TWI557190B - Colorant dispersion and colored resin composition - Google Patents

Description

Coloring material dispersion and photosensitive colored resin composition

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

In recent years, color liquid crystal display devices (LCDs), which are lithographic displays such as personal computers and mobile phones, have rapidly become popular. For example, a color filter for an LCD is usually manufactured by sequentially forming a color pattern such as a stripe shape or a mosaic shape of red, green, and blue phases on a transparent substrate surface such as a glass or a plastic sheet forming a black matrix. Both the colored layer and the black matrix play an important role in the coloring material dispersion technology.

In addition, the color characteristics of the color filter for LCD are improved by the rise of various display devices such as organic EL and the diversification of display information. In particular, the demand for a wide range of color reproducibility is enhanced, and in the case of a coloring material for a color filter, a technique of stably dispersing a coloring material at a high concentration becomes important. Usually, the coloring material dispersion liquid is formed of a coloring material, a solvent, a dispersing agent, and a binder resin, and the coloring material can be stably dispersed by adding a dispersing agent in a large amount in the composition, but the coloring material is manufactured by a color filter. In the heating process, the dispersant will be yellowed, resulting in a decrease in brightness, and the concentration of the alkali-soluble photocurable resin is diluted to cause a decrease in sensitivity, poor hardening, and reduction in film strength. Problems such as poor developability occur. In particular, poor developability causes serious problems in production. Therefore, the problem of the coloring material dispersion liquid is to impart high dispersion stability to the binder resin itself with a small amount of a dispersing agent as much as possible to ensure the stability of the pigment dispersion liquid. In addition, in recent years, the requirements for color characteristics have been diversified. Therefore, in terms of coloring materials, not only conventional organic pigments, but also development of coloring materials using dyes and inorganic pigments have progressed, and conventional techniques are difficult to diversify. The coloring material is dispersed and stabilized at a high concentration.

Further, in the field of touch panel displays with remarkable technological innovations, black matrices are also formed as light-shielding films in the same manner as color filters, usually in cover glass or protection against the sensor substrate. The cover film is formed using a printing ink. On the other hand, the demand for weight reduction of the touch panel has been improved, and the development of a technology for forming a light shielding film and a touch sensor on the protective glass has been developed. In this case, since it is necessary to form an electrode or the like after forming a black matrix on the cover glass, it is required to be able to withstand high heat resistance in a process of forming an electrode under high-temperature vacuum.

As the pigment for the black matrix, a metal oxide such as titanium black or iron oxide such as carbon black, low-order titanium oxide or titanium oxynitride, or a mixed color of other organic pigments is used, but carbon black and titanium oxynitride are used. Mainstream. In order to obtain a black matrix having high insulating properties, a carbon black or an organic pigment which has been surface-treated with titanium black or a resin may be used as a light-shielding material (for example, see Patent Document 1). However, in order to obtain high light-shielding properties, it is necessary to stably disperse various pigments in a high pigment concentration, and there is still a shortage in terms of long-term preservation stability in the prior art.

As a technique for stabilizing dispersion with a small amount of dispersant, it has been disclosed A polymer dispersant having both an acid value and an amine value, and a copolymer having a copolymer of a quinone imine group and a photocurable functional group (for example, refer to Patent Document 2), but The dispersion stability of a coloring material such as titanium black or carbon black which is difficult to disperse is still insufficient. In addition, as a technique for stably dispersing a pigment even at a high pigment concentration, a technique of using an acid value dispersant having an acid value and an amine value dispersant having an amine value in combination (for example, refer to Patent Document 3), or A technique of using a resin type dispersant having a block structure of both an alkaline block and an acidic block (for example, refer to Patent Document 4). Although it is useful as a coloring liquid for inkjet coating, it is difficult to apply to a coloring liquid for photolithography which requires photosensitivity and developability.

On the other hand, as the acrylic resin for pigment dispersion, an acrylic copolymer having a carboxyl group and an acryloyl group or a methacrylonitrile group in a side chain (for example, refer to Patent Document 5), or having a specific molecular weight or a hydroxyl value may be mentioned. (hydroxyl value) An acrylic resin having an acid value or an amine value (for example, refer to Patent Document 6), but any of the dispersion stability, photosensitivity, and developability are not sufficient.

Advanced technical literature

Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2010-95716

Patent Document 2 Japanese Patent No. 4195323

Patent Document 3 Japanese Patent No. 4544292

Patent Document 4 Japanese Patent Laid-Open Publication No. 2009-167303

Patent Document 5 Japanese Patent No. 3120476

Patent Document 6 Japanese Patent Laid-Open Publication No. 2003-171605

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

In order to solve the problems of the prior art, the inventors of the present invention have found that the problem of the present invention can be solved by using an acrylic copolymer having the following specific structure when the coloring material is dispersed.

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

(1) A coloring material dispersion liquid containing a coloring material, an acrylic copolymer, and an organic solvent, wherein the acrylic copolymer has at least an ethylenically unsaturated group in a side chain. a structure represented by (A), a structure represented by the following formula (B) having a tertiary amino group in a side chain, and/or a structure represented by the formula (C) having a quaternary ammonium salt in a side chain, on the side The chain has a carboxyl group structure (D), a structure having an aromatic ring (E), a base number of 5 to 70 mmol/100 g, and an acid value of 50 to 120 mgKOH/g, which is converted into polystyrene by gel permeation chromatography. The weight average molecular weight is 5,000 to 30,000.

(wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and carbon. Any of a number of 6 to 10 divalent aromatic hydrocarbon groups).

(wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alkoxy group having 1 to 4 carbon atoms, and a divalent alicyclic ring having 3 to 6 carbon atoms. Any one of a hydrocarbon group and a quaternary aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Any one of an alicyclic hydrocarbon group having 3 to 6 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms).

(wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alkoxy group having 1 to 4 carbon atoms, and a divalent alicyclic ring having 3 to 6 carbon atoms. Any one of a hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. Any of an oxy group, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms, and 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 a carboxyl group is represented by the following formula (D1).

(wherein R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alicyclic hydrocarbon chain having 3 to 6 carbon atoms, and a carbon number of 6 to 10; Any of the aromatic hydrocarbon chains, n represents an integer of 0 to 6, and may be a single or a complex number of n.

(3) The colored 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).

(wherein R ¹⁵ represents a hydrogen atom or a methyl group, and R ¹⁶ represents an alicyclic hydrocarbon group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a carbon number of 3 to 6, Any of an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, an ester group, an anthracenyl group, and a nitro group).

(wherein R ¹⁷ represents a hydrogen atom or a methyl group, and R ¹⁸ represents an alkyl group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alicyclic hydrocarbon group having 3 to 6 carbon atoms; Any of an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, an ester group, an anthracenyl group, and a nitro group).

(4) The coloring material dispersion liquid according to (1), (2) or (3), wherein the acrylic copolymer further has a structure represented by the formula (F) in a side chain having a carboxylate.

(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 colored material dispersion liquid according to the item (4), wherein the total carbon number of R ²⁰ and R ²¹ is 4 or more.

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

(7) The coloring material dispersion liquid according to any one of (1) to (6), which further comprises a polymer dispersing agent having at least a tertiary amino group in addition to the acrylic copolymer.

(8) A photosensitive colored resin composition containing at least the coloring material dispersion liquid according to any one of (1) to (7), a polyfunctional acrylic monomer, and a photoradical polymerization initiator.

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

The invention is further described in detail below.

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

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

The acrylic copolymer used in the present invention is a photosensitive property, that is, when an active energy ray such as ultraviolet (UV) is used to generate a radical, an anion or a cationic initiator, in order to visualize the acrylic copolymer itself The function of the coupling reaction must have an acrylic acid unit or a methacrylic acid unit represented by the formula (A) having an ethylenically unsaturated group in its side chain.

(wherein R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a carbon number; Any of 6 to 10 divalent aromatic hydrocarbon groups).

In the above formula (A), R ¹ and R ² are each independently a hydrogen atom or a methyl group, and when R ¹ is hydrogen, it becomes an acrylic unit, and when R ¹ is a methyl group, it becomes a methacrylic unit. R ³ is selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably 1 to 3 carbon atoms. An alkyl group, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

The introduction method of the (meth)acrylic acid unit represented by the above formula (A) is not particularly limited, and can be introduced by a usual method. For example, a method of performing an addition reaction of a polymerizable unsaturated monomer containing a glycidyl group on a (meth)acrylic copolymer obtained by copolymerizing an unsaturated monomer having a carboxyl group can be mentioned. In this case, the unsaturated monomer having a carboxyl group as a copolymerization is acrylic acid, methacrylic acid or the like, and as the unsaturated monomer containing a glycidyl group, an epoxypropyl acrylate or a propylene methacrylate can be exemplified. Wait. In the present invention, these acrylic single systems may be used singly or in combination of two or more.

The acrylic copolymer used in the present invention exhibits high dispersion stability and must contain a (meth)acrylic unit represented by the formula (B) in the side chain having a tertiary amino group and/or a quaternary ammonium salt in the side chain. The (meth)acrylic unit represented by the formula (C) below.

The (meth)acrylic acid 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 the coloring material. It can improve the dispersion stability, so it is suitable to introduce either one or both. Applied to developability as in the present invention In the case of use, it is preferred to introduce a (meth)acrylic unit of the formula (B) having a tertiary amino group from the viewpoint of easy balance between developability and dispersion stability.

(wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alkoxy group having 1 to 4 carbon atoms, and a divalent alicyclic ring having 3 to 6 carbon atoms. Any one of a hydrocarbon group and a quaternary aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Any one of an alicyclic hydrocarbon group having 3 to 6 carbon atoms and an aromatic hydrocarbon group having 6 to 10 carbon atoms).

In the above formula (B), R ⁴ represents a hydrogen atom or a methyl group, and when R ⁴ is hydrogen, it becomes an acrylic acid unit, and when R ⁴ is a methyl group, it becomes a methacrylic acid unit. R ⁵ is selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, a divalent alkoxy group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon having 6 to 10 carbon atoms. The hydrocarbon group is preferably an alkylene group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms.

R ⁶ and R ⁷ may be the same or different, and are selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a carbon number of 6 The aromatic hydrocarbon group of ~10 is preferably an alkylene group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, and a carbon number of 6 to 8. A divalent aromatic hydrocarbon group.

As the (meth)acrylic acid monounsaturated monomer having a tertiary amino group represented by the formula (B), -2-dimethylaminoethyl acrylate and 2-diethylaminoethyl acrylate can be exemplified. Ester, 2-dipropylaminoethyl acrylate, 2-diphenylaminoethyl acrylate, 2-dibenzylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate Ester, 2-diethylaminoethyl methacrylate, 2-dipropylaminoethyl methacrylate, 2-diphenylaminoethyl methacrylate, methacrylic acid-2- Benzylaminoethyl ester or the like is not particularly limited. These (meth)acrylic single systems may be used singly or in combination of two or more.

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

(wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alkoxy group having 1 to 4 carbon atoms, and a divalent alicyclic ring having 3 to 6 carbon atoms. Any one of a hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. Any of an oxy group, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, and X represents any one of bromine, chlorine, iodine, hydrogen sulfate, and hydroxide.

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

R ¹⁰ , R ¹¹ and R ¹² may be the same or different, and are selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alicyclic hydrocarbon group having 3 to 6 carbon atoms. The aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably an alkylene group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, and a carbon number of 6 ~8 of a divalent aromatic hydrocarbon group.

X is selected from the group consisting of bromine, chlorine, iodine, hydrogen sulfate and hydroxide, preferably bromine or chlorine.

As the (meth)acrylic acid unit-unsaturated monomer having a quaternary ammonium salt represented by the formula (C), an acryl-dimethylaminoethyl methyl chloride salt or a dimethylamino group acrylate can be exemplified. Ethylbenzyl chloride salt, methacrylic acid-dimethylaminoethyl methyl chloride salt, dimethylaminoethyl benzyl methacrylate salt, and the like are not particularly limited. These (meth)acrylic single systems may be used singly or in combination of two or more.

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

From the viewpoint of industrial use, it is preferably methacrylic acid-2-dimethyl A tertiary amine such as a arylaminoethyl ester. The acrylic single system represented by the formula (B) and/or (C) in the present invention may be used singly or in combination of two or more kinds.

Since the acrylic copolymer used in the present invention imparts alkali developability, it is necessary to have an acidic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group in the side chain, and the present invention is required to have a structure (D) having a carboxyl group in a molecular side chain.

Such a structure (D) having a carboxyl group can be introduced by copolymerizing an unsaturated monomer having a carboxyl group. Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, decanoic acid, decanoic anhydride, and crotonic acid. As the structure (D) having a carboxyl group, a (meth)acrylic unit having an ethylenically unsaturated group in a molecular side chain represented by the above formula (A) is introduced, and from the viewpoint of control and stability of the reaction, A carboxyl group-containing unsaturated monomer represented by the following formula (D1) is preferred.

(wherein R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alicyclic hydrocarbon chain having 3 to 6 carbon atoms, and a carbon number of 6 to 10; Any of the aromatic hydrocarbon chains, n represents an integer of 0 to 6, and may be a single or a complex number of n.

In the above formula (D1), R ¹³ represents a hydrogen atom or a methyl group, and when R ¹³ is hydrogen, it becomes acrylic acid, and when R ¹³ is a methyl group, it becomes methacrylic acid. R ¹⁴ is selected from the group consisting of an alkylene group having 1 to 4 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably 1 to 3 carbon atoms. An alkyl group, a divalent alicyclic hydrocarbon group having 5 to 6 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 8 carbon atoms. n is an integer from 0 to 6, preferably 0. n can be an integer, or a multiple of 0 to 6.

The carboxyl group-containing unsaturated monomer (D1) represented by the above structure may, for example, be acrylic acid, methacrylic acid, 2-carboxyethyl acrylate oligomer or 2-carboxyethyl methacrylate oligomer. These (meth)acrylic single systems may be used singly or in combination of two or more.

Since the acrylic copolymer of the present invention exhibits high heat resistance, it is necessary to have a structure (E) having an aromatic ring in a side chain. The structure (E) having an aromatic ring in a side chain can be introduced by copolymerizing an unsaturated monomer having an aromatic ring, and is particularly preferably a derivative of a benzyl group and a benzyl group of the following formula (E1), or The phenyl and phenyl derivatives of E2) give a higher heat resistance enhancement effect.

(wherein R ¹⁵ represents a hydrogen atom or a methyl group, and R ¹⁶ represents an alkyl group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and an alicyclic hydrocarbon group having 3 to 6 carbon atoms; Any of an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, an ester group, an anthracenyl group, and a nitro group).

In the above formula (E1), R ¹⁵ represents a hydrogen atom or a methyl group, and when R ¹⁵ is hydrogen, it becomes an acrylic acid unit, and when R ¹⁵ is a methyl group, it becomes a methacrylic acid unit. R ¹⁶ is selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, Any one of an ester group, a mercapto group and a nitro group, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alicyclic hydrocarbon group having 5 to 6 carbon atoms, and a carbon number 6 to 8 aromatic hydrocarbon groups.

The (meth)acrylic acid monomer having an aromatic ring represented by the above formula (E1) may, for example, be benzyl acrylate or benzyl methacrylate, but is not limited thereto. In the present invention, these (meth)acrylic acid single systems may be used singly or in combination of two or more.

(wherein R ¹⁷ represents a hydrogen atom or a methyl group, wherein R ¹⁸ represents an alicyclic ring selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a carbon number of 3 to 6; Any of a hydrocarbon group, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, an ester group, an anthracenyl group and a nitro group.

In the above formula (E2), R ¹⁷ represents a hydrogen atom or a methyl group, and when R ¹⁷ is hydrogen, it becomes an acrylic acid unit, and when R ¹⁷ is a methyl group, it becomes a methacrylic acid unit. R ¹⁸ is selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, Any one of an ester group, a mercapto group and a nitro group, preferably hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alicyclic hydrocarbon group having 5 to 6 carbon atoms, and a carbon number 6 to 8 aromatic hydrocarbon groups.

The aromatic ring-containing unsaturated monomer represented by the above formula (E2) may, for example, be styrene, α-methylstyrene, 4-vinyltoluene or a structural isomer thereof, 4-methoxystyrene. And its structural isomers, 4-butoxystyrene and its structural isomers, 4-tert-butoxystyrene and its structural isomers, 4-vinylbiphenyl, 2-vinylnaphthalene and The structural isomer, 9-vinyl anthracene, 9-vinylcarbazole, etc. are not limited thereto. In the present invention, these acrylic single systems may be used singly or in combination of two or more.

The acrylic copolymer is composed of a structural unit containing a polymerizable unsaturated bond, a tertiary amino group, and/or a quaternary ammonium salt, a carboxyl group, or an aromatic ring in a side chain. In particular, it is preferably a (meth)acrylic acid unit containing a tertiary amino group in a side chain, and a particularly preferred acrylic copolymer is an acrylic copolymer containing a structural unit represented by the following formula (1), and may optionally contain Other main chains constitute units.

(wherein R ¹ , R ² , R ⁴ , R ¹³ and R ¹⁷ each independently represent a hydrogen atom or a methyl group, and R ³ represents an alkylene group selected from a carbon number of 1 to 4 and a carbon number of 3 to 6; Any one of a divalent alicyclic hydrocarbon group and a hexavalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms and a carbon number of 1 to 4; Any one of an alkoxy group, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms; and R ¹⁸ represents an alkyl group selected from hydrogen, 1 to 4 carbon atoms, and carbon number 1 to 4; Any of an alkoxy group, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 10 carbon atoms, a halogen atom, an ester group, an anthracenyl group and a nitro group.

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

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

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

The carboxylic acid ester-containing unsaturated monomer represented by the formula (F) may, for example, be 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate, but is not particularly limited. These acrylic single systems may be used singly or in combination of two or more.

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

The acrylic copolymer of the present invention may be copolymerized with any (meth) acrylate as a monomer, in addition to the above-mentioned structural unit. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methyl Acrylate or A for cyclohexyl acrylate or isodecyl methacrylate The acrylate or the (fluoro)alkyl ester monomer is not limited thereto.

