TWI836850B - Photosensitive resin composition, color filter, image display element, and method for producing a color filter - Google Patents

Abstract

A photosensitive resin composition for a color filter comprises: a copolymer (A), a solvent (B), a reactive diluent (C), and a photopolymerization initiator (D). The copolymer (A) comprises: a constituent unit (a) having a blocked isocyanate group, a constituent unit (b) having an acid group, a constituent unit (c) having an epoxy group, and a constituent unit (d) having a hydroxyl group.

Description

Photosensitive resin composition, color filter, image display element, and method for manufacturing color filter

The present invention relates to a novel copolymer, a photosensitive resin composition for a color filter containing the copolymer, a color filter, an image display device having the copolymer, and a method for manufacturing the color filter.

In recent years, from the perspective of saving resources or energy, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays or electron beams have been widely used in the fields of various coatings, printing, coatings, adhesives, etc. In addition, in the field of electronic materials such as printed wiring boards, photosensitive resin compositions that can be cured by active energy rays are also used as solder resists or color filter resistors. In addition, the properties required of curable photosensitive resin compositions have gradually become more diverse and advanced, among which short-time curing properties considering productivity and low-temperature curing properties that suppress heat damage to applicable components are also required.

A color filter is generally composed of a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed on the pixel boundaries, and a protective film formed on the pixels and the black matrix. A color filter having such a structure is usually manufactured by sequentially forming a black matrix, pixels, and a protective film on a transparent substrate. Various methods have been proposed as methods for forming pixels and a black matrix (hereinafter, pixels and black matrix are referred to as "coloring patterns"). Among them, the pigment/dye dispersion method, which uses a photolithography process that uses a photosensitive resin composition as a resist and repeatedly coats, exposes, develops, and bakes, has become the mainstream today because it can provide a coloring pattern with excellent durability and few defects such as pinholes.

Generally speaking, the photosensitive resin composition used in photolithography contains alkaline soluble resin, reactive diluent, photopolymerization initiator, colorant and solvent. Although the pigment/dye dispersion method has the above advantages, on the other hand, it requires high heat resistance because it repeatedly forms the black matrix, R, G, B patterns, and has limitations such as the colorant that can withstand high baking temperatures and the types of colorants that can be used are also limited, which often causes problems.

Patent document 1 discloses a coloring composition that can be cured at low temperature and has improved storage stability by using an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a coloring agent, and a compound such as ethyl 3-aminobenzenesulfonate.

Patent Document 2 discloses that low-temperature curing can be achieved by using a photosensitive resin composition that contains an alkaline substance or by heating in the presence of an alkaline substance to promote the reaction toward the final product. Polymer precursor, a specific base generator that generates a base by irradiation and heating of electromagnetic waves. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 2013-68843 [Patent Document 2] Japanese Patent Publication No. 2014-70148

[Problem to be solved by the invention]

In recent years, flexible displays such as electronic paper have become increasingly popular. As a substrate for this flexible display, plastic substrates made of polyethylene terephthalate or the like have been studied. This substrate has the property of stretching or shrinking during baking, so the temperature of the baking step must be lowered. However, the degree achieved by Patent Document 1 is not sufficient to satisfy the above requirements. Furthermore, although Patent Document 2 can improve low-temperature curability, its storage stability is low and it is difficult to put it into practical use.

The present invention is completed to solve the above-mentioned problems, and its purpose is to provide a photosensitive resin composition for a color filter that has good developing properties and storage stability, and can still provide a coloring pattern with excellent solvent resistance even when hardened at low temperatures, and a copolymer useful for preparing the photosensitive resin composition. In addition, the purpose of the present invention is to provide a color filter with a coloring pattern with excellent solvent resistance, a method for manufacturing the same, and an image display element having the color filter. [Means for solving the problem]

That is, the present invention is as shown in the following [1] to [25]. [1] A copolymer (A) characterized by containing a structural unit (a) having a blocked isocyanate group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group. [2] The copolymer of [1], wherein the aforementioned structural unit (a) having a blocked isocyanate group is a structural unit derived from a (meth)acrylate containing a blocked isocyanate group, and the aforementioned structural unit (a) having a blocked isocyanate group The dissociation rate of the blocked isocyanate group of the isocyanate group-terminated (meth)acrylate is 5 to 99 mass % after heating at 100°C for 30 minutes. [3] The copolymer of [1] or [2], wherein the blocking agent of the structural unit (a) having a blocked isocyanate group is selected from diethyl malonate, 3,5-dimethyl One or more species of the group consisting of pyrazole, methyl ethyl ketoxime, 2-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester and 3,5-stylphenol. [4] The copolymer according to any one of [1] to [3], wherein the aforementioned structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid. [5] The copolymer according to any one of [1] to [4], wherein the aforementioned structural unit (c) having an epoxy group is a structural unit derived from (meth)acrylate containing an epoxy group. [6] The copolymer according to any one of [1] to [5], wherein the aforementioned copolymer (A) contains 1 to 60 mol% of the aforementioned structural unit (a) having blocked isocyanato groups, and the aforementioned having The acid group constituent unit (b) is 5 to 65 mol% and the aforementioned constituent unit (c) having an epoxy group is 5 to 65 mol%. [7] The copolymer of any one of [1] to [6], wherein the aforementioned structural unit (a) having a blocked isocyanate group and the aforementioned structural unit having an epoxy group in the aforementioned copolymer (A) The molar ratio of (c) is 10:90~75:25. [8] The copolymer of any one of [1] to [7], wherein the aforementioned copolymer (A) contains: derived from 2-(3,5-dimethylpyrazole-1-methacrylate) methyl)carbonylaminoethyl ester, 2-[O-(1'-methylpropylidenelamino)carboxylamino]ethyl methacrylate, 2-[[[[[2- Methyl-1-side-oxy-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, benzoic acid-4-[[[[2-[(2- Methyl-1-side-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2- Methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3, At least one structural unit (a) of the group of 5-dimethylphenoxy)carbonyl]amino]ethyl ester, a structural unit (b) derived from (meth)acrylic acid, and a structural unit derived from epoxypropyl The structural unit (c) of methacrylate, and the structural unit (e) derived from at least one selected from the group consisting of dicyclopentyl methacrylate and methyl (meth)acrylate. [9] The copolymer according to any one of [1] to [8], wherein the aforementioned copolymer (A) further contains: a structural unit (d) having a hydroxyl group. [10] The copolymer of [9], wherein the aforementioned copolymer (A) contains: derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate , 2-[O-(1'-methylpropyleneamine)carboxylamino]ethyl methacrylate, malonate-2-[[[[[2-methyl-1-side oxy -2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid-4-[[[2-[(2-methyl-1-side oxy- 2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl-1-oxy-2) -propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3,5-dimethylphenoxy) At least one structural unit (a) of the group consisting of carbonyl]amino]ethyl ester, a structural unit (b) derived from (meth)acrylic acid, and a structural unit derived from glycidyl (meth)acrylate (c), structural unit (d) derived from 2-hydroxyethyl methacrylate, and derived from the group consisting of dicyclopentyl (meth)acrylate and meth (meth)acrylate At least one constituent unit (e). [11] The copolymer of [8], wherein the copolymer (A) contains: a composition derived from 2-[O-(1'-methylpropyleneamino)carboxylamino]ethyl methacrylate Unit (a), structural unit (b) derived from (meth)acrylic acid, structural unit (c) derived from glycidyl (meth)acrylate, and dicyclopentyl (meth)acrylic acid The constituent unit of ester (e). [12] The copolymer of [8], wherein the aforementioned copolymer (A) contains: a composition derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate Unit (a), structural unit (b) derived from (meth)acrylic acid, structural unit (c) derived from glycidyl (meth)acrylate, and dicyclopentyl (meth)acrylic acid The constituent unit of ester (e). [13] The copolymer of [10], wherein the copolymer (A) contains: a composition derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate Unit (a), structural unit (b) derived from (meth)acrylic acid, structural unit (c) derived from glycidyl (meth)acrylate, derived from 2-hydroxyethyl methacrylate Structural unit (d), and structural unit (e) derived from dicyclopentyl (meth)acrylate. [14] The copolymer of [8], wherein the aforementioned copolymer (A) contains: derived from malonic acid-2-[[[2-methyl-1-side oxy-2-propenyl]oxy] The structural unit (a) of ethyl]amino]carbonyl]-1,3-diethyl ester, the structural unit (b) derived from (meth)acrylic acid, and the structural unit (b) derived from epoxypropyl (meth)acrylate The structural unit (c), and the structural unit (e) derived from dicyclopentyl (meth)acrylate. [15] The copolymer of any one of [1] to [5], wherein the aforementioned copolymer (A) further contains: a structural unit (d) having a hydroxyl group and a structural unit other than the aforementioned structural units (a) to (d). Constituent unit (e), and The aforementioned copolymer (A) contains: 1 to 40 mol% of the aforementioned structural unit (a) having a blocked isocyanate group, 1 to 60 mol% of the aforementioned structural unit (b) having an acid group, and the aforementioned structural unit having an epoxy group. The constituent unit (c) of the base exceeds 1 to 70 mol%, the aforementioned constituent unit (d) having a hydroxyl group exceeds 0 mol% to 50 mol%, and the aforementioned constituent unit (e) exceeds 0 mol% to 80 mol%. . [16] The copolymer of any one of [1] to [5], wherein the aforementioned copolymer (A) further contains: a structural unit (d) having a hydroxyl group and a structural unit other than the aforementioned structural units (a) to (d). Constituent unit (e), and The aforementioned copolymer (A) contains: 3 to 20 mol% of the aforementioned structural unit (a) having a blocked isocyanate group, 20 to 50 mol% of the aforementioned structural unit (b) having an acid group, and the aforementioned structural unit having an epoxy group. The base constituent unit (c) exceeds 20 to 40 mol%, the aforementioned constituent unit (d) having a hydroxyl group exceeds 0 mol% to 20 mol%, and the aforementioned constituent unit (e) exceeds 20 to 40 mol%.

