TWI836851B - 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 color filters containing the same, a color filter, an image display element having the same, and a method for manufacturing the color filter.

In recent years, from the viewpoint of saving resources or energy, photosensitive resins that can be hardened by active energy rays such as ultraviolet rays or electron rays are widely used in various fields such as coating, printing, paints, adhesives, etc. composition. Furthermore, 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 in solder resists, color filter resists, and the like. In addition, the characteristics required for curable photosensitive resin compositions are gradually becoming diversified and advanced. Among them, short-time curing properties that take into account productivity and low-temperature curing properties that suppress thermal damage to the components to which they are applied are also required. .

Color filters generally consist 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 boundaries of the pixels, and a It consists of pixels and a protective film on a black substrate. Color filters with such a structure are usually manufactured by sequentially forming a black matrix, pixels and protective film on a transparent substrate. Various methods have been proposed as methods for forming pixels and black matrices (hereinafter, pixels and black matrices will be referred to as "coloring patterns"). Among them, the pigment/dye dispersion method, which uses a photosensitive resin composition as a resist and repeatedly coats, exposes, develops, and bakes the photolithographic process, can impart excellent durability and eliminate pinholes, etc. Colored graphics with fewer defects have become the mainstream today.

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

[The problem that the invention wants to solve]

In recent years, flexible displays such as electronic paper have become increasingly popular. As substrates for such flexible displays, plastic substrates such as polyethylene terephthalate have been explored. These substrates have the property of stretching or shrinking during baking, so the baking step must be lowered in temperature. However, the degree achieved by Patent Document 1 is insufficient to meet the above requirements. In addition, although Patent Document 2 can improve low-temperature curing properties, the storage stability is low and it is difficult to put into practical use.

The present invention was completed in order to solve the above-mentioned problems, and its object is to provide a photosensitizer for color filters that has excellent developability and storage stability and can provide a color pattern with excellent solvent resistance even if it is cured at a low temperature. A resin composition and a copolymer useful for preparing the photosensitive resin composition. Furthermore, an object of the present invention is to provide a color filter having a color pattern excellent in solvent resistance, a manufacturing method thereof, and an image display element provided with the color filter. [Means used to solve problems]

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 color filters, characterized by containing: the copolymer (A) of any one of [1] to [16], a solvent (B), a reactive diluent (C), Photopolymerization initiator (D) and coloring agent (E). [20] The photosensitive resin composition for color filters according to [19], which contains 10 parts by mass of the copolymer (A) based on 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). ~100 parts by mass, 30~1,000 parts by mass of the aforementioned solvent (B), 0~90 parts by mass of the aforementioned reactive diluent (C), 0.1~30 parts by mass of the aforementioned photopolymerization initiator (D), and the aforementioned coloring Agent (E) 3~80 parts by mass. [21] The photosensitive resin composition for color filters according to [19] or [20], wherein the aforementioned solvent (B) includes: a hydroxyl-containing organic solvent. [22] The photosensitive resin composition for color filters according to any one of [19] to [21], wherein the colorant (E) contains a pigment.

[23] A color filter characterized by having a colored pattern formed by a cured product of a photosensitive resin composition for a color filter as described in 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, it is possible to provide a photosensitive resin composition for color filters that has good developability and storage stability and provides a colored pattern with excellent solvent resistance even when cured at a low temperature, and to prepare the photosensitive resin composition. Useful copolymers. Furthermore, according to the present invention, it is possible to provide a color filter having a color pattern excellent in solvent resistance, a manufacturing method thereof, and an image display element provided with the color filter.

＜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.

<Constituent unit (a) having a blocked isocyanate group> The constituent unit (a) having a blocked isocyanate group contained in the copolymer (A) is a constituent unit derived from a monomer containing a blocked isocyanate group. Examples of such monomers include monomers having an ethylenic unsaturated bond and a blocked isocyanate group, and examples thereof include compounds obtained by blocking an isocyanate group in an isocyanate compound having a vinyl group, a (meth)acryloyloxy group, etc. in the molecule with a blocking agent. The reaction between the isocyanate compound and the blocking agent can be carried out in the presence or absence of a solvent. In the case of using a solvent, it is necessary to use a solvent that is inert to the isocyanate group. During the capping reaction, organic metal salts such as tin, zinc, and lead, tertiary amines, etc. can be used as catalysts. The reaction can generally be carried out at -20 to 150°C, preferably at 0 to 100°C. As an example of the above-mentioned isocyanate compound, the compound shown in the following formula (1) can be cited.

In the above formula (1), R ¹ represents a hydrogen atom or a methyl group, and R ² represents -CO-, -COOR ³ - (here, R ³ is an alkylene group having 1 to 6 carbon atoms) or -COO-R ⁴ O-CONH-R ⁵ -(Here, R ⁴ is an alkylene group having 2 to 6 carbon atoms, and R ⁵ is an alkylene group having 2 to 12 carbon atoms or an alkylene group having 6 carbon atoms which may have a substituent. 12 aryl). R ² is preferably -COOR ³ -, and here R ³ 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.