In the acrylic copolymer used in the present invention, it is important to make the acid value and the base value in a suitable range. The base number must be 5 to 70 mmol/100 g, preferably 10 to 30 mmol/100 g. When the base value is lower than this range, the pigment dispersion stability is deteriorated, and when the base value is high, the developability is deteriorated. The base number can be made to be within a predetermined range by modulating the composition ratio of the constituent units of the acrylic copolymer, particularly the constituent unit ratios of the formulae (B) and (C). Further, the base number of the acrylic copolymer is defined as the number of moles of perchloric acid (unit: mmol/100 g) required to neutralize 100 g of the acrylic copolymer.

The acid value of the acrylic copolymer must be 50 to 120 mgKOH/g, and it is preferred to carry out copolymerization so as to be 50 to 100 mgKOH/g. When the upper limit is exceeded, the dispersion stability tends to be deteriorated, and if it exceeds the lower limit, alkaline development tends to be difficult. The acid value can be made to be within a predetermined range by modulating the constituent unit composition ratio of the acrylic copolymer. Further, the acid value of the acrylic copolymer is defined as the number of mg of potassium hydroxide required to neutralize 1 g of the acrylic copolymer (unit: mgKOH/g).

In the present invention, the acrylic copolymer has a weight average molecular weight (Mw) of 5,000 to 30,000, preferably 5,000 to 20,000. When the weight average molecular weight is 5,000 hours, sufficient steric hindrance cannot be formed, and the dispersion of the coloring materials interferes with each other. On the other hand, when the weight average molecular weight is larger than 30,000, the resin adsorption accuracy per unit of the coloring material is lowered, and the dispersion is not stabilized, which causes a problem of deterioration in developability. Further, the weight average molecular weight (Mw) of the acrylic copolymer is measured by gel permeation chromatography using tetrahydrofuran as a carrier, and the amount of standard polystyrene is used. The line is converted.

In the acrylic copolymer used in the present invention, the structural unit represented by the above formula (B) (C) (D1) (E1) (E2) and (F), and any other arbitrary (meth) acrylate unit system can be borrowed It is obtained by a general radical polymerization reaction such as solution polymerization, emulsion polymerization or bulk polymerization, and is obtained in the form of a random copolymer or a block copolymer. Particularly preferred is the form of a random copolymer. Further, the (meth)acrylic acid unit represented by the formula (A) can be introduced by subjecting a monomer having a functional group reactive therewith to an addition reaction on the side chain functional group of the acrylic copolymer obtained above. The general method is to import.

The organic solvent to be used in the coloring matter dispersion liquid of the present invention is not particularly limited, and specific one or more selected from the group consisting of aliphatic hydrocarbons, carboxylic acid esters, ketones, ethers, and alcohols. Among them, one or more selected from the group consisting of a carboxylic acid ester, a ketone, and an ether can be used. The carboxylic acid ester to be preferably used is an ester composed of a saturated aliphatic carboxylic acid and a saturated alcohol.

Specific examples of the esters include benzyl acetate, ethyl benzoate, γ-butyrolactone, methyl benzoate, diethyl malonate, and 2-ethylhexyl acetate. , 2-butoxyethyl acetate, 3-methoxy-3-methyl-butyl acetate, diethyl oxalate, ethyl acetate, cyclohexyl acetate, 3-methoxy Base-butyl acetate, methyl acetate methyl acetate, ethyl-3-ethoxypropionate, 2-ethylbutyl acetate, isoamyl propionate, propylene glycol monomethyl ether propionic acid The ester, propylene glycol monoethyl ether acetate, amyl acetate, propylene glycol monomethyl ether acetate, and the like are not limited thereto.

Among these organic solvents, the solvent of the acetate type or the propionate type is particularly preferably 3-methoxy-3-methyl-butyl acetate or propylene glycol monoethyl ether acetate. Ester, propylene glycol monomethyl ether propionate, 3-methoxy-butyl acetate, propylene glycol monomethyl ether acetate.

Further, as the organic solvent other than the above, an aliphatic ether such as a propylene glycol derivative such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol tert-butyl ether or dipropylene glycol monomethyl ether may be used in combination; Aliphatic esters such as ethyl acetate, butyl acetate, isoamyl acetate; or aliphatic groups such as butanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol Alcohols; ketones such as cyclopentanone and cyclohexanone; organic solvents such as xylene, ethylbenzene, and solvent petroleum brain.

In the color material dispersion liquid of the present invention, any of an organic pigment, an inorganic pigment, and a dye is suitably used as the coloring material.

Examples of the organic pigment include a diketopyrrolopyrrole pigment, an azo pigment such as azo, diazo, or polyazo, a copper phthalocyanine, a copper halide phthalocyanine, or a metal-free phthalocyanine. Cyanine pigment, amine guanidine, diaminodiguanide, pyrimidine, yellow ketone, anthanthrone, indanthrone, pyranthrone, or An anthraquinone pigment such as violanthrone, a quinophthalone pigment, a bisoxazine pigment, a perinone pigment, an anthraquinone pigment, a thioindigo pigment, an isoporphyrin pigment, An isoindolinone pigment, a quinoline yellow pigment, a threne pigment, or a metal complex pigment.

Examples of the inorganic pigment include titanium oxide, zinc oxide, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin, talc, bentonite, black iron oxide, cadmium red, and red oxidation. Iron, molybdenum red, molybdenum orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, Chromium oxide, chrome green, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, blue, indigo, cobalt blue, sky blue, cobalt vermiculite blue, cobalt zinc vermiculite blue, manganese violet, or cobalt violet.

Examples of the dye include an azo dye, an anthraquinone dye, a condensed polycyclic aromatic carbonyl dye, an indigo dye, a gold carbocation dye, a phthalocyanine dye, a methine group, a polymethine dye, and the like.

When a specific example of a representative pigment and a dye is represented by a color index (CI) number, it is preferably used as follows, but is not limited thereto.

As examples of the red pigment, Pigment Red (hereinafter abbreviated 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.

As an example of the orange pigment, Pigment Orange (hereinafter abbreviated as PO) 13, PO36, PO38, PO43, PO51, PO55, PO59, PO61, PO64, PO65, PO71, or the like can be used.

As an example of the yellow pigment, pigment yellow (hereinafter abbreviated 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.

Further, as an example of the violet pigment, pigment violet (hereinafter abbreviated as PV) 19, PV23, PV29, PV30, PV32, PV37, PV40, PV50, or the like can be used.

Further, as an example of the blue pigment, pigment blue (hereinafter abbreviated as PB) 15, PB15:3, PB15:4, PB15:6, PB22, PB60, PB64 or the like can be used.

Further, as an example of the green pigment, pigment green (hereinafter abbreviated as PG) 7, PG10, PG36, PG58, or the like can be used.

As an example of the black pigment, a black organic pigment, a mixed color organic pigment, an inorganic pigment, or the like can be used. Examples of the black organic pigment include carbon black, phthalocyanine, and aniline black. Examples of the mixed color organic pigment include at least two pigments selected from the group consisting of red, blue, green, purple, yellow, magenta, and cyan. Examples of the inorganic pigments include graphite, and metal fine particles such as titanium, copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, and silver, metal oxides, and composite oxides. , metal sulfides, metal nitrides, metal oxynitrides, and the like. These may be used alone or in combination of two or more. Due to its high light-shielding properties, carbon black and titanium nitride are particularly preferred.

Further, examples of the white pigment include titanium dioxide, barium carbonate, zirconium oxide, calcium carbonate, barium sulfate, alumina white, and cerium oxide.

Examples of the dye include CIDirect 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; CIAcid 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; CIReactive Red 3, 13, 17, 19, 21, 22, 23, 24, 29, 35, 37, 40, 41, 43, 45, 49, 55; CIBasic Red 12, 13, 14, 15, 18, 22, 23, 24, 25, 27, 29, 35 , 36, 38, 39, 45, 46; CIDirect Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101; CIAcid Violet 5, 9, 11, 34 , 43, 47, 48, 51, 75, 90, 103, 126; CIReactive Violet 1, 3, 4, 5, 6, 7, 8, 9, 16, 17, 22, 23, 24, 26, 27, 33, 34; CIBasic Violet 1, 2, 3, 7, 10, 15, 16, 20, 21, 25, 27, 28, 35, 37, 39, 40, 48; CIDirect 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; CIAcid 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; CIReactive Yellow 2, 3, 13, 14, 15, 17, 18, 23, 24, 25, 26, 27, 29, 35, 37, 41, 42; CIBasic Yellow 1, 2, 4, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 39, 40; CIAcid Green 16; CIAcid Blue 9, 45, 80 , 83, 90, 185; CIBasic Orange 21, 23, etc.

In the color material dispersion liquid of the present invention, in order to uniformly and stably disperse the coloring material in the resin solution, it is more preferable to add a polymer dispersant. Examples of the polymer dispersant include a polyester polymer dispersant, an acrylic polymer dispersant, a polyurethane polymer dispersant, a polyallylamine polymer dispersant, and a carbodiimide system. Dispersing agents, etc. These polymeric dispersants It is suitably selected and used according to the kind of coloring material.

The polymer dispersant includes various dispersants having only an amine value dispersant, a dispersant having only an acid value, a dispersant having an amine value and an acid value, and a dispersant having no amine value or acid value, but In order to make the effect of the present invention remarkable, it is more preferable to use a dispersant having an amine value, and still more preferably a polymer dispersant having only an amine value.