[17] A polymer composition comprising: a copolymer (A) as described in any one of [1] to [16], and at least one of a solvent (B) and a reactive diluent (C).

[18] A photosensitive resin composition comprising a copolymer (A) as described in any one of [1] to [16], a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D).

[19] A photosensitive resin composition for a color filter, characterized by comprising: a copolymer (A) as described in any one of [1] to [16], a solvent (B), a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E). [20] The photosensitive resin composition for a color filter as described in [19], wherein the copolymer (A) is contained in an amount of 10 to 100 parts by mass, the solvent (B) is contained in an amount of 30 to 1,000 parts by mass, the reactive diluent (C) is contained in an amount of more than 0 to 90 parts by mass, the photopolymerization initiator (D) is contained in an amount of 0.1 to 30 parts by mass, and the colorant (E) is contained in an amount of 3 to 80 parts by mass, relative to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). [21] A photosensitive resin composition for a color filter as described in [19] or [20], wherein the solvent (B) comprises: a hydroxyl-containing organic solvent. [22] A photosensitive resin composition for a color filter as described in any one of [19] to [21], wherein the colorant (E) comprises a pigment.

[23] A color filter characterized by having a colored pattern composed of a cured product of the photosensitive resin composition for a color filter according to any one of [19] to [22].

[24] An image display element, characterized by having a color filter as in [23].

[25] A method for manufacturing a color filter, characterized by comprising: coating the photosensitive resin composition for color filters according to any one of [19] to [22] on a substrate, exposing it, and developing it with alkali , the step of baking at a temperature below 160°C to form a colored pattern. [Effects of the invention]

According to the present invention, a photosensitive resin composition for a color filter having good developing properties and storage stability and imparting a coloring pattern with excellent solvent resistance even when hardened at low temperature, and a copolymer useful for preparing the photosensitive resin composition can be provided. In addition, according to the present invention, a color filter having a coloring pattern with excellent solvent resistance, a method for manufacturing the same, and an image display element having the color filter can be provided.

＜Copolymer (A)＞ The copolymer (A) of the present invention is characterized by containing a structural unit (a) having a blocked isocyanate group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group.

<Constituting unit (a) having blocked isocyanate group> The structural unit (a) having a blocked isocyanate group contained in the copolymer (A) is a structural unit derived from a monomer containing a blocked isocyanate group. Examples of the monomer include monomers having an ethylenically unsaturated bond and a blocked isocyanate group. For example, an isocyanate compound having a vinyl group, a (meth)acryloxy group, etc. in the molecule can be used. Cyanate group is a compound that is blocked with a blocking agent. The reaction between the isocyanate compound and the blocking agent can be carried out with or without the presence of a solvent. When using a solvent, it is necessary to use a solvent that is inert to isocyanato groups. During the blocking reaction, organic metal salts of tin, zinc, lead, etc., and tertiary amines can be used as catalysts. The reaction can generally be carried out at -20~150°C, preferably at 0~100°C. Examples of the isocyanate compound include compounds represented by the following formula (1).

In the above formula (1), ^R1 represents a hydrogen atom or a methyl group, and ^R2 represents -CO-, ^-COOR3- (herein, ^R3 is an alkylene group having 1 to 6 carbon atoms) or -COO- ^R4O -CONH- ^R5- (herein, ^R4 is an alkylene group having 2 to 6 carbon atoms, and ^R5 is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms which may have a substituent). ^R2 is preferably ^-COOR3- , and ^R3 is preferably an alkylene group having 1 to 4 carbon atoms.

Specific examples of the isocyanate compound represented by the formula (1) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. In addition, an equimolar (1 mol:1 mol) reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. The alkyl group of the 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, and more preferably an ethyl group. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-)tolyl diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-)xylene diisocyanate, 1,3- (or 1,4-)bis (isocyanatomethyl) cyclohexane, and lysine diisocyanate.

Among these isocyanate compounds, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate and methacryloyl isocyanate are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.

In addition, in this specification, the term "(meth)acrylate" means that it can be either acrylate or methacrylate, and the term "(meth)acrylic acid" means that it can be either acrylic acid or methacrylate. Any of acrylic.

As the blocking agent for blocking the isocyanate group in the isocyanate compound, for example, there can be cited lactams such as ε-caprolactam, δ-valerolactamide, γ-butyrolactam, β-propiolactamide, etc.; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl solvent, butyl solvent, methyl carbitol, benzyl alcohol, phenyl solvent, furfuryl alcohol, cyclohexanol, etc.; phenol, cresol, 2,6-phenol, 3,5-diphenylphenol, ethylphenol, o-isopropylphenol, butylphenol such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol and other phenols; dimethyl malonate, diethyl malonate, methyl acetylacetate, ethyl acetylacetate, acetylacetate active methylene series such as methyl acetone; thiol series such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; amine series such as diphenylamine, phenylnaphthylamine, aniline, carbazole; acid amide series such as acetanilide, methoxyacetanilide (Acetanisidide), acetamide, benzylamide; acid amide series such as succinimide, maleic acid amide; imidazole, 2-methylimidazole, 2-ethylimidazole imidazole series such as oxazole; pyrazole series such as pyrazole and 3,5-dimethylpyrazole; urea series such as urea, thiourea, ethyleneurea; carbamate series such as N-phenylcarbamate phenyl ester and 2-oxazolidinone; imine series such as ethyleneimine and polyethyleneimine; oxime series such as formaldehyde oxime, acetaldehyde oxime, acetaldehyde oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime; bisulfite series such as sodium bisulfite and potassium bisulfite, etc. These blocking agents can be used alone or in combination of two or more.