Furthermore, in this specification, the term "(meth)acrylate" means that it may be either acrylate or methacrylate, and the term "(meth)acrylic acid" means that it may be either acrylic acid or methacrylic acid.

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 the highly reactive isocyanate groups, but the blocked isocyanate groups will dissociate and regenerate isocyanate groups by heating. In the present invention, the isocyanate groups react with the reactive functional groups contained in the copolymer (A) or the reactive diluent (C), i.e., acid groups or hydroxyl groups, amine groups, etc. as desired, to form a hardened material with a high crosslinking density.

From the viewpoint of low temperature curing property or storage stability of the photosensitive resin composition for color filters described later, it is preferred to use a (meth)acrylate containing a blocked isocyanate group as the monomer for imparting the constituent unit (a) having a blocked isocyanate group. It is preferred to use a (meth)acrylate containing a blocked isocyanate group whose dissociation rate after heat treatment at 100°C for 30 minutes is 5 to 99% by mass, more preferably 8 to 97% by mass, and most preferably 10 to 95% by mass. Furthermore, the dissociation rate of the blocked isocyanate group of the blocked isocyanate group-containing (meth)acrylate is measured by HPLC analysis to determine the mass reduction ratio of the blocked isocyanate group-containing (meth)acrylate after preparing a 20 mass % n-octanol solution of the blocked isocyanate group-containing (meth)acrylate, adding 1 mass % dibutyltin laurate and 3 mass % phenothiazine (polymerization inhibitor) to the solution, and heating the solution at 100°C for 30 minutes. When the blocked isocyanate group-containing (meth)acrylate having a dissociation rate within the above range is used, the stability of the copolymer during synthesis can be fully ensured, the baking temperature during the preparation of the hardened coating can be fully reduced, and the solvent resistance of the hardened coating can be fully ensured. As the blocking agent of the (meth)acrylate containing a blocked isocyanate group having such a dissociation rate, there can be mentioned diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, 3,5-hydroxyphenol, γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol and diisopropylamine. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate and 3,5-hydroxyphenol are preferred from the viewpoint of low temperature curability.

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 blocked isocyanate group-containing (meth)acrylate include Karenz (registered trademark) MOI-DEM (methacryloxyethyl isocyanate and Reaction product of diethyl malonate, manufactured by Showa Denko Co., Ltd., dissociation temperature of blocked isocyanate group: 90°C, dissociation rate: 90 mass %), Karenz MOI represented by the following formula (3) -BP (reaction product of methacryloxyethyl isocyanate and 3,5-dimethylpyrazole, manufactured by Showa Denko Co., Ltd., dissociation temperature of blocked isocyanate group: 110°C, dissociation rate: 70% by mass), Karenz MOI-BM (reaction product of methacryloxyethyl isocyanate and methyl ethyl ketoxime) represented by the following formula (4), manufactured by Showa Denko Co., Ltd., blocked iso Dissociation temperature of cyanate group: 130°C, dissociation rate: 18% by mass), general methacrylates and corresponding acrylates, etc. These blocked isocyanato group-containing (meth)acrylates 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 constituent unit (c) having an epoxy 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 constituent units (c) having an epoxy group contained in the copolymer (A) is not particularly limited, and is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and most preferably 10 to 40 mol%. When the proportion of the constituent units (c) having an epoxy group is 1 to 60 mol%, the solvent resistance of the cured coating and the storage stability of the copolymer (A) can be achieved simultaneously.

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 structural unit (d) having an acid group contained in the copolymer (A) is not particularly limited, but it is preferably more than 0 mol% to 50 mol%, more preferably more than 0 mol% to 40 mol%. %, the best is over 0 mol% to 30 mol%. When the ratio of the structural unit (d) having a hydroxyl group exceeds 0 mol% to 50 mol%, the solvent resistance of the cured coating film and the storage stability of the copolymer (A) can coexist.

<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%.

Monomers containing blocked isocyanato groups (a0), monomers containing acid groups (b0), monomers containing epoxy groups (c0), monomers containing hydroxyl groups (d0) and other monomers (e0) The copolymerization reaction can be carried out in the presence or absence of a polymerization solvent according to the known free radical polymerization method in this technical field. For example, after dissolving these monomers in a desired solvent, a polymerization initiator is added to the solution, and a polymerization reaction is carried out at 50 to 100° C. for 1 to 20 hours. At this time, when the polymerization reaction is carried out at a temperature at which the blocked isocyanate group of the blocked isocyanate group-containing monomer (a0) is dissociated, the isocyanate generated due to the dissociation of the blocked isocyanate group The acid group will react with the acid group to produce a gel, so the temperature should be lower than the dissociation temperature of the blocked isocyanate group, preferably 20 to 50°C lower than the dissociation temperature of the blocked isocyanate group. It is better to carry out polymerization at high temperature.