Specific examples of the dispersant having only an amine value include DISPERBYK 102, DISPERBYK 160, DISPERBYK 161, DISPERBYK 162, DISPERBYK 2163, DISPERBYK 2164, DISPERBYK 166, DISPERBYK 167, DISPERBYK 168, DISPERBYK 2000, DISPERBYK 2050, DISPERBYK 2150 DISPERBYK 2155, DISPERBYK LPN6919, DISPERBYK LPN21116, DISPERBYK LPN21234, DISPERBYK 9075, DISPERBYK 9077 (above BYK Chemical Company); 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 (above), AJISPER PB711 (manufactured by AJINOMOTO FINE-TECHNO Co., Ltd.), but not limited thereto .

Among the dispersants having only an amine value, in particular, a polymer dispersant having at least a tertiary amino group is preferably used, and specific examples thereof include DISPERBYK LPN6919, DISPERBYK LPN21116 and the like.

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, Anti-Terra-205 (above BYK Chemical Company); SOLSPERSE 24000 (manufactured by Lubrizol); AJISPER PB821, AJISPER PB880, AJISPER PB881 (above is AJINOMOTO FINE-TECHNO company) and the like.

These polymer dispersing agents may be used singly or in combination of two or more kinds. Since such a polymer dispersing agent does not have photosensitivity, when the amount of the photosensitive resin composition is deteriorated, the photosensitive performance of the target photosensitive resin composition is deteriorated, and it is desirable to appropriately adjust the dispersion stability and the photosensitivity. When the addition of 1 to 50 (% by mass) to the coloring material, and more preferably 3 to 30 (% by mass), it is more preferable because the photosensitive performance is not deteriorated and the effect of high dispersion is stabilized.

In the color material dispersion liquid of the present invention, the weight composition of the coloring material component/resin component is preferably in the range of 90/10 to 20/80, more preferably 90/10 to 40/60. Here, the resin component means a total of additives such as a polymer dispersant other than the acrylic copolymer. When the amount of the resin component is too small, the dispersion stability of the coloring material is not good. On the other hand, when the amount of the coloring material component is too small, it is difficult to form a coating film having high coloring power when the colored coating film is formed by the coloring material dispersion liquid. Not good.

In the color material dispersion liquid of the present invention, the solid content concentration of the total of the resin component and the coloring material component is preferably 2% by mass or more and 60% by mass or less, more preferably 5% by mass, from the viewpoint of dispersion stability and productivity. The above quality is 30% or less.

The method for producing the colored material dispersion liquid of the present invention is not particularly limited, and is usually a method of dispersing a coloring material in an acrylic copolymer solution by a disperser.

As the dispersing machine for dispersing the coloring material, various methods such as a ball mill, a sand mill, a three-roll mill, and a high-speed punching mill can be used, but from the viewpoint of dispersion efficiency and micro-dispersion, a bead mill is preferred. As the bead mill, a CoBall Mill, a basket mill, a pin mill, a DYNO Mill or the like can be used. The beads of the bead mill preferably use titanium oxide beads, zirconia beads, zircon beads, and the like.

The particle diameter for dispersion is preferably 0.01 mm or more and 5.0 mm or less, more preferably 0.03 mm or more and 1.0 mm or less. When the primary particle diameter of the coloring material and the particle diameter of the secondary particles formed by the aggregation of the primary particles are small, it is preferable to use finely dispersed beads of 0.03 mm or more and 0.10 mm or less. In this case, it is preferred to use a bead mill having a separator capable of separating minute dispersion beads and a dispersion liquid to carry out dispersion. On the other hand, when dispersing a coloring material containing coarse particles having a size of about several micrometers, it is preferable to use a dispersion bead of 0.10 mm or more to obtain a sufficient pulverization force, and to disperse the pigment finely.

The photosensitive colored resin composition using the color material dispersion liquid of the present invention is exemplified below, but is not limited thereto.

The photosensitive colored resin composition of the present invention comprises at least an alkali-soluble polymer, a reactive monomer, and a photopolymerization initiator added to the color material dispersion of the present invention. The content ratio of these is usually from 10/90 to 90/10 by weight of the alkali-soluble polymer and the reactive monomer, and the addition of the photopolymerization initiator The amount is about 1 to 20% by weight based on the weight of the polymer to the monomer. Here, the weight of the alkali-soluble polymer is the sum of the acrylic copolymers contained in the dispersion of the coloring material in addition to the weight of the newly added alkali-soluble polymer.

As the alkali-soluble polymer of the photosensitive colored resin composition of the present invention, an acrylic copolymer used for a coloring material dispersion can be used, and a new alkali-soluble polymer can also be used. The newly used alkali soluble polymer is detailed below.

As the alkali-soluble polymer, an alkali-soluble polymer having a carboxyl group is preferred, and a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound is preferably used. Examples of the unsaturated carboxylic acid include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and vinyl acetic acid; dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid or anhydrides thereof; A polycarboxylic acid monoester such as citric acid mono(2-(methyl) propylene methoxyethyl ester). In particular, an acrylic polymer containing a constituent unit derived from (meth)acrylic acid is preferred, and a carboxylic acid contained in a constituent unit and a compound containing an ethylenically unsaturated group and an epoxy group are preferably used. In the case of the acrylic polymer obtained by the reaction, the sensitivity at the time of exposure and development is improved, so that it can be preferably used. As the ethylenically unsaturated group, an acryl group or a methacryl group is preferred.

These may be used alone or in combination with other copolymerizable ethylenically unsaturated compounds. The copolymerizable ethylenically unsaturated compound, specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, isopropyl acrylate, methacrylic acid n -propyl ester, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, iso-butyl acrylate, methacrylic acid - Butyl ester, tert-butyl acrylate, tert-butyl methacrylate, n-amyl acrylate, n-pentyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl Alkyl ester of unsaturated carboxylic acid such as acrylate or benzyl methacrylate, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, α -methylstyrene An aromatic vinyl compound, a (crosslinked) cyclic hydrocarbon group such as a tricyclodecyl (meth) acrylate, an aminoalkyl ester of an unsaturated carboxylic acid such as an aminoethyl acrylate, or a glycidyl group Acrylate, epoxy propyl methacrylate, etc., unsaturated carboxylic acid glycidyl ester, vinyl acetate, propionic acid Alkenyl carboxylic acid vinyl esters, etc., acrylonitrile, methacrylonitrile Bing Xixi nitrile, α - chloro acrylonitrile, the vinyl cyanide compound, 1,3-butadiene, isoprene and the like of the aliphatic conjugated a conjugated diene, a polystyrene, a polymethacrylate, a polymethyl methacrylate, a polybutyl acrylate, a polybutyl methacrylate or the like having an acryl fluorenyl group or a methacryl fluorenyl group at the terminal, respectively. However, it is not limited to this.

In particular, an acrylic polymer containing (meth)acrylic acid and benzyl (meth) acrylate is particularly preferable from the viewpoint of dispersion stability and pattern processability.

Further, in addition to the acrylic polymer obtained by reacting (meth)acrylic acid contained in the constituent unit described above with a compound containing an ethylenically unsaturated group and an epoxy group, it may be preferably used in the side chain. An acrylic polymer having an ethylenically unsaturated group. Specific examples thereof include a copolymer of Japanese Patent Publication No. 3120476, Japanese Laid-Open Patent Publication No. Hei 8-262221, or a commercially available acrylic polymer photocurable resin "CYCLOMER (registered trademark) P". (DAICEL Chemical Industry Co., Ltd.), alkali-soluble cardo resin, and the like.

The weight average molecular weight (Mw) of the alkali-soluble polymer is preferably from 5,000 to 40,000 (measured by gel permeation chromatography using tetrahydrofuran as a carrier, converted from a standard polystyrene calibration line), Further, a polymer having an average molecular weight of 8,000 to 40,000 and an acid value of 60 to 150 (mgKOH/g) is sensitive to photosensitivity, solubility in an ester solvent, solubility in an alkaline developer, and residue. It is the best for every point of view.

As the reactive monomer of the photosensitive colored resin composition of the present invention, a polyfunctional or monofunctional acrylic monomer or oligomer can be used. Among them, a polyfunctional monomer is preferable, and as the polyfunctional monomer, for example, bisphenol A diepoxypropyl ether (meth) acrylate or poly(meth) acrylate urethane may be mentioned. Bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylate, phthalic anhydride propylene oxide (meth) acrylate, trimellitic acid diethylene glycol Alcohol (meth) acrylate, rosin modified epoxy di(meth) acrylate, alkyd modified (meth) acrylate, such as Japanese Patent No. 3621533 or Japanese Patent Laid-Open No. 8-278630 The geminal diacrylate oligomer described in the publication, or tripropylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A diglycidyl ether di Methyl) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl alcohol tri (meth) acrylate, tripropylene formaldehyde, neopentyl alcohol tetra (meth) acrylate and its acid modification Sex, dipentaerythritol hexa(meth) acrylate and its acid modified body, dipentaerythritol penta (meth) acrylate and its acid modified body, 2,2-bis[4-( 3-propenyloxy-2-hydroxypropane Phenyl]propane, bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]methane, bis[4-(3-propenyloxy-2-hydroxypropoxy) Phenyl]anthracene, bis[4-(3-propenyloxy-2-hydroxypropoxyl) Phenyl]ether, 4,4'-bis[4-(3-propenyloxy-2-hydroxypropoxy)phenyl]cyclohexane, 9,9-bis[4-(3-propene)醯oxy-2-hydroxypropoxy)phenyl]anthracene, 9,9-bis[3-methyl-4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, 9 ,9-bis[3-chloro-4-(3-propenyloxy-2-hydroxypropoxy)phenyl]anthracene, bisphenoxyethanol oxime diacrylate, bisphenoxyethanol oxime dimethyl Acrylate, biscresol oxime diacrylate, biscresol oxime dimethacrylate, and the like. These can be used singly or in combination.

