Chemie) Production) 0.04 g was mixed, the photosensitive coloring resin composition was produced, and developability evaluation was performed by the method similar to Example 1. Table 3 shows the evaluation results of the dispersion stability of the coloring material dispersion and the developability of the photosensitive resin composition.

(Comparative Example 10)

Table 3 shows the evaluation results of the dispersion stability of the coloring material dispersion prepared in the same manner as in Example 28 and the developability of the photosensitive resin composition, except that P-6 was used instead of P-3 as the acrylic copolymer.

EXAMPLE 29

120 g of organic pigment PR177 (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) and 114 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of the acrylic copolymer (P-3) as a polymer dispersant 100 g of LPN-21116 (manufactured by BYK-Chemie, a 40% by weight solution of propylene glycol monoethyl ether acetate) and 666 g of propylene glycol monoethyl ether acetate (PMA) were added to a tank, and a homomixer (made by PRIIMIX Corporation) The mixture was stirred for 20 minutes to obtain a preliminary dispersion. Subsequently, preliminary dispersion was supplied to an ultra apex mill (manufactured by Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 75% of 0.05 mm zirconium oxide beads (manufactured by Neturen Co., Ltd., YTZ ball). The dispersion was carried out at a rotational speed of 8 m / s for 3 hours to obtain a coloring 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 in the same manner as in Example 1.

37.50 g of this colorant dispersion 39 and 7.29 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of the acrylic copolymer (P-1), 50.26 g of propylene glycol monoethyl ether acetate, "Adeka (TM) Opomer" N -1919 (manufactured by Asahi Denka Kogyo KK) 0.41 g, dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.) 4.05 g, 0.45 g of 3-acryloxypropyltrimethoxysilane, BYK333 (BYK-Chemie) Production) 0.04 g was mixed, the photosensitive coloring resin composition was produced, and developability evaluation was performed by the method similar to Example 1.

Comparative Example 11

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

EXAMPLE 30

Disperbyk LPN-21116 (DP, 50 g of dye AR289 (R-2, manufactured by Chugai kasei Co., Ltd.), 357 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of an acrylic copolymer (P-3) as a polymer dispersant) -1, BYK-Chemie, 63 g of propylene glycol monoethyl ether acetate) and 530 g of propylene glycol monoethyl ether acetate (PMA) were added to a tank, followed by stirring for 20 minutes with a homomixer (manufactured by PRIMIX Corporation). A preliminary dispersion was obtained. Thereafter, a preliminary dispersion was supplied to an ultra apex mill (Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 0.05% φ zirconium oxide beads (manufactured by Neturen Co., Ltd., YTZ balls) 75%, It disperse | distributed for 3 hours at the rotation speed of 8 m / s, and obtained the coloring material dispersion 41 of 20 weight% of solid content concentration, and coloring material / resin (weight ratio) = 25/75. The dispersion stability of the obtained coloring material dispersion was evaluated in the same manner as in Example 1.

45.00 g of this colorant dispersion 41 and 1.03 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of the acrylic copolymer (P-1), 48.33 g of propylene glycol monoethyl ether acetate, "Adeka (TM) Optomer" N -1919 (manufactured by Asahi Denka Kogyo KK) 0.29 g, dipentaerythritol hexa acrylate (DHPA made by Nippon Kayaku Co., Ltd.) 4.86 g, 0.45 g of 3-acrylooxypropyltrimethoxysilane, BYK333 (BYK-Chemie) Production) 0.04 g was mixed, the photosensitive coloring resin composition was produced, and developability evaluation was performed by the method similar to Example 1.

(Comparative Example 12)

Table 3 shows the evaluation results of the dispersion stability of the coloring material dispersion prepared in the same manner as in Example 30 and the developability of the photosensitive resin composition, except that P-6 was used instead of P-3 as the acrylic copolymer.

[Example 31]

160 g of Ag nanoparticles (Ag-1, manufactured by DaiwaKasei Co., Ltd.), 57 g of 35% by weight solution of propylene glycol monoethyl ether acetate of an acrylic copolymer (P-3), and Disperbyk LPN-21116 (DP) -1, BYK-Chemie, 50 g of propylene glycol monoethyl ether acetate) and 733 g of propylene glycol monoethyl ether acetate (PMA) were added to a tank, and stirred for 20 minutes with a homomixer (manufactured by PRIMIX Corporation). A preliminary dispersion was obtained. Thereafter, a preliminary dispersion was supplied to an ultra apex mill (Kotobuki Kogyou Co., Ltd.) equipped with a centrifugal separator filled with 0.05% zirconium oxide beads (manufactured by Neturen Co., Ltd., YTZ ball) 75%, It disperse | distributed for 3 hours at the rotation speed of 8 m / s, and obtained the coloring material dispersion 43 of 20 weight% of solid content concentration, and coloring material / resin (weight ratio) = 80/20. The dispersion stability of the obtained coloring material dispersion was evaluated in the same manner as in Example 1.

46.88 g of this colorant dispersion 43 and 6.37 g of a 35% by weight solution of propylene glycol monoethyl ether acetate of the acrylic copolymer (P-1), 43.36 g of propylene glycol monoethyl ether acetate, "Adeka (TM) Optomer" N 0.719 g of 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-acrylooxypropyltrimethoxysilane, BYK333 (BYK-Chemie) Production) 0.04 g was mixed, the photosensitive coloring resin composition was produced, and developability evaluation was performed by the method similar to Example 1.