The blocking agent protects highly reactive isocyanate groups, but by heating the blocked isocyanate groups will dissociate and regenerate isocyanate groups. In the present invention, the isocyanate group reacts with the reactive functional group contained in the copolymer (A) or the reactive diluent (C), that is, an acid group or a hydroxyl group, an amine group, etc. included if desired, To form a hardened material with high cross-linking density.

From the viewpoint of low-temperature curability or storage stability of the photosensitive resin composition for color filters described later, a monomer containing blocked isocyanate is used as the monomer that provides the structural unit (a) having a blocked isocyanate group. The base (meth)acrylate is preferred. The dissociation rate of the blocked isocyanate group after heat treatment at 100°C for 30 minutes is preferably 5 to 99 mass %, more preferably 8 to 97 mass %, and most preferably 10 to 95 mass %. (Meth)acrylate with blocked isocyanate group is preferred. Moreover, the dissociation rate of the blocked isocyanate group of the blocked isocyanate group-containing (meth)acrylate is measured by HPLC analysis to prepare the blocked isocyanate group-containing (meth)acrylic acid. An n-octanol solution with an ester concentration of 20% by mass was added to the solution, equivalent to 1% by mass of dibutyltin laurate and equivalent to 3% by mass of phenothiazine (polymerization inhibitor), and then heated at 100°C for 30 The value obtained by reducing the mass of the (meth)acrylate containing blocked isocyanato groups after separation. When using a (meth)acrylate containing a blocked isocyanate group with a dissociation rate in the above range, the stability of the copolymer during synthesis can be fully ensured, and the baking temperature during the production of the hardened coating film can be sufficiently reduced. And it can fully ensure the solvent resistance of the hardened coating film. Examples of the blocking agent containing a (meth)acrylate containing a blocked isocyanate group having such a dissociation rate include diethyl malonate, 3,5-dimethylpyrazole, and methylethyl malonate. Ketone oxime, 2-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester, 3,5-phenol, γ-butyrolactamine, 1-methoxy-2-propanol, 2,6-di Methylphenol and diisopropylamine. Among these blocking agents, from the viewpoint of low-temperature curability, diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, 2-hydroxybenzoic acid methyl ester, 4- Methyl hydroxybenzoate and 3,5-stylphenol are preferred.

Furthermore, it is also preferred to use a blocked isocyanate group-containing (meth)acrylate whose dissociation temperature of the blocked isocyanate group is 80°C or higher. . When using (meth)acrylate containing blocked isocyanate groups with a dissociation temperature of 80°C or above, the stability of the copolymer during synthesis can be fully ensured, and unwanted cross-linking during the denaturation reaction described later can be reduced. reaction. On the other hand, when the dissociation temperature of the blocked isocyanate group is 160°C or lower, the baking temperature can be sufficiently reduced and the solvent resistance of the hardened coating film can be fully ensured. Moreover, the dissociation temperature of the blocked isocyanate group of the blocked isocyanate group-containing (meth)acrylate is measured by HPLC analysis to prepare the blocked isocyanate group-containing (meth)acrylic acid. An n-octanol solution with an ester concentration of 20% by mass was added to the solution with the equivalent of 1% by mass of dibutyltin laurate and the equivalent of 3% by mass of phenothiazine (polymerization inhibitor), and then heated at a specified temperature. , the mass reduction ratio of the (meth)acrylate containing blocked isocyanate groups after 30 minutes, and the temperature at which the mass reduction ratio becomes more than 80 mass% is regarded as the dissociation temperature of the blocked isocyanate groups.

Examples of the above-mentioned (meth)acrylate containing a blocked isocyanate group include Karenz (registered trademark) MOI-DEM represented by the following formula (2) (reaction product of methacryloyloxyethyl isocyanate and diethyl malonate, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 90°C, dissociation rate: 90% by mass), Karenz MOI-BP represented by the following formula (3) (reaction product of methacryloyloxyethyl isocyanate and 3,5-dimethylpyrazole, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 110°C, dissociation rate: 70% by mass), and Karenz MOI-BP represented by the following formula (4) MOI-BM (reaction product of methacryloyloxyethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Denko Co., Ltd., dissociation temperature of blocked isocyanate group: 130°C, dissociation rate: 18% by mass%), general methacrylates and corresponding acrylates, etc. These (meth)acrylates containing blocked isocyanate groups can be used alone or in combination of two or more.

The proportion of the constituent unit (a) having a blocked isocyanate group contained in the copolymer (A) is not particularly limited, and is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, and most preferably 3 to 25 mol%. When the proportion of the constituent unit (a) having a blocked isocyanate group is 1 to 40 mol%, the solvent resistance of the cured coating is improved, and the storage stability of the copolymer (A) is also maintained.

＜Constituting unit (b) having an acid group＞ The structural unit (b) having an acid group contained in the copolymer (A) is a structural unit derived from a monomer containing an acid group (except for the aforementioned structural unit (a) having a blocked isocyanato group. ). Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phospho group, and the like. Among these, a carboxyl group is preferred because it is easy to obtain. Examples of the monomer that provides the structural unit (b) having an acid group include monomers having a polymerizable unsaturated bond and an acid group, such as unsaturated carboxylic acid or its anhydride, unsaturated sulfonic acid, and unsaturated phosphonic acid. wait. Specific examples of preferred monomers include (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propynoic acid, cinnamic acid, α- Cyanocinnamic acid, maleic acid, anhydrous maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, anhydrous itaconic acid, citric acid Unsaturated carboxylic acids such as conic acid, anhydrous citraconic acid or their anhydrides; unsaturated carboxylic acids such as 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, p-styrenesulfonic acid, etc. Saturated sulfonic acid; vinylphosphonic acid, unsaturated phosphonic acid, etc. These single systems can be used alone or in combination of two or more. Among these, unsaturated carboxylic acid is preferred, and (meth)acrylic acid is preferred from the viewpoint of excellent alkali developability and ease of acquisition.

In the present invention, by including the structural unit (b) having an acid group in the copolymer (A), the alkali developability of the copolymer (A) is greatly improved when the copolymer (A) is used as a photosensitive material.

The proportion of the acid group-containing constituent units (b) in the copolymer (A) is not particularly limited, and is preferably 1 to 60 mol%, more preferably 10 to 50 mol%, and most preferably 15 to 40 mol%. When the proportion of the acid group-containing constituent units (b) is 1 to 60 mol%, the speed of alkaline development can be appropriate, and a fine pattern can be formed.

<Constituent unit (c) having an epoxy group> The constituent unit (c) having an epoxy group contained in the copolymer (A) is a constituent unit derived from a monomer containing an epoxy group (however, it is excluding the aforementioned constituent unit (a) having a blocked isocyanate group and the aforementioned constituent unit (b) having an acid group). As the monomer for providing the constituent unit (c) having an epoxy group, there can be mentioned monomers having a polymerizable unsaturated bond and an epoxy group, for example, (meth)acrylate derivatives containing an epoxy group such as glycidyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-glycidylethyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3-glycidoxypropyl (meth)acrylate, glycidoxyphenyl (meth)acrylate, etc. Biologicals; (meth)acrylate derivatives of alicyclic carbon rings containing an epoxide group such as 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethoxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethoxy)propyl (meth)acrylate, etc.; vinyl ether compounds containing an epoxy group; allyl ether compounds containing an epoxy group, etc. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of polymerizability and easy acquisition, epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-glycidylethyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3-glycidoxypropyl (meth)acrylate, and glycidoxyphenyl (meth)acrylate are preferred, and glycidyl (meth)acrylate is more preferred.

In the present invention, by including the structural unit (c) having an epoxy group in the copolymer (A), the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

The proportion of the constituent unit (c) having an epoxy group contained in the copolymer (A) is not particularly limited, but is preferably 1 to 60 mol %, more preferably 5 to 50 mol %, and most preferably 10 to 10 mol %. 40 mol%. When the proportion of the structural unit (c) having an epoxy group is 1 to 60 mol%, the solvent resistance of the hardened coating film and the storage stability of the copolymer (A) will coexist.