By the selection and combination of such polyfunctional monomers or oligomers, the characteristics of the sensitivity and processability of the photoresist can be controlled. In particular, in order to improve sensitivity, it is preferred to use a compound having a functional group of 3 or more, more preferably 5 or more, and particularly preferably dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, and Its acid modified body. Further, a reaction product of an epoxy group having two epoxypropyl ether groups and methacrylic acid, and a polybasic acid carboxylic acid or an anhydride thereof are reacted, and the obtained alkali-soluble monomer containing an unsaturated group is developed, It is also preferably used from the viewpoint of workability. Further, it is preferable to use a combination of a (meth) acrylate having a plurality of aromatic rings and a high water-repellent anthracene ring in the molecule, since the pattern can be controlled to a desired shape during development.

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

Examples of the alkylphenone-based photopolymerization initiator include an α -aminoalkylphenone or an α -hydroxyalkylphenone, and particularly an α -aminoalkylbenzophenone from a high sensitivity viewpoint. It is better. For example, 2,2-diethoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinylpropan-1-one, Ciba. Specialty. Chemical, "IRGACURE (registered trademark)" 369 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, Ciba. Specialty. Chemical (share) "IRGACURE (registered trademark)" 379 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) Phenyl]-1-butanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and the like.

Specific examples of the oxime ester photopolymerization initiator include Ciba. Specialty. Chemical, "IRGACURE (registered trademark)" OXE01 1,2-octanedione, 1-[4-(phenylsulfanyl)-2-(O-benzylidenehydrazide)], Ciba. Specialty. Chemical (R) "IRGACURE (registered trademark)" OXE02 ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1- (0-Ethyl group), "ADEKA (registered trademark) OPTOMER" N-1818, N-1919, "ADEKA CRUISE" NCI-831, etc., manufactured by Asahi Kasei Co., Ltd.

Further, in addition to the photopolymerization initiator, a benzophenone compound, a xanthone compound, an imidazole compound, a benzothiazole compound, a benzoxazole compound, or a carbazole may be used in combination. A known photopolymerization initiator such as an inorganic photopolymerization initiator such as a compound, a triazine compound, a phosphorus compound or a titanate. For example, benzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzophenone Ingredients, benzoin methyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, α -hydroxyisobutyl benzophenone, thioxanthone, 2-chlorothioxanthone, t-butyl hydrazine Bismuth, 1-chloropurine, 2,3-dichloropurine, 3-chloro-2-methylindole, 2-ethylanthracene, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 1 , 2-benzoxanthene, 1,4-dimethylhydrazine, 2-phenylindole, 2-(o-chlorophenyl)-4,5-diphenylimidazolium 2-mer, 2-mercapto Benzothiazole, 2-mercaptobenzoxazole, 4-(p-methoxyphenyl)-2,6-di-(trichloromethyl)-s-triazine, and the like.

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

Specific esters include benzyl acetate (boiling point 214 ° C), ethyl benzoate (boiling point 213 ° C), γ-butyrolactone (boiling point 204 ° C), methyl benzoate (boiling point 200) °C), diethyl malonate (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 acetate (boiling point 181 ° C), cyclohexyl acetate (boiling point 174 ° C), 3 -methoxy-butyl acetate (boiling point 173 ° C), ethyl acetonitrile acetate (boiling point 172 ° C), ethyl-3-ethoxy propionate (boiling point 170 ° C), 2-ethylbutyl Acetate (boiling point 162 ° C), isoamyl propionate (boiling point 160 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), propylene glycol monoethyl ether acetate (boiling point 158 ° C), acetic acid Amyl ester (boiling point: 150 ° C), propylene glycol monomethyl ether acetate (boiling point: 146 ° C), and the like, but is not limited thereto.

Among these solvents, 3-methoxy-3-methyl-butyl acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ester are particularly preferred as the solvent of the acetate or propionate type. Ethyl ether propionate, 3-methoxy-butyl acetate, propylene glycol monomethyl ether acetate.

Further, a solvent other than the above may be used in combination with propylene glycol monomethyl ether (boiling point: 120 ° C), propylene glycol monoethyl ether (boiling point: 133 ° C), propylene glycol, tert-butyl ether (boiling point: 153 ° C), dipropylene glycol monomethyl ether. Propylene glycol (boiling point 188 ° C) An aliphatic ether such as a derivative; an aliphatic ester other than the above, such as ethyl acetate (boiling point 77 ° C), butyl acetate (boiling point 126 ° C), isoamyl acetate (boiling point 142 ° C); or butanol ( An aliphatic alcohol such as a boiling point of 118 ° C), 3-methyl-2-butanol (boiling point 112 ° C), 3-methyl-3-methoxybutanol (boiling point 174 ° C); cyclopentanone, cyclohexyl Ketones such as ketones; solvents such as xylene (boiling point: 144 ° C), ethylbenzene (boiling point: 136 ° C), solvent petroleum brain (petroleum fraction: boiling point: 165 to 178 ° C).

In addition, as the size of the substrate is increased, the application by the die coating device is mainstream. Therefore, in order to achieve appropriate volatility and drying properties, it is preferably composed of a mixed solvent of two or more components. When the boiling point of all the solvents constituting the mixed solvent is 150° C. or less, uniformity of film thickness cannot be obtained, and the film thickness at the end of coating is increased, and aggregates of pigments are generated from the die portion of the coating liquid discharged from the slit. There are many problems such as streaks in the coating film. On the other hand, when the solvent having a boiling point of 200 ° C or higher is contained in the mixed solvent, the surface of the coating film becomes adhesive and sticks. Therefore, it is preferred to contain a mixed solvent of 30 to 75% by mass of a solvent having a boiling point of 150 ° C or more to 200 ° C.

In the photosensitive colored resin composition of the present invention, in order to improve the adhesion between the coating film and the base substrate, it is preferred to add an adhesion improving agent to the colored resin composition, and a decane coupling agent is suitably used. The decane coupling agent is not particularly limited, and examples thereof include a decane coupling agent having a functional group such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, or an amine group, but are not limited thereto. This is the case. Specifically, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxyl is preferred. Baseline, 3-glycidoxypropylmethyldiethoxydecane, 2-(3,4-Epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, vinyltrimethoxydecane, Vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy decane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-propenyloxypropyltrimethoxydecane, 3- Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, 3- Mercaptopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, 3-isocyanatepropyltriethoxydecane, p-styryltrimethoxydecane, and the like.

The amount of the adhesion improving agent added is preferably from 1 to 15 by mass based on the total amount of the solid content of the colored resin composition, that is, the sum of the coloring material, the acrylic copolymer, the alkali-soluble polymer, and the reactive monomer. %, more preferably 2 to 10% by mass. When the amount is less than 1% by mass, the effect of improving the adhesion is insufficient. When the amount is more than 15% by mass, fine patterns are missing during alkaline development, and the resolution is lowered.

Further, in the photosensitive colored resin composition of the present invention, a surfactant may be added for the purpose of applicability, smoothness of a colored film, or prevention of a Benard cell. The amount of the surfactant added is usually 0.001 to 10% by mass, preferably 0.01 to 1% by mass based on the pigment. When the amount of addition is too small, there is no coating property, smoothness of the colored film, or effect of preventing Benard's acupoint flow. When the amount is too large, the coating film may have poor physical properties.

Specific examples of the surfactant include an anionic surfactant such as ammonium lauryl sulfate or polyoxyethylene ethyl ether sulfate triethanolamine, and stearin. Amphoteric surfactants such as nucleoside acetate, lauryl trimethylammonium chloride, etc., lauryl dimethylamine oxide, lauryl carboxymethyl hydroxyethyl imidazolium betaine, etc. a nonionic surfactant such as oxyethyl lauryl ether, polyoxyethylidene stearyl ether, sorbitan monostearate or the like, and polypyrene having a main skeleton such as polydimethyl siloxane Oxygen surfactant, fluorine surfactant, and the like. The present invention is not limited thereto, and one or two or more kinds of surfactants may be used.

In the photosensitive colored resin composition of the present invention, the weight composition ratio of the coloring material component/resin component is preferably in the range of 80/20 to 10/90 because a film having sufficient coloring power can be obtained. Here, the resin component means a reactive monomer, an oligomer, a photopolymerization initiator, a polymer, in addition to an acrylic copolymer used for a coloring material dispersion or an alkali-soluble polymer added to a colored resin composition. The total of additives such as dispersants.

In the photosensitive colored resin composition of the present invention, the solid component concentration of the total of the resin component and the coloring material component is from the coating property. From the viewpoint of drying property, it is preferably 2% or more and 60% or less, more preferably 5% or more and 30% or less.

Example

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited to the following examples.