Comparative Example 13

Table 3 shows the evaluation results of the dispersion stability of the coloring material dispersion prepared in the same manner as in Example 31 and the developability of the photosensitive resin composition except that P-6 was used instead of P-3 as the acrylic copolymer.

From the results of Examples 28 to 31 and Comparative Examples 10 to 13, it was found that dispersion stabilization is possible not only for inorganic pigments but also organic pigments, dyes and metal fine particles by using the acrylic copolymer of the present invention.

(Industrial availability)

The coloring material dispersion liquid of this invention is excellent in dispersion stability and the viscosity stability over time also in the composition containing a coloring material in high concentration. Moreover, it becomes possible to form the coating film excellent in alkali image development solubility and heat resistance by preparing the photosensitive colored resin composition using the coloring material dispersion liquid of this invention. Therefore, it becomes possible to form efficiently high performance coloring patterns, such as a color filter substrate for liquid crystal display devices, and a sensor substrate for touch panels.

Claims (8)

As a coloring material dispersion liquid containing at least a coloring material, an acrylic copolymer, and an organic solvent,
The acrylic copolymer has at least a structure represented by the following formula (A) having an ethylenically unsaturated group in the side chain, 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. It has a structure represented by following formula (C), the structure (D) which has a carboxyl group in a side chain, and the structure (E) which has an aromatic ring, and have a base value of 10-30 mmol / 100g, and an acid value of 50-100 mgKOH / g. The polystyrene reduced weight average molecular weight by gel permeation chromatography is 5,000-30,000, The coloring matter dispersion liquid characterized by the above-mentioned.

[In formula, R <^1> , R <^2> is a hydrogen atom or a methyl group independently of each other, R <^3> is a C1-C4 alkylene group, a C3-C6 bivalent alicyclic hydrocarbon group, a C6-C10 divalent aromatic hydrocarbon Any one selected from the group]

[In formula, R <^4> is a hydrogen atom or a methyl group, R <^5> is a C1-C4 alkylene group, a C1-C4 divalent alkoxy group, a C3-C6 bivalent alicyclic hydrocarbon group, C6-C10 Any one selected from a divalent aromatic hydrocarbon group, R ⁶ and R ⁷ independently of each other, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, 6 to 10 carbon atoms Any one selected from aromatic hydrocarbon groups]

[In formula, R <^8> is a hydrogen atom or a methyl group, R <^9> is a C1-C4 alkylene group, a C1-C4 divalent alkoxy group, a C3-C6 bivalent alicyclic hydrocarbon group, a C6-C10 Any one selected from a divalent aromatic hydrocarbon group, R ¹⁰ , R ¹¹ , and R ¹² independently of one another are an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, an alicyclic hydrocarbon group of 3 to 6 carbon atoms, and carbon 6 Any one selected from -10 aromatic hydrocarbon groups, X represents any one of bromine, chlorine, iodine, hydrogen sulfate and hydroxide] The method of claim 1,
The structure (D) which has the said carboxyl group is represented by a following formula (D1), The coloring material dispersion liquid characterized by the above-mentioned.

[In formula, R <^13> is a hydrogen atom or a methyl group, R <^14> is a C1-C4 alkylene group, a C3-C6 bivalent alicyclic hydrocarbon chain, a C6-C10 divalent aromatic hydrocarbon chain is any one selected. N represents an integer of 0 to 6, and may be a single type or a mixture of a plurality of n.] The method of claim 1,
Structure (E) which has the said aromatic ring is represented by following formula (E1) or (E2), The coloring matter dispersion liquid characterized by the above-mentioned.

[In formula, R <^15> is a hydrogen atom or a methyl group, R <^16> is hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 alicyclic hydrocarbon group, a C6-C10 aromatic hydrocarbon group , Halogen atom, ester group, acyl group, and nitro group.

[In formula, R <^17> is a hydrogen atom or a methyl group, R <^18> is hydrogen, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C3-C6 alicyclic hydrocarbon group, a C6-C10 aromatic hydrocarbon group , Halogen atom, ester group, acyl group, and nitro group. The method of claim 1,
The acrylic copolymer further has a structure represented by the following formula (F) having a carboxylic acid ester in the side chain.

[Wherein, R ¹⁹ represents a hydrogen atom or a methyl group, R ²⁰ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ²¹ represents an alkyl group having 2 to 40 carbon atoms] The method of claim 4, wherein
The total carbon number of said R <^20> and R <^21> is four or more, The coloring matter dispersion liquid characterized by the above-mentioned. The method of claim 3, wherein
It has a structure represented by said formula (E2), The coloring matter dispersion liquid characterized by the above-mentioned. The method of claim 1,
In addition to the said acrylic copolymer, the coloring material dispersion liquid containing the polymeric dispersing agent which has an at least tertiary amino group is contained. At least the coloring material dispersion liquid of Claim 1, a polyfunctional acrylic monomer, and a photoradical polymerization initiator are contained, The photosensitive coloring resin composition characterized by the above-mentioned.