In the copolymer (A), the molar ratio of the structural unit (a) having a blocked isocyanate group to the structural unit (c) having an epoxy group may be, for example, 1:99 to 99:1. From the hard coating From the viewpoint of the solvent resistance of the film and the storage stability of the copolymer (A), 5:95~85:15 is preferred, and 10:90~75:25 is preferred.

<Constituent unit (d) having a hydroxyl group> The copolymer (A) may further contain: a constituent unit (d) having a hydroxyl group. The constituent unit (d) having a hydroxyl group contained in the copolymer (A) is a constituent unit derived from a monomer containing a hydroxyl group (however, it is excluding the aforementioned constituent unit (a) having a blocked isocyanate group, the aforementioned constituent unit (b) having an acid group, and the aforementioned constituent unit (c) having an epoxy group). Examples of the monomer that imparts the constituent unit (d) having a hydroxyl group include monomers having a polymerizable unsaturated bond and a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate. These monomers may be used alone or in combination of two or more. Among these, from the viewpoint of polymerizability, (meth)acrylate derivatives containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate are preferred, and 2-hydroxyethyl (meth)acrylate is more preferred.

In the present invention, the constituent unit (d) having a hydroxyl group is not essential, but by including the constituent unit (d) having a hydroxyl group in the copolymer (A), the solvent resistance of the copolymer (A) when used as a photosensitive material is greatly improved.

The proportion of the acid group-containing constituent units (d) in the copolymer (A) is not particularly limited, but is preferably greater than 0 mol% to 50 mol%, more preferably greater than 0 mol% to 40 mol%, and most preferably greater than 0 mol% to 30 mol%. When the proportion of the hydroxyl group-containing constituent units (d) is greater than 0 mol% to 50 mol%, the solvent resistance of the cured coating and the storage stability of the copolymer (A) are achieved simultaneously.

<Other constituent units (e)> In the present invention, as constituent units contained in the copolymer (A), in addition to the constituent units (a) having a blocked isocyanate group, the constituent units (b) having an acid group, the constituent units (c) having an epoxy group, and the constituent units (d) having a hydroxyl group, other constituent units (e) copolymerizable with these constituent units may also be contained (however, the constituent units are excluding the aforementioned constituent units (a) having a blocked isocyanate group, the aforementioned constituent units (b) having an acid group, the aforementioned constituent units (c) having an epoxy group, and the constituent units (d) having a hydroxyl group). As specific examples of the monomer to which the other constituent unit (e) is assigned, there can be cited aromatic vinyl compounds such as styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene, etc.; norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ] dec-8-ene, tricyclo[5.2.1.0 ^2,6 ] dec-3-ene, tricyclo[4.4.0.1 ^2,5 ] undec-3-ene, tricyclo[6.2.1.0 ^1,8 ] undec-9-ene, tricyclo[6.2.1.0 ^1,8 ] undec-4-ene, tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,12 ] dodeca-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] pentadeca-4-ene, pentacyclo[7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13 ] cycloolefins with a norbornene structure such as pentadecene-3-ene; dienes such as butadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate Ester, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methyl cyclohexyl (meth)acrylate, ethyl cyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, (Meth)acrylates such as fluoro-n-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, isopropyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, etc.; (meth)acrylate amide, N,N-dimethyl (meth)acrylate amide, N,N-(meth)acrylate (Meth)acrylic acid amides such as (meth)diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenamide, etc.; vinyl compounds such as (meth)acrylic acid amide benzene, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene, etc.; unsaturated dicarboxylic acid diesters such as diethyl liconate, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc.; monomaleimide such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc. Among these, (meth)acrylate is preferred, and methyl (meth)acrylate and dicyclopentyl (meth)acrylate are particularly preferred. These monomers may be used alone or in combination of two or more.

The proportion of other structural units (e) contained in the copolymer (A) is not particularly limited. It is preferably more than 0 mol% to 80 mol%, more preferably 5 to 70 mol%, and most preferably 10 to 10 mol%. 60 mol%. In the present invention, other structural units (e) are not essential, but by including other structural units (e) in the copolymer (A), solvent resistance and coating film characteristics can be appropriately improved. .

＜Production method of copolymer (A)＞ There is no particular ratio of the blocked isocyanato group-containing monomer (a0), the acid group-containing monomer (b0), and the epoxy group-containing monomer (c0) used in the production of the copolymer (A). Limits are preferably (a0) 1~60 mol%, (b0) 5~65 mol% and (c0) 5~65 mol%, preferably (a0) 5~50 mol%, (b0) ) 15~55 mol% and (c0) 15~55 mol%, the best ones are (a0) 10~40 mol%, (b0) 25~45 mol% and (c0) 25~45 mol% . When the copolymer (A) further contains a structural unit (d) having a hydroxyl group and another structural unit (e), the blocked isocyanate group-containing monomer (a0) used when producing the copolymer (A) , the proportion of acid group-containing monomer (b0), epoxy group-containing monomer (c0), hydroxyl-containing monomer (d0) and other monomers (e0) is (a0) 1~40 mol% , (b0) 1~60 mol%, (c0) 1~70 mol%, (d0) exceeding 0 mol%~50 mol% and (e0) exceeding 0 mol%~80 mol% is preferred. , preferably (a0) 2~30 mol%, (b0) 10~55 mol%, (c0) 10~60 mol%, (d0) more than 0 mol%~30 mol% and (e0) ) 5~60 mol%, optimally (a0) 3~20 mol%, (b0) 20~50 mol%, (c0) 20~40 mol%, (d0) more than 0 mol%~ 20 mol% and (e0) 20~40 mol%.

The copolymerization reaction of the monomer containing a blocked isocyanate group (a0), the monomer containing an acid group (b0), the monomer containing an epoxy group (c0), the monomer containing a hydroxyl group (d0) and other monomers (e0) can be carried out according to a free radical polymerization method known in the art in the presence or absence of a polymerization solvent. For example, after dissolving these monomers in a desired solvent, a polymerization initiator is added to the solution, and the polymerization reaction is carried out at 50-100° C. for 1-20 hours. At this time, when the polymerization reaction is carried out at a temperature at which the blocked isocyanate group of the monomer (a0) containing a blocked isocyanate group dissociates, the isocyanate group generated by the dissociation of the blocked isocyanate group reacts with the acid group to produce a gel. Therefore, it is preferred to carry out the polymerization at a temperature lower than the dissociation temperature of the blocked isocyanate group, preferably at a temperature lower than the dissociation temperature of the blocked isocyanate group by about 20 to 50°C.

The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inert to the reaction. Examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and diethylene glycol monomethyl ether. ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol mono Ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether and other (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl Other ethers such as methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate. , ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyethyl acetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-Methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, acetic acid i -Propyl ester, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyrate - Esters of propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-ketobutyrate, etc. Aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.; Diethylene glycol, etc. These solvents can be used alone or in combination of two or more.

Among these solvents, ether solvents are preferred, with propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether and ethylene glycol monomethyl ether being more preferred.

The amount of the solvent used in the copolymerization reaction is not particularly limited. When the total amount of the monomers input is set to 100 parts by mass, it is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass. In particular, by making the amount of the solvent less than 1,000 parts by mass, the molecular weight reduction of the copolymer (A) due to chain transfer can be suppressed, and the viscosity of the copolymer (A) can be controlled within an appropriate range. In addition, by making the amount of the solvent more than 30 parts by mass, abnormal polymerization reaction can be prevented, the polymerization reaction can be carried out stably, and at the same time, coloring or gelling of the copolymer (A) can be prevented.

In addition, the polymerization initiator that can be used in the copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, peroxybenzylidene, t-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more. The amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers.

The weight average molecular weight of the copolymer (A) in terms of polystyrene is not particularly limited. By the above production method, the copolymer (A) can be obtained with a weight average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 40,000. ). When the weight average molecular weight of the copolymer (A) is 1,000 or more, it becomes less likely to cause color pattern defects after alkali development when used as a photosensitive resin composition. On the other hand, when the weight average molecular weight of the copolymer (A) is 50,000 or less, the development time becomes appropriate and practicality can be ensured.