<Evaluation method>

"acid value"

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

"base value"

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

"Molecular weight"

The weight average molecular weight (Mw) value measured by gel permeation chromatography (GPC) "HLC-8220GPC" (TOSOH (test) test apparatus) using tetrahydrofuran as a carrier and polystyrene as a molecular weight standard was used.

"viscosity"

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

"distributed stability"

The dispersion of the initial viscosity of the coloring material dispersion and the viscosity after one week, that is, the percentage of the viscosity after one week to the initial viscosity (growth, unit %), was comprehensively evaluated as follows. Although it is preferable to increase the viscosity by the time, it is thickened by the interaction of the finely dispersed pigments, and the allowable standard is Δ, which is evaluated as follows.

○The dispersion state is extremely good (the viscosity increase within one week is less than 50%)

△The dispersion state is good (the viscosity increase in the first week is more than 50%, within 100%)

×Dispersion state is unstable (increased viscosity greater than 100% in 1 week)

"developability"

With respect to the dissolution time of the non-photosensitive portion of the developed coating film with a 0.045% potassium hydroxide aqueous solution, the allowable reference was evaluated as Δ from the viewpoint of industrial utilization as follows.

○The developability is extremely good (the unexposed part of the photoresist film is dissolved within 50 seconds) End)

△The developability is good (the dissolution of the unexposed portion of the photoresist film is completed within 50 seconds and within 100 seconds)

×The developability is poor (it takes 100 seconds or more until the dissolution of the unexposed part of the photoresist coating film is completed)

"heat resistance"

The thermogravimetric analysis apparatus (Q50 manufactured by TA Instruments) was heated in the order of prebaking at 150 ° C for 30 minutes, and then post-baked at 280 ° C × 60 minutes, and evaluated for heat resistance according to the change in the weight of the sample before and after the post-baking. From the viewpoint of industrial utilization, the allowable reference is regarded as Δ, and evaluation is performed as follows.

○Excellent heat resistance (weight change of 1.5% or less)

△The heat resistance is good (more than 1.5% and the weight change of 2.0% or less)

×The heat resistance is poor (more than 2.0% of the weight change)

<Synthesis of Acrylic Copolymer>

The synthesis examples of the acrylic copolymer in the present invention are shown below. Further, the present invention is not limited to the following methods. The manufacturing method and characteristic values of the acrylic copolymer in this synthesis example are shown in Table 1. Moreover, the mark of "part" in each synthesis example shows a weight part.

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

. Methyl methacrylate (MMA)

. Dodecyl methacrylate (DOMA)

. Stearic acid methacrylate (SLMA)

n is a structure of the formula (D1) of 0;

. Methacrylic acid (MAA)

. Acrylic acid (AA)

a structure represented by the formula (E2);

. Styrene (St)

. 4-methylstyrene (4MSt)

a structure represented by the formula (E1);

. Benzyl methacrylate (Bz-MA)

a structure represented by the formula (B);

. 2-dimethylaminoethyl methacrylate (MLDA)

. 2-dimethylaminoethyl acrylate (ALDA)

a structure represented by the formula (C);

. 2-dimethylaminoethyl hydrochloride methacrylate (MLDA-Cl)

a structure represented by the formula (F);

. 2-ethylhexyl acrylate (2EHA),

. 2-ethylhexyl methacrylate (2EHMA)

a structure represented by the formula (D1);

. Monomer mixture containing acidic functional groups (made by Rhône. Poulenc) (β-CEA)

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

. Epoxypropyl methacrylate (GMA)

Polymerization initiator

. Azobisisobutyronitrile (AIBN)

. N-dodecyl mercaptan (MDM)

As shown in Table 1, the adjustment of the base value is based on the addition or subtraction of the amount of the monomer containing the amine group (MLDA, ALDA, MLDA-Cl), and the adjustment of the acid value is a monomer containing a carboxyl group (AA, MAA). The increase or decrease of the addition amount of β- CEA) was carried out separately.

As shown in Table 1, the adjustment of the weight average molecular weight was carried out in accordance with the increase or decrease in the addition amount of the polymerization initiator (AIBN) and/or n-dodecyl mercaptan (MDM).

[Synthesis Example 1]

200 parts of propylene glycol monoethyl ether acetate solvent was placed in a pressure-resistant container equipped with a stirring device, a thermometer, a reflux condenser, and a drip pump, and the reaction vessel was filled with nitrogen gas, and then the temperature was raised to 90 ° C, and the liquid was used for dripping. The pump took 3 hours to mix 1 part of 2-methylaminoethyl methacrylate (MLDA), 32 parts of methyl methacrylate (MMA), and 2-ethylhexyl methacrylate (2EHMA) 20 Parts, 30 parts of styrene (St), 17 parts of methacrylic acid (MAA), 2.0 parts of azobisisobutyronitrile (AIBN) as a polymerization initiator, 3.0 parts of n-dodecyl mercaptan (MDM) , for copolymerization. Then, the inside of the reaction container was replaced with air, and 10 parts of glycidyl methacrylate (GMA) was dropped by a dripping liquid for 1 hour to carry out an addition reaction, and further stirred in a container for 2 hours. As a result, an acrylic copolymer (P-1) having a characteristic value of a base value of 5 mmol/100 g, an acid value of 75 mgKOH/g, and a weight average molecular weight of 7,000 was obtained.

[Synthesis Example 2]

The preparation was carried out in the same manner as in Synthesis Example 1 except that the amount of MMA and MLDA added was changed to 31 parts and 2 parts, respectively. As a result, it is obtained as shown in Table 1. The characteristic value of the acrylic copolymer (P-2).

[Synthesis Example 3]

The production was carried out in the same manner as in Synthesis Example 1 except that the amount of MMA and MLDA added was changed to 30 parts and 3 parts, respectively. As a result, an acrylic copolymer (P-3) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 4]

The production was carried out in the same manner as in Synthesis Example 1 except that the amount of MMA and MLDA added was changed to 29 parts and 4 parts, respectively. As a result, an acrylic copolymer (P-4) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 5]

The production was carried out in the same manner as in Synthesis Example 1 except that the amount of MMA and MLDA added was changed to 26 parts and 7 parts, respectively. As a result, an acrylic copolymer (P-5) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 6]

The production was carried out in the same manner as in Synthesis Example 1, except that MLDA was not used and the amount of MMA added was 33 parts. As a result, an acrylic copolymer (P-6) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 7]

The preparation was carried out in the same manner as in Synthesis Example 1 except that the amount of MMA and MLDA added was changed to 17 parts and 16 parts, respectively. As a result, an acrylic copolymer (P-7) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 8]

Production was carried out in the same manner as in Synthesis Example 3 except that MLDA was changed to ALDA. As a result, an acrylic copolymer having the characteristic values shown in Table 1 was obtained. (P-8).

[Synthesis Example 9]

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

[Synthesis Example 10]

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

[Synthesis Example 11]

The production was carried out in the same manner as in Synthesis Example 3 except that the amount of MMA and MAA added was changed to 27 parts and 20 parts, respectively. As a result, an acrylic copolymer (P-11) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 12]

The 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]

The production was carried out in the same manner as in Synthesis Example 3 except that the amount of MMA added was changed to 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]

The preparation was carried out in the same manner as in Synthesis Example 3 except that the amounts of MMA and MAA added were 40 parts and 7 parts, respectively. As a result, it is obtained as shown in Table 1. The characteristic value of the acrylic copolymer (P-14).

[Synthesis Example 15]

The production was carried out in the same manner as in Synthesis Example 3 except that the amounts of MMA and MAA added were 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]

Production was carried out in the same manner as in Synthesis Example 3 except that MAA was changed to AA. As a result, an acrylic copolymer (P-16) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 17]

The preparation was carried out in the same manner as in Synthesis Example 3 except that the amount of MMA added was 14 parts, and 17 parts of MAA was changed to 33 parts of β- CEA. 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 changed to 2EHA. As a result, an acrylic copolymer (P-18) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 19]

Production was carried out in the same manner as in Synthesis Example 3 except that 2EHMA was changed to dodecyl methacrylate (DOMA). As a result, an acrylic copolymer (P-19) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 20]

Production was carried out in the same manner as in Synthesis Example 3 except that 2EHMA was changed to stearyl methacrylate (SLMA). As a result, an acrylic copolymer (P-20) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 21]

The production was carried out in the same manner as in Synthesis Example 3 except that 2EHMA was not used and the amount of MMA added was 50 parts. 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 added 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 added was changed 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]

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

[Synthesis Example 25]

Production was carried out 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 added was 6.0. As a result, an acrylic copolymer (P-26) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 27]

The production was carried out in the same manner as in Synthesis Example 3 except that MDM was not used and the amount of AIBN added was changed to 0.8 parts. As a result, an acrylic copolymer (P-27) having the characteristic values shown in Table 1 was obtained.

[Synthesis Example 28]

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

[Synthesis Example 29]

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

[Synthesis Example 30]

The production was carried out in the same manner as in Synthesis Example 3 except that St was not used and the amount of MMA added was 60 parts. As a result, an acrylic copolymer (P-30) having the characteristic values shown in Table 1 was obtained.