In addition, the acid value (JIS K6901 5.3) of the copolymer (A) can be appropriately selected. When blended into a photosensitive resin composition, it is preferably 20 to 300 KOHmg/g, and more preferably 30 to 200 KOHmg/g. Scope. When the acid value of the copolymer (A) is 20 KOHmg/g or more, the alkali developability when used as a photosensitive resin composition becomes good. On the other hand, when the acid value of the copolymer (A) is 300 KOHmg/g or less, the exposed portion (photohardened portion) of the copolymer is less likely to dissolve in the alkali developer, so that the pattern shape becomes good.

Furthermore, the epoxy equivalent of the copolymer (A) is not particularly limited, and is preferably in the range of 200 to 2,000 g/mol, more preferably 300 to 1500 g/mol, and most preferably 480 to 900 g/mol. When the epoxy equivalent of the copolymer (A) is 200 g/mol or more, the stability becomes good. On the other hand, if the epoxy equivalent is below 2,000 g/mol, the solvent resistance can be fully ensured. Moreover, the epoxy equivalent refers to the mass of the polymer per 1 mol of epoxy groups of the polymer, and can be obtained by dividing the mass of the polymer by the amount of epoxy groups of the polymer (g/mol). In the present invention, the epoxy equivalent is a theoretical value calculated from the amount of raw materials used to introduce epoxy groups.

The copolymer (A) of the present invention contains blocked isocyanate groups in the molecule. The content of blocked isocyanate groups can be appropriately selected, and the blocked isocyanate group equivalent is usually selected in the range of 400 to 6,000, preferably 1,000 to 5,000. The blocked isocyanate group equivalent is the mass of the polymer relative to 1 mol of blocked isocyanate groups contained in the polymer, and can be obtained by dividing the mass of the polymer by the molar number of blocked isocyanate groups contained in the polymer (g/mol). In the present invention, the blocked isocyanate group equivalent is a theoretical value calculated from the input amount of the monomer containing the blocked isocyanate group.

＜Polymer composition＞ In the present invention, there is provided a polymer composition including the above-mentioned copolymer (A) and at least one of a solvent (B) and a reactive diluent (C). The solvent (B) is not particularly limited as long as it is an inert solvent that does not react with the copolymer (A). The solvent (B) can be used in the same category as the solvent used when producing the copolymer (A). From the viewpoint of preventing abnormal polymerization and allowing the polymerization reaction to proceed stably, the solvent (B) is preferably a hydroxyl-containing organic solvent such as propylene glycol monomethyl ether or diethylene glycol.

The polymer composition of the present invention can also be prepared by suitably mixing the copolymer (A) isolated from the polymerization system with a desired solvent (B). It is not necessary that the copolymer (A) is isolated from the polymerization system. The solvent contained at the end of the copolymerization reaction can be used directly, and at this time, the desired solvent can be added if necessary. Moreover, the solvent contained in other components used when preparing a polymer composition can also be used as a component of solvent (B).

The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and a compound having a plurality of polymerizable functional groups is preferred. By using this reactive diluent (C) together with the copolymer (A), the viscosity can be adjusted, thereby improving the strength of the formed hardened material or the adhesion to the base material.

Examples of the monofunctional monomer used as the reactive diluent (C) include (meth)acrylamide, hydroxymethyl(meth)acrylamide, and methoxymethyl(meth)acrylamide. Amide, ethoxymethyl(meth)acrylamide, propoxymethyl(meth)acrylamide, butoxymethoxymethyl(meth)acrylamide, methyl(meth)acrylamide ) Acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloxy-2 -Hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, epoxypropyl(meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate esters such as methyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, phthalic acid derivatives such as hemi(meth)acrylate; benzene Aromatic vinyl compounds such as ethylene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; carboxylic acid esters such as vinyl acetate and vinyl propionate, etc. In addition, these single systems can be used alone, or two or more types can be used in combination.

Examples of the polyfunctional monomer used as the reactive diluent (C) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. Meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 6-Hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxypropyl(meth)acrylate, ethylene glycol Alcohol Diglycidyl Ether Di(meth)acrylate, Diethylene Glycol Diglycidyl Ether Di(meth)acrylate, Diglycidyl Phthalate Di(meth)acrylate, Propylene glycol Diglycidyl Ether Di(meth)acrylate, Triol triacrylate, glycerol polyepoxypropyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolyl diisocyanate), trimethylhexamethylene Reaction products of hydroxyethyl diisocyanate and hexamethylene diisocyanate with 2-hydroxyethyl (meth)acrylate, tri(meth)acrylate of ginseng (hydroxyethyl)isocyanurate, etc. Meth)acrylates; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, diallylphenylphosphonate, etc.; dicarboxylic acid esters such as divinyl adipate; Triallyl cyanurate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, polyvalent alcohol and N-hydroxymethyl(meth)acrylamide The condensate, etc. These single systems can be used alone or in combination of two or more.

The blending amounts of the copolymer (A), solvent (B) and reactive diluent (C) in the polymer composition can be appropriately adjusted according to the purpose of use. When the polymer composition contains a copolymer (A), a solvent (B), and a reactive diluent (C), it is usually 100 parts by mass relative to the total amount of the copolymer (A) and the reactive diluent (C). , the copolymer (A) is 10 to 90 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, the reactive diluent (C) is 10 to 90 parts by mass, and the copolymer (A) is 20 to 80 parts by mass , the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, and the copolymer (A) is preferably 30 to 75 parts by mass, and the solvent (B) is 100 to 100 parts by mass. 700 parts by mass, and 25 to 70 parts by mass of reactive diluent (C). If the blending amount is within this range, the polymer composition will have an appropriate viscosity and can be used not only for preparing the photosensitive resin composition for color filters described below, but also for various coatings, adhesives, Binders for printing ink, etc.

<Photosensitive resin composition> The present invention provides a photosensitive resin composition containing a copolymer (A), a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D). As the solvent (B) and the reactive diluent (C), the above-mentioned ones can be used.

The photopolymerization initiator (D) is not particularly limited, and examples thereof include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenone, 2,2-di Methoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl -1-[4-(Methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl ) Acetophenones such as butanone-1; anthraquinones such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, etc.; xanthones, Thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc.; acetophenone dimethyl ketal, benzyl Ketals such as dimethyl ketal; benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4 Benzophenones such as '-(t-butyldioxycarbonyl) benzophenone; acylphosphine oxides, etc. These photopolymerization initiators (D) can be used alone or in combination of two or more types.

<Photosensitive resin composition for color filter> The present invention provides a photosensitive resin composition for color filter containing a copolymer (A), a solvent (B), a reactive diluent (C), a photopolymerization initiator (D) and a coloring agent (E). As the solvent (B), the reactive diluent (C) and the photopolymerization initiator (D), the above-mentioned ones can be used.

The coloring agent (E) is not particularly limited as long as it is soluble or dispersed in the solvent (B), and examples thereof include dyes and pigments. As the dye, from the viewpoints of solubility in the solvent (B) or the alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., it is preferred to use an acid dye having an acid group such as carboxylic acid or sulfonic acid, a salt of an acid dye and a nitrogen compound, a sulfonamide of an acid dye, etc.

As examples of such dyes, there may be cited acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chromium violet K; acid fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow and their derivatives, etc. Among these, azo, xanthane, anthraquinone or phthalocyanine acid dyes are preferred. These dyes may be used alone or in combination of two or more depending on the color of the target pixel.

Examples of pigments include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; and red pigments such as C.I. Pigment Red 9, 97, 105, 122, 1 Red pigments such as C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc.; blue pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc.; green pigments such as C.I. Pigment Green 7, 36, 58, 59, etc.; brown pigments such as C.I. Pigment Brown 23, 25, etc.; black pigments such as C.I. Pigment Black 1, 7, carbon black, titanium black, ferric oxide, etc.

These colorants (E) can be used individually or in combination of two or more types according to the color of the target pixel. Furthermore, depending on the color of the target pixel, the above-mentioned dyes and pigments can also be used in combination.

When a pigment is used as a coloring agent (E), from the viewpoint of improving the dispersibility of the pigment, a known dispersant may be mixed with the photosensitive resin composition. As a dispersant, it is preferred to use a polymer dispersant with excellent dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, arbutus aliphatic ester dispersants, aliphatic modified ester dispersants, etc. As such polymer dispersants, those commercially available under the trade names EFKA (manufactured by EFKA chemicals BV (EFKA)), Disperbyk (manufactured by BYK-Chemie), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (manufactured by Zeneca), etc. may also be used. The amount of dispersant to be added can be appropriately set according to the type of pigment etc. to be used.

The amount of copolymer (A), solvent (B), reactive diluent (C), photopolymerization initiator (D) and colorant (E) is 10 to 100 parts by mass of copolymer (A), 30 to 1,000 parts by mass of solvent (B), more than 0 to 90 parts by mass of reactive diluent (C), 0.1 to 30 parts by mass of photopolymerization initiator (D), and 3 to 80 parts by mass of colorant (E) relative to 100 parts by mass of the total amount of copolymer (A) and reactive diluent (C) in the photosensitive resin composition. The copolymer (A) is preferably 20-80 parts by weight, the solvent (B) is 50-800 parts by weight, the reactive diluent (C) is 20-80 parts by weight, the photopolymerization initiator (D) is 0.5-20 parts by weight, and the colorant (E) is 5-70 parts by weight. More preferably, the copolymer (A) is 30-75 parts by weight, the solvent (B) is 100-700 parts by weight, the reactive diluent (C) is 25-70 parts by weight, the photopolymerization initiator (D) is 1-15 parts by weight, and the colorant (E) is 10-60 parts by weight. If the compounding amount is within this range, a photosensitive resin composition with appropriate viscosity is obtained. Even in the case of a photosensitive resin composition that does not contain a colorant (E), the amounts of the copolymer (A), the solvent (B), the reactive diluent (C) and the photopolymerization initiator (D) can be within the above numerical ranges.

In addition to the above-mentioned components, the polymer composition and photosensitive resin composition of the present invention may also be mixed with known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors in order to impart the specified properties. The amount of such additives is not particularly limited as long as it is within the range that does not hinder the effect of the present invention.

The photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components using a known mixing device. Alternatively, the photosensitive resin composition can be prepared by pre-preparing a polymer composition comprising a copolymer (A) and a solvent (B), and then mixing the reactive diluent (C), a photopolymerization initiator (D) and a coloring agent (E).

The photosensitive resin composition obtained by the above operation is suitable as a resist because it has alkaline developing properties. The curing of the photosensitive resin composition is preferably carried out at a baking temperature below 250°C. Since the copolymer (A) of the present invention has excellent curing properties at low temperatures, the baking temperature can be lowered compared to previous materials. When a pigment is used as a colorant (E) in the photosensitive resin composition, sufficient curing properties can be obtained even if the baking temperature is below 160°C. The photosensitive resin composition of the present invention is more advantageous in terms of energy consumption because the cross-linking reaction can still proceed sufficiently even if the baking temperature is lowered. Furthermore, it becomes possible to use even a colorant (E) or substrate with poor heat resistance, and it becomes possible to obtain the characteristics of the colorant itself and be applied to various substrates. Based on this view, the baking temperature is preferably set to below 210°C, preferably below 180°C, and optimally below 160°C. The lower limit of the baking temperature does not necessarily need to be the same depending on the type of blocked isocyanate groups contained in the copolymer (A), but it must be above the dissociation temperature of the blocked isocyanate groups, usually above 80°C, preferably above 90°C, and preferably above 100°C. When the baking temperature becomes too low, it becomes difficult to fully improve the solvent resistance of the coating. In addition, the baking time can be appropriately selected, usually 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

The photosensitive resin composition of the present invention is suitable as various resists, and is particularly suitable as a resist used for manufacturing color filters assembled in organic EL displays (for black PDL), liquid crystal display devices, CCD or CMOS solid-state imaging devices, etc. In addition, the photosensitive resin composition of the present invention can also be used in various coatings, adhesives, adhesives for printing inks, etc. because it can provide a cured coating film with excellent solvent resistance and low-temperature curing characteristics.

The photosensitive resin composition of the present invention can form a colored pattern with good developing properties and storage stability, and even if the baking temperature during pattern formation is reduced, the solvent resistance is still excellent, so it is extremely useful as a photosensitive material for color filters. In addition, the photosensitive resin composition of the present invention is hardened at a low temperature, so it can contribute to the development of flexible displays, reduce energy consumption in the manufacturing process, and alleviate the restrictions on the coloring agents used.

＜Color filter＞ Next, a color filter having a colored pattern composed of a cured product of the photosensitive resin composition of the present invention will be described. The color filter of the present invention has a colored pattern formed using the above-mentioned photosensitive resin composition. A color filter is usually composed of a substrate, RGB pixels formed on it, a black matrix formed on the boundaries of individual pixels, and a protective film formed on the pixels and the black matrix. In this structure, except that the pixels and the black matrix (colored pattern) are formed using the above-mentioned photosensitive resin composition, the other structures can be all known ones.

Next, an implementation form of a method for manufacturing a color filter is described. First, a coloring pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamide imide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, etc. can be appropriately used.

The coloring pattern can be formed by photolithography. Specifically, after the above-mentioned photosensitive resin composition is applied on the substrate to form a coating film, the coating film is exposed through a photomask of a predetermined pattern to photoharden the exposed portion. Afterwards, the unexposed portion is developed with an alkaline aqueous solution and baked to form a predetermined coloring pattern.

There is no particular limitation on the method of applying the photosensitive resin composition, and methods such as screen printing, roll coating, curtain coating, spray coating, and rotary coating can be used. Furthermore, after applying the photosensitive resin composition, the solvent (B) can be volatilized by heating using a circulating oven, infrared heater, heating plate, etc., if necessary. The heating conditions are not particularly limited and can be appropriately set according to the type of photosensitive resin composition used. Generally, heating at a temperature of 50°C to 120°C for 30 seconds to 30 minutes is sufficient.

Next, the formed coating is partially exposed to active energy rays such as ultraviolet rays, excimer laser light, etc. through a negative mask. The amount of energy irradiated can be appropriately selected according to the composition of the photosensitive resin composition, for example, 30 to 2000 mJ/ ^cm2 is preferred. There is no particular limitation on the light source used for exposure, and low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halogen lamps, etc. can be used.

The alkali aqueous solution used for development is not particularly limited, and aqueous solutions such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; ethylamine, diethylamine, and dimethylethanolamine can be used. Aqueous solutions of amine compounds such as; tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β -Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N- Aqueous solutions of β-methoxyethylaniline and p-phenylenediamine compounds such as sulfate, hydrochloride or p-toluenesulfonate. Furthermore, defoaming agents or surfactants can also be added to these aqueous solutions as necessary. Moreover, it is preferable to wash with water and dry after the above-mentioned development with an alkali aqueous solution.

There is no particular limitation on the baking conditions, and heat treatment can be applied according to the type of photosensitive resin composition used. If the baking temperature of the previous photosensitive resin composition becomes below 200°C, the solvent resistance of the colored pattern will be insufficient, but the photosensitive resin composition of the present invention can still form a colored pattern that exhibits sufficient solvent resistance even when baked at a temperature below 120°C. Therefore, the baking temperature can be lowered, and the processing time can be shortened when baking at a high temperature, which becomes a great advantage in manufacturing. Based on this view, the baking temperature is usually set below 210°C, preferably below 160°C, and preferably below 120°C. The baking time is usually set to 10 minutes to 4 hours, and preferably 20 minutes to 2 hours.