<Production of Coloring Material Dispersion Liquid and Photosensitive Colored Resin Composition>

[Example 1]

200 g of titanium nitride particles (Bk-1, manufactured by Nissin Engineering Co., Ltd.) and 114 g of a propylene glycol monoethyl ether acetate solution of acrylic acid copolymer (P-1) produced by a thermoelectric plasma method were used. DISPERBYK LPN-21116 (DP-1, BYK Chemical Co., propylene glycol monoethyl ether acetate 40% by weight solution) having a tertiary amino group and a quaternary ammonium salt, 25 g of a polymer dispersant, and propylene glycol monoethyl ether 661 g of acetate (PMA) was placed in a tank, and stirred by a homomixer (manufactured by PRIMIX) for 20 minutes to obtain a preliminary dispersion. Then, the preliminary dispersion was supplied to an Ultra Apex Mill (manufactured by Shou Industrial Co., Ltd.) equipped with a centrifugal separation separator filled with 75% of 0.05 mmφ zirconia beads (manufactured by NETUREN, YTZ balls) to rotate The dispersion was carried out at a speed of 8 m/s for 3 hours to obtain a color material dispersion liquid 1 having a solid content concentration of 25% by weight and a coloring material/resin (weight ratio) = 80/20. The viscosity of the obtained coloring material dispersion 1 immediately after preparation was 3.4 mPa. s, after 1 week, the viscosity is 5.5mPa. s.

33.00 g of this coloring material dispersion 1 and acrylic acid copolymer (P-1) propylene glycol monoethyl ether acetate 35% by weight solution 7.53 g, propylene glycol monoethyl ether acetate 55.36 g, "ADEKA (registered trademark ) OPTOMER" N-1919 (made by Asahi Kasei Co., Ltd.) 0.99g, dipentaerythritol hexaacrylate (DHPA made by Nippon Kayaku Co., Ltd.) 2.64g, 3-propenyloxypropyltrimethoxy 0.45 g of decane and 0.04 g of BYK333 (manufactured by BYK Chemical Co., Ltd.) were mixed and prepared into a photosensitive colored resin composition.

The obtained photosensitive colored resin composition was applied onto a non-alkaline glass ("1737 material" manufactured by CORNING) on a spin coater, and prebaked at 90 ° C. Bake for 10 minutes. Subsequently, the exposure machine "XG-5000" manufactured by Dainippon SCREEN was used, exposed through a gray dimmer, and developed with a negative resist of 0.045% potassium hydroxide aqueous solution. The development time is 33 seconds.

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

In addition, in Table 2, the coloring material, the acrylic copolymer, the polymer dispersing agent, and the type of the solvent constituting the coloring material dispersion liquid are described as abbreviations, and the respective compounding amounts (% by weight) are described.

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

The same as in Example 1 except that the acrylic acid copolymer (P-2 to P-30) having a change in acid value, base value, and weight average molecular weight and a partially unsaturated monomer were used instead of the acrylic copolymer (P-1). The results of Examples 2 to 22 and Comparative Examples 1 to 8 in which the coloring material dispersion and the photosensitive colored resin composition were produced were shown in Table 2.

Further, with respect to the photosensitive colored resin compositions obtained in Examples 3, 21, and 22 and Comparative Example 8, the heat resistance before and after the post-baking was evaluated by the above method. The results are shown in Table 2.

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

Further, it was found that the stability of the pigment dispersion liquid can be made higher by introducing a long-chain acrylic group into the side chain.

[Example 23]

In addition to the titanium nitride particles (Bk-1, manufactured by Nissin Engineering Co., Ltd.) manufactured by the thermoelectric plasma method, 175 g of a propylene glycol monoethyl ether acetate solution of the acrylic copolymer (P-3) was used as a 35 wt% solution. In the same manner as in Example 3 except that the polymer dispersant and the propylene glycol monoethyl ether acetate (PMA) were not added, the dispersion stability and the photosensitive colored resin composition of the prepared color material dispersion were 214 g. The evaluation results of the developability of the object are shown in Table 3.

In addition, in Table 3, the coloring material, the acrylic copolymer, the polymer dispersing agent, and the type of the solvent constituting the coloring material dispersion liquid are described as abbreviations, and the respective blending amounts (% by weight) are described.

[Comparative Example 9]

The development of the dispersion of the prepared coloring material dispersion and the development of the photosensitive colored resin composition were carried out in the same manner as in Example 23 except that the acrylic copolymer (P-6) was used instead of the acrylic copolymer (P-3). The results of the evaluation of the sex are shown in Table 3.

[Example 24]

In addition to DISPERBYK LPN-6919 (DP-2, a propylene glycol monoethyl ether acetate 40% by weight solution) having a tertiary amine group, DISPERBYK LPN-21116 (DP-1, BYK Chemical Co., Ltd., In the same manner as in Example 3, the dispersion stability of the produced coloring material dispersion and the developability of the photosensitive colored resin composition were carried out in the same manner as in Example 3 except that the propylene glycol monoethyl ether acetate (40% by weight solution) was used as the polymer dispersant. The evaluation results are shown in Table 3.

[Example 25]

In addition to DISPERBYK 2001 (DP-3, BYK Chemical Co., Ltd., propylene glycol monoethyl ether acetate 40% by weight solution) with quaternary ammonium salt and carboxyl group, DISPERBYK LPN-21116 (DP-1, BYK Chemical Co., Ltd., In the same manner as in Example 3, the dispersion stability of the produced coloring material dispersion and the developability of the photosensitive colored resin composition were carried out in the same manner as in Example 3 except that the propylene glycol monoethyl ether acetate (40% by weight solution) was used as the polymer dispersant. The evaluation results are shown in Table 3.

From the results of Examples 23 to 25 and Comparative Example 9, it was found that by using the acrylic copolymer of the present invention, dispersion stabilization can be achieved without adding a polymer dispersant, and it is preferable to increase the dispersion in order to stabilize the dispersion. The molecular dispersant, in particular, more preferably a polymer dispersant having a tertiary amino group.

[Example 26]

In addition to the titanium nitride particles (Bk-1, manufactured by Nissin Engineering Co., Ltd.) produced by the pyroelectric method, 220 g of a propylene glycol monoethyl ether acetate solution of the acrylic copolymer (P-3) was used. As a polymer dispersant, DISPERBYK LPN-21116 (DP-1, a BYK Chemical Co., Ltd., propylene glycol monoethyl ether acetate 40% by weight solution) was 25 g and propylene glycol monoethyl ether acetate (PMA). The evaluation results of the dispersion stability of the prepared color material dispersion liquid and the developability of the photosensitive colored resin composition were shown in Table 3, except that the amount was 698 g.

[Example 27]

In addition to the titanium nitride particles (Bk-1, manufactured by Nissin Engineering Co., Ltd.) manufactured by the thermoelectric plasma method, 175 g of propylene glycol monoethyl ether of the acrylic copolymer (P-3) The solution of 35 wt% acetate was 186 g, and DISPERBYK LPN-21116 (DP-1, a 40 wt% solution of propylene glycol monoethyl ether acetate) as a polymer dispersant was 25 g and propylene glycol monoethyl The evaluation results of the dispersion stability of the prepared color material dispersion and the developability of the photosensitive colored resin composition are shown in Table 3, except that the ether acetate (PMA) was 614 g.

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

[Example 28]

175 g of a high-resistance carbon black (Bk-2, manufactured by CABOT Co., Ltd.), a propylene glycol monoethyl ether acetate (35 wt%) solution of an acrylic copolymer (P-3), 171 g, and a DISPERBYK LPN- as a polymer dispersant 21116 (DP-1, BYK Chemical Co., Ltd., propylene glycol monoethyl ether acetate 40% by weight solution) 38g and propylene glycol monoethyl ether acetate (PMA) 616g were placed in the tank to be a homomixer (PRIMIX) ) Stir for 20 minutes to obtain a preliminary dispersion. Then, the preliminary dispersion liquid was supplied to an ultrafine grinder (manufactured by Shou Industrial Co., Ltd.) equipped with a centrifugal separation separator filled with 75% of 0.05 mm φ zirconia beads (manufactured by NETUREN, YTZ balls) at a rotation speed of 8 m/s. The dispersion was carried out for 3 hours to obtain a color material dispersion liquid 37 having a solid content concentration of 25% by weight and a coloring material/resin (weight ratio) = 70/30.

37.71 g of the coloring material dispersion 37, propylene glycol monoethyl ether acetate 35% by weight solution of the acrylic copolymer (P-1) 4.48 g, propylene glycol monoethyl ether acetate 53.80 g, "ADEKA (registered) trademark) OPTOMER"N-1919 (made by Asahi Kasei Co., Ltd.) 0.96g, dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.) 2.55g, 3-propenyloxypropyltrimethoxydecane 0.04 g of BYK333 (manufactured by BYK Chemical Co., Ltd.) was used to prepare a photosensitive colored resin composition, and the developability was evaluated in the same manner as in Example 1. The dispersion stability of the coloring material dispersion and the photosensitive resin composition were measured. The evaluation results of the developability are shown in Table 3.

[Comparative Example 10]

In the same manner as in Example 28 except that P-6 was used as the acrylic acid copolymer, the evaluation results of the dispersion stability of the prepared color material dispersion and the developability of the photosensitive resin composition are shown in the table. 3.