By using the photosensitive resin composition for the black matrix and the photosensitive resin composition for the red, green, and blue pixels, and sequentially repeating the above-mentioned coating, exposure, development, and baking, it can be formed Color the pattern you want. Furthermore, the method of forming a colored pattern by photocuring has been described above. However, instead of the photopolymerization initiator (D), a photosensitive resin composition containing a curing accelerator and a known epoxy resin is used. , after coating by inkjet method, the desired color pattern can also be formed by heating. Secondly, a protective film is formed on the colored pattern (each pixel of RGB and black matrix). There is no particular limitation on the protective film, and any known method may be used to form the protective film.

The color filter produced by this operation is produced using a photosensitive resin composition that imparts a colored pattern that is excellent in sensitivity and developability, can be cured at low temperatures, and has excellent solvent resistance, so it has the following advantages: Excellent coloring pattern with few color changes.

＜Image display component＞ The image display element of the present invention is an image display element provided with the above-described color filter. Specific examples thereof include solid-state imaging elements such as liquid crystal display elements, organic EL display elements, CCD elements, or CMOS elements. The image display element of the present invention can be manufactured according to conventional methods except for using the above-mentioned color filter. For example, when manufacturing a liquid crystal display element, the above-mentioned color filter is formed on a substrate, and then electrodes, spacers, etc. are formed in sequence. Then, electrodes, etc. are formed on another substrate, the two are bonded together, a predetermined amount of liquid crystal is injected, and the sealing is performed. [Example]

Hereinafter, the present invention will be described in detail with reference to the examples, but the present invention is not limited to the examples. In addition, in the examples, parts and percentages are all based on mass unless otherwise specified. In addition, the measurement methods of acid value and weight average molecular weight are as follows. (1) Acid value: The acid value of the copolymer (A) measured in accordance with JIS K6901 5.3, and refers to the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the copolymer (A). (2) Weight average molecular weight (Mw) refers to the weight average molecular weight converted to standard polystyrene measured using gel permeation chromatography (GPC) under the following conditions. Column: Shodex (registered trademark) LF-804+LF-804 (Showa Denko Co., Ltd.) Column temperature: 40°C Sample: 0.2% tetrahydrofuran solution of copolymer Developing solvent: tetrahydrofuran Detector: Differential refractometer (Shodex RI-71S) (Showa Denko Co., Ltd.) Flow rate: 1 mL/min

[Example 1] After placing 257.3 g of diethylene glycol methyl ethyl ether into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, nitrogen substitution was performed while stirring, and the temperature was raised to 78°C. Next, 110.0g of dicyclopentyl methacrylate, 17.0g of epoxypropyl methacrylate, 28.4g of methacrylic acid and 12.1g of 2-[O-(1'-methyl methacrylate) A monomer mixture composed of propyleneamine)carboxylamino]ethyl ester (Karenz MOI-BM, manufactured by Showa Denko Co., Ltd., dissociation rate of blocked isocyanate group: 18 mass %), and 13.4 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator), add to 78.7g of diethylene glycol methyl ethyl ether and dissolve it, and add This was dropped from the dropping funnel into the flask. After completion of the dropping, the copolymerization reaction was performed by stirring at 78° C. for 3 hours to generate a copolymer, and the polymer composition of sample No. 1 (concentration of components other than the solvent: 40% by mass) was obtained. The weight average molecular weight of the copolymer in the obtained polymer composition is 7,500, and the acid value is 102.3KOHmg/g.

[Examples 2 to 12 and Comparative Examples 1 to 3] Except for using the raw materials listed in Table 1, a copolymerization reaction was performed under the same conditions as in Example 1 to obtain polymer compositions of sample Nos. 2 to 15 (concentration of components other than solvent: 40% by mass). The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Table 1. Incidentally, in Table 1, 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate is Karenz MOI-BP manufactured by Showa Denko Co., Ltd. and has a blocked isocyanate group. Dissociation rate: 70 mass%, malonate-2-[[[[[2-methyl-1-sideoxy-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 - Diethyl ester is Karenz MOI-DEM manufactured by Showa Denko Co., Ltd., dissociation rate of blocked isocyanate group: 90% by mass, benzoic acid-4-[[[[2-[(2-methyl-1 -Dissociation rate of blocked isocyanato group of pendant oxy-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester: 40 mass%, benzoic acid-2- Blocked isocyanate group of [[[[2-[(2-methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester Dissociation rate: 75% by mass, dissociation rate of blocked isocyanate group of 2-acrylic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl ester :28% by mass.

[Examples 13~24 and Comparative Examples 4~6] <Preparation of photosensitive resin composition (pigment type)> By adding 100 parts by mass of C.I Pigment Green 36 (colorant), 44.98 parts by mass of propylene glycol monomethyl ether acetate, and a dispersant (BYK-Chemie) into a stainless steel container filled with 200 parts by mass of zirconia beads with a diameter of 0.5 mm. 25 parts by mass of Disperbyk-161 (manufactured by Japan Co., Ltd.) were mixed and dispersed with a paint shaker for 2 hours to prepare a green pigment dispersion liquid. This green pigment dispersion was mixed with other compounding components shown in Table 3 (ie, polymer composition, reactive diluent, photopolymerization initiator, and solvent) to prepare a photosensitive resin composition. The blending amounts of individual components are shown in Table 3. In addition, the photosensitive resin compositions of Examples 13 to 24 were prepared using the polymer compositions of Examples 1 to 12 (sample Nos. 1 to 12), respectively, and the photosensitive resin compositions of Comparative Examples 4 to 6 were respectively prepared. The polymer compositions of Comparative Examples 1 to 3 (sample Nos. 13 to 15) were used for preparation. In addition, the amount of the polymer composition includes the solvent contained at the end of the copolymer reaction, and the amount of the solvent contained in each sample is also included in the solvent as the compounding component.

<Evaluation of Photosensitive Resin Composition> (1) Alkali Development The photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 were respectively applied on a 5 cm square glass substrate (alkali-free glass substrate) in a manner such that the thickness after exposure was 2.5 μm. The solvent was then evaporated by heating at 90°C for 3 minutes. Next, a predetermined pattern mask was set at a distance of 100 μm from the coated film, and the coated film was exposed through the mask (exposure amount: 150 mJ/cm ² ) to photoharden the exposed portion. Next, an aqueous solution containing 0.1 mass % sodium carbonate was sprayed at a temperature of 23°C and a pressure of 0.3 MPa to dissolve the unexposed portion and develop the image, and then the image was baked at 100°C for 20 minutes to form a prescribed pattern. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Co., Ltd. The evaluation criteria are as follows. ○: No residue ×: Residue The evaluation results of alkali developability are shown in Table 4.

(2) Evaluation of solvent resistance The photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 were rotationally coated on a 5 cm square glass substrate (alkali-free glass substrate) in a manner such that the thickness after baking was 2.5 μm, and then heated at 90°C for 3 minutes to evaporate the solvent. Next, the coated film was exposed to light with a wavelength of 365 nm, and after the exposed part was photohardened, it was placed in a dryer at a baking temperature of 100°C for 20 minutes to prepare a hardened coating. 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL glass bottle with a cap and allowed to stand at 80°C. The above-mentioned test piece with the hardened coating was immersed in it and allowed to stand at 80°C for 5 minutes. The color change (ΔE ^* ab) of the test piece before and after immersion in propylene glycol monomethyl ether acetate was measured using a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). The measurement results of ΔE ^* ab are shown in Table 4. If ΔE ^* ab is less than 1.5, it can be said that the solvent resistance is excellent.

(3) Evaluation of storage stability The copolymers of Examples 1 to 12 and Comparative Examples 1 to 3 were measured in equal amounts into a glass container, and aluminum foil was used to seal the mouth so that dust would not enter. Secondly, these samples were placed in a thermostat maintained at 23°C, and the weight average molecular weight (Mw) of the samples was measured after one month. The change rate of Mw after one month is shown in Table 5. If the change rate of Mw after one month is within 20%, it can be said that the storage stability of the copolymer is excellent.

From the results in Table 4, it is clear that the photosensitive resin compositions of Examples 13 to 24 using the polymer compositions of Samples No. 1 to 12 are good in both alkali developability and solvent resistance. In addition, since the storage stability of the copolymer is related to the storage stability of the photosensitive resin composition formulated therewith, from the results in Table 5, it can be seen that the photosensitive resin compositions of Examples 13 to 24 using the polymer compositions of Samples No. 1 to 12 are also good in storage stability. In contrast, the photosensitive resin compositions of Comparative Examples 4 to 6 using the polymer compositions of Sample Nos. 13 to 15 had good storage stability, but were insufficient in solvent resistance. Furthermore, the photosensitive resin composition of Comparative Example 6 also had insufficient alkali developability.

From the above results, it can be seen that the present invention can provide a photosensitive resin composition that has good developability and is excellent in both solvent resistance and storage stability. Furthermore, the present invention can provide a copolymer useful for preparing a photosensitive resin composition having the above characteristics.

Furthermore, this international application claims priority based on Japanese Patent Application No. 2017-150501 filed on August 3, 2017, and all the contents of the Japanese Patent Application are incorporated herein by reference.

Claims (18)

A photosensitive resin composition characterized by containing copolymer (A), solvent (B), reactive diluent (C) and photopolymerization initiator (D), wherein, It contains 10 to less than 100 parts by mass of the copolymer (A), 30 to 1,000 parts by mass of the solvent (B), based on 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). The aforementioned reactive diluent (C) exceeds 0 to 90 parts by mass, and the aforementioned photopolymerization initiator (D) exceeds 0.1 to 30 parts by mass, The aforementioned copolymer (A) contains: a structural unit (a) having a blocked isocyanate group, a structural unit (b) having an acid group, a structural unit (c) having an epoxy group, and a structural unit having a hydroxyl group ( d), The aforementioned copolymer (A) contains 1 to 40 mol% of the aforementioned structural unit (a) having a blocked isocyanate group, 1 to 60 mol% of the aforementioned structural unit (b) having an acid group, and the aforementioned structural unit (b) having an epoxy group. The constituent unit (c) of 1 to 70 mol%, and the aforementioned constituent unit (d) with hydroxyl group exceeds 0 mol% to 50 mol%, The aforementioned structural unit (a) having a blocked isocyanate group is a structural unit derived from a (meth)acrylate containing a blocked isocyanate group, and the aforementioned (meth)acrylate containing a blocked isocyanate group The dissociation rate of the blocked isocyanate group after heating at 100°C for 30 minutes is 5 to 99 mass%. The acid value of the aforementioned copolymer (A) is 20 to 300 KOHmg/g. The photosensitive resin composition of claim 1, wherein the blocking agent of the constituent unit (a) having a blocked isocyanate group is at least one selected from the group consisting of diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketone oxime, 2-hydroxybenzoic acid methyl ester, 4-hydroxybenzoic acid methyl ester and 3,5-hydroxyphenol. In the photosensitive resin composition of claim 1, the molar ratio of the aforementioned constituent unit (a) having a blocked isocyanate group to the aforementioned constituent unit (c) having an epoxy group in the aforementioned copolymer (A) is 10:90~75:25. The photosensitive resin composition of claim 1, wherein the copolymer (A) contains: 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate, 2-[O-(1'-methylpropyleneamino)carboxylamino]ethyl methacrylate, 2-[[[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonic acid, 4-[[[[2-[(2-methyl-1-oxo-2-propenyl)oxy]ethyl benzoate, The present invention further comprises a constituent unit (a) of at least one of the group consisting of 2-[[[[2-[(2-methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl benzoate and 2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl 2-acrylate, a constituent unit (b) derived from (meth)acrylic acid, a constituent unit (c) derived from epoxypropyl (meth)acrylate, and a constituent unit (d) derived from 2-hydroxyethyl methacrylate. The photosensitive resin composition of claim 1, wherein the copolymer (A) contains: a methyl methacrylate selected from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate, 2-[O-(1'-methylpropyleneamino)carboxylamino]ethyl methacrylate, 2-[[[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl malonic acid, 4-[[[[2-[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]oxy]methyl benzoate, 2-[[ The present invention comprises a constituent unit (a) derived from at least one of the group consisting of [[2-[(2-methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl ester, a constituent unit (b) derived from (meth)acrylic acid, a constituent unit (c) derived from glycidyl (meth)acrylate, a constituent unit (d) derived from 2-hydroxyethyl methacrylate, and a constituent unit (e) derived from at least one selected from the group consisting of dicyclopentyl (meth)acrylate and methyl (meth)acrylate. The photosensitive resin composition of claim 4, wherein the copolymer (A) contains: a composition derived from 2-[O-(1'-methylpropyleneamino)carboxylamino]ethyl methacrylate. Unit (a), structural unit (b) derived from (meth)acrylic acid, structural unit (c) derived from glycidyl (meth)acrylate, and 2-hydroxyethyl methacrylate Its constituent unit (d). A photosensitive resin composition as claimed in claim 4, wherein the copolymer (A) contains: a constituent unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate, a constituent unit (b) derived from (meth)acrylic acid, a constituent unit (c) derived from epoxypropyl (meth)acrylate, and a constituent unit (d) derived from 2-hydroxyethyl methacrylate. A photosensitive resin composition as claimed in claim 7, wherein the copolymer (A) contains: a constituent unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate, a constituent unit (b) derived from (meth)acrylic acid, a constituent unit (c) derived from glycidyl (meth)acrylate, a constituent unit (d) derived from 2-hydroxyethyl methacrylate, and a constituent unit (e) derived from dicyclopentyl (meth)acrylate. The photosensitive resin composition of claim 4, wherein the copolymer (A) contains: derived from malonic acid-2-[[[[[2-methyl-1-side oxy-2-propenyl]oxy The structural unit (a) of ethyl]amino]carbonyl]-1,3-diethyl ester, the structural unit (b) derived from (meth)acrylic acid, and the structural unit (b) derived from epoxypropyl (methyl) The structural unit (c) of acrylate, and the structural unit (d) derived from 2-hydroxyethyl methacrylate. The photosensitive resin composition of claim 1, wherein the copolymer (A) further comprises a constituent unit (e) other than the constituent units (a) to (d), and the copolymer (A) comprises the constituent unit (e) in an amount exceeding 0 mol% to 80 mol%. The photosensitive resin composition of claim 1, wherein the copolymer (A) further contains a constituent unit (e) other than the constituent units (a) to (d), and the copolymer (A) contains: 3 to 20 mol% of the constituent unit (a) having a blocked isocyanate group, 20 to 50 mol% of the constituent unit (b) having an acid group, 20 to 40 mol% of the constituent unit (c) having an epoxy group, more than 0 mol% to 20 mol% of the constituent unit (d) having a hydroxyl group, and 20 to 40 mol% of the constituent unit (e). The photosensitive resin composition of claim 1 further contains a colorant (E). The photosensitive resin composition of claim 12, wherein the colorant (E) is contained in an amount of 3 to 80 parts by weight relative to 100 parts by weight of the total amount of the copolymer (A) and the reactive diluent (C). The photosensitive resin composition of claim 12, wherein the solvent (B) comprises: a hydroxyl-containing organic solvent. The photosensitive resin composition according to claim 12, wherein the colorant (E) contains a pigment. A color filter characterized by having a colored pattern composed of a cured product of the photosensitive resin composition according to claim 12. An image display element is characterized by having a color filter as claimed in claim 16. A method for manufacturing a color filter, characterized by comprising: coating the photosensitive resin composition of claim 12 on a substrate, exposing it, alkali development, and baking at a temperature below 160°C to form a color pattern Type steps.