[Example 29]

120 g of an organic pigment PR177 (R-1, manufactured by Daisei Seiki Co., Ltd.), and a solution of propylene glycol monoethyl ether acetate (35 wt%) of an acrylic copolymer (P-3): 114 g, DISPERBYK LPN as a polymer dispersant -21116 (DP-1, manufactured by BYK Chemical Co., Ltd., propylene glycol monoethyl ether acetate 40% by weight solution) 100 g and 666 g of propylene glycol monoethyl ether acetate (PMA) were placed in a tank to homogenize the mixer (PRIMIX) The mixture was stirred for 20 minutes to obtain a preliminary dispersion. Then, the preliminary dispersion liquid was supplied to an ultrafine grinder (manufactured by Shou Industrial Co., Ltd.) equipped with a centrifugal separation separator filled with 75% of 0.05 mm φ zirconia beads (manufactured by NETUREN, YTZ balls) at a rotation speed of 8 m/s. The dispersion was carried out for 3 hours to obtain a color material dispersion liquid 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 liquid was evaluated in the same manner as in Example 1.

37.50 g of this coloring material dispersion 39, acrylic copolymer (P-1) Propylene glycol monoethyl ether acetate 35% by weight solution 7.29g, propylene glycol monoethyl ether acetate 50.26g, "ADEKA (registered trademark) OPTOMER" N-1919 (made by Asahi Kasei Co., Ltd.) 0.41g, Dipentaerythritol hexaacrylate (DHPA manufactured by Nippon Kayaku Co., Ltd.) 4.05g, 3-propenyloxypropyltrimethoxydecane 0.45g, BYK333 (BYK Chemical Co., Ltd.) 0.04g, photosensitive The developability evaluation was carried out in the same manner as in Example 1 except for the coloring resin composition.

[Comparative Example 11]

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

[Example 30]

50 g of a dye AR289 (R-2, manufactured by a Chinese company), 357 g of a propylene glycol monoethyl ether acetate solution of an acrylic copolymer (P-3), 357 g, and DISPERBYK LPN-21116 as a polymer dispersant (DP-1, BYK Chemical Co., Ltd., propylene glycol monoethyl ether acetate 40% by weight solution) 63 g and propylene glycol monoethyl ether acetate (PMA) 530 g were placed in a tank to homogenize a mixer (manufactured by PRIMIX) Stir for 20 minutes to obtain a preliminary dispersion. Then, the preliminary dispersion liquid was supplied to an ultrafine grinder (manufactured by Shou Industrial Co., Ltd.) equipped with a centrifugal separation separator filled with 75% of 0.05 mm φ zirconia beads (manufactured by NETUREN, YTZ balls) at a rotation speed of 8 m/s. The dispersion was carried out for 3 hours to obtain a color material dispersion liquid 41 having a solid content concentration of 20% by weight and a coloring material/resin (weight ratio) = 25/75. The dispersion stability of the obtained coloring material dispersion liquid was evaluated in the same manner as in Example 1.

45.00 g of the coloring material dispersion liquid 41, a polypropylene glycol copolymer (P-1) propylene glycol monoethyl ether acetate 35% by weight solution 1.03 g, propylene glycol monoethyl ether acetate 48.33 g, "ADEKA (registered) Trademark) OPTOMER"N-1919 (made by Asahi Kasei Co., Ltd.) 0.29g, dipentaerythritol hexaacrylate (DHPA made by Nippon Kayaku Co., Ltd.) 4.86g, 3-propenyloxypropyltrimethoxy The photosensitive colored resin composition was produced by making 0.45 g of decane hexane and 0.04 g of BYK333 (manufactured by BYK Chemical Co., Ltd.), and the developability was evaluated in the same manner as in Example 1.

[Comparative Example 12]

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

[Example 31]

160 g of Ag nanoparticle (made of Ag-1, manufactured by Yamato Chemical Co., Ltd.), 57 g of a propylene glycol monoethyl ether acetate solution of an acrylic copolymer (P-3), and DISPERBYK LPN as a polymer dispersant -21116 (DP-1, manufactured by BYK Chemical Co., Ltd., propylene glycol monoethyl ether acetate 40% by weight solution) 50 g and propylene glycol monoethyl ether acetate (PMA) 733 g were placed in a tank to homogenize the mixer (PRIMIX) The mixture was stirred for 20 minutes to obtain a preliminary dispersion. Then, the preliminary dispersion liquid was supplied to an ultrafine grinder (manufactured by Shou Industrial Co., Ltd.) equipped with a centrifugal separation separator filled with 75% of 0.05 mm φ zirconia beads (manufactured by NETUREN, YTZ balls) at a rotation speed of 8 m/s. The dispersion was carried out for 3 hours to obtain a color material dispersion liquid 43 having a solid content concentration of 20% by weight and a coloring material/resin (weight ratio) = 80/20. The dispersion stability of the obtained coloring material dispersion liquid was evaluated in the same manner as in Example 1.

46.88 g of the coloring material dispersion 43, a propylene glycol monoethyl ether acetate solution of the acrylic copolymer (P-1), a 35 wt% solution of 6.37 g, propylene glycol monoethyl ether acetate, 43.36 g, "ADEKA (registered) Trademark) OPTOMER"N-1919 (made by Asahi Kasei Co., Ltd.) 0.79g, dipentaerythritol hexaacrylate (DHPA made by Nippon Chemical Co., Ltd.) 2.11g, 3-propenyloxypropyltrimethoxy The photosensitive colored resin composition was produced by making 0.45 g of decane hexane and 0.04 g of BYK333 (manufactured by BYK Chemical Co., Ltd.), and the developability was evaluated in the same manner as in Example 1.

[Comparative Example 13]

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

From the results of Examples 28 to 31 and Comparative Examples 10 to 13, it was found that by using the acrylic copolymer of the present invention, not only inorganic pigments but also organic pigments, dyes, and metal fine particles can be dispersed and stabilized.

Industrial availability

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

Claims (8)

A coloring material dispersion liquid comprising at least a coloring material, an acrylic copolymer, and an organic solvent, the acrylic copolymer having at least a structure represented by the formula (A) having an ethylenically unsaturated group in a side chain, and a side chain a structure represented by the formula (B) having a tertiary amino group and/or a structure represented by the formula (C) having a quaternary ammonium salt in a side chain, a structure (D) having a carboxyl group in a side chain, and having The structure of the aromatic ring (E), the base value is 5 to 70 mmol/100 g and the acid value is 50 to 120 mgKOH/g, and the weight average molecular weight in terms of polystyrene by gel permeation chromatography is 5,000 to 30,000; In the formula, R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and R ³ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms, and a carbon number of 6 Any of the divalent aromatic hydrocarbon groups of ~10; In the formula, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alkoxy group having 1 to 4 carbon atoms, and a divalent alicyclic ring having 3 to 6 carbon atoms. Any one of a hydrocarbon group and a quaternary aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ⁶ and R ⁷ each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and carbon. Any one of 3 to 6 alicyclic hydrocarbon groups and 6 to 10 carbon atoms; In the formula, R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents an alkylene group selected from carbon atoms 1 to 4, a divalent alkoxy group having 1 to 4 carbon atoms, and a divalent alicyclic ring having 3 to 6 carbon atoms. Any one of a hydrocarbon group and a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and R ¹⁰ , R ¹¹ and R ¹² each independently represent an alkyl group selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an alkyl group having 1 to 4 carbon atoms. Any of the alicyclic hydrocarbon group having 3 to 6 carbon atoms and the aromatic hydrocarbon group having 6 to 10 carbon atoms, and X represents any one of bromine, chlorine, iodine, hydrogen sulfate, and hydroxide. The colored material dispersion liquid according to claim 1, wherein the structure (D) having a carboxyl group is represented by the following formula (D1), Wherein R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkylene group selected from the group consisting of carbon atoms of 1 to 4, a divalent alicyclic hydrocarbon chain having 3 to 6 carbon atoms, and a divalent aromatic having a carbon number of 6 to 10. Any of the hydrocarbon chains, n represents an integer from 0 to 6, and may be a single or a complex number of n. The colored material dispersion according to claim 1 or 2, wherein the structure (E) having an aromatic ring is represented by the following formula (E1) or (E2), In the formula, R ¹⁵ represents a hydrogen atom or a methyl group, and R ¹⁶ represents an alkyl group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and carbon. Any of 6 to 10 aromatic hydrocarbon groups, halogen atoms, ester groups, sulfhydryl groups and nitro groups; In the formula, R ¹⁷ represents a hydrogen atom or a methyl group, and R ¹⁸ represents an alkyl group selected from the group consisting of hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 6 carbon atoms, and carbon. Any of 6 to 10 aromatic hydrocarbon groups, halogen atoms, ester groups, mercapto groups and nitro groups. The coloring material dispersion according to claim 1 or 2, wherein the acrylic copolymer further has a structure represented by the following formula (F) having a carboxylate in a side chain, In the formula, 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 colored material dispersion liquid according to claim 4, wherein the total carbon number of R ²⁰ and R ²¹ is 4 or more. The colored material dispersion liquid according to claim 3, which has the structure represented by the formula (E2). The coloring material dispersion according to claim 1 or 2, which further comprises a polymer dispersing agent having at least a tertiary amino group in addition to the acrylic copolymer. A photosensitive colored resin composition containing at least the coloring matter dispersion liquid according to any one of claims 1 to 7, a polyfunctional acrylic monomer, and a photoradical polymerization initiator.