The solvent that can be used in the copolymerization reaction is not particularly limited as long as it is inert to the reaction, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl 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 ether acetates such as 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; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones; 2-hydroxy Methyl propionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate Esters such as methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, ethyl acetylacetate, 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 may 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 solvent used in the copolymerization reaction is not particularly limited. When the total input amount of monomers is 100 parts by mass, it is generally 30 to 1,000 parts by mass, and preferably 50 to 800 parts by mass. In particular, by setting the amount of the solvent to 1,000 parts by mass or less, the decrease in the molecular weight 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. Furthermore, by setting the amount of the solvent to 30 parts by mass or more, abnormal polymerization reaction can be prevented, the polymerization reaction can proceed stably, and at the same time, coloring or gelation of the copolymer (A) can be prevented.

In addition, the polymerization initiator that can be used in this copolymerization reaction is not particularly limited, and examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, peracidized benzyl group, and t-butyl group. Peroxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more types. When the total input amount of monomers is set to 100 parts by mass, the usage amount of the polymerization initiator is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass.

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> The present invention provides a polymer composition comprising 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), and can be the same range of solvents as those used in the production of the copolymer (A). From the perspective 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 and 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 preferably a compound having multiple polymerizable functional groups. By using such a reactive diluent (C) together with the copolymer (A), the viscosity can be adjusted, so that the strength of the formed hardened material or the adhesion to the substrate can be improved.

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 multifunctional monomer used as the reactive diluent (C) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trihydroxymethylpropane tri(meth)acrylate, and the like. Acids, glycerol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ether di(meth)acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolyl diisocyanate), trimethyl hexamethylene diisocyanate and hexamethylene diisocyanate, etc. and 2-hydroxyethyl (meth)acrylate. (Meth)acrylates such as reactants of acrylates, tri(meth)acrylate of tris(hydroxyethyl)isocyanurate, etc.; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, diallylphenylphosphonate, etc.; dicarboxylic acid esters such as divinyl adipate, etc.; triallylcyanurate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, condensates of polyvalent alcohols and N-hydroxymethyl(meth)acrylamide, etc. These monomers may be used alone or in combination of two or more.

The amounts of the copolymer (A), the solvent (B) and the reactive diluent (C) in the polymer composition can be appropriately adjusted according to the intended use. When the polymer composition comprises a copolymer (A), a solvent (B) and a reactive diluent (C), the copolymer (A) is usually present in an amount of 10 to 90 parts by mass, the solvent (B) is present in an amount of 30 to 1,000 parts by mass, and the reactive diluent (C) is present in an amount of 10 to 90 parts by mass, preferably 20 to 80 parts by mass of the copolymer (A), 50 to 800 parts by mass of the solvent (B), and 20 to 80 parts by mass of the reactive diluent (C), more preferably 30 to 75 parts by mass of the copolymer (A), 100 to 700 parts by mass of the solvent (B), and 25 to 70 parts by mass of the reactive diluent (C), relative to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). When the amount is within this range, a polymer composition having an appropriate viscosity is obtained, and in addition to being used for preparing the photosensitive resin composition for color filters described later, it can also be used for various coatings, adhesives, adhesives for printing inks, and the like.

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

The coloring agent (E) is not particularly limited as long as it can be dissolved or dispersed in the solvent (B), and examples thereof include dyes and pigments. As the dye, those having acidity such as carboxylic acid or sulfonic acid are used from the viewpoint of solubility in the solvent (B) or alkali developing solution, interaction with other components in the photosensitive resin composition, heat resistance, etc. Base acid dyes, salts of acid dyes and nitrogen compounds, sulfonamides of acid dyes, etc. are preferred.

Examples of such dyes include 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 magenta; 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; edible yellow and their derivatives, etc. Among these, acid dyes of azo series, xanthene series, anthraquinone series or phthalocyanine series are preferred. These dyes can be used individually, 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 using a pigment as the colorant (E), a known dispersant may be blended with the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As a dispersant, it is preferable to use a polymer dispersant that has excellent dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, Rowandan aliphatic ester dispersants, aliphatic modified ester dispersants, etc. As such polymer dispersants, for example, those with the trade names EFKA (manufactured by EFKA chemicals BV (EFKA) Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), Disparlon (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (Zeneca Co., Ltd.) can also be used. (manufactured by) and other commercially available places. The amount of the dispersant can be appropriately set according to the type of pigment used.

The blending amounts of the copolymer (A), solvent (B), reactive diluent (C), photopolymerization initiator (D) and colorant (E) are relative to the copolymer (A) in the photosensitive resin composition ) and the reactive diluent (C) are 100 parts by mass, the copolymer (A) is 10 to 100 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, and the reactive diluent (C) is more than 0 to 90 parts by mass, the photopolymerization initiator (D) is 0.1 to 30 parts by mass, the colorant (E) is 3 to 80 parts by mass, the copolymer (A) is 20 to 80 parts by mass, and the solvent ( B) is 50 to 800 parts by mass, reactive diluent (C) is 20 to 80 parts by mass, photopolymerization initiator (D) is 0.5 to 20 parts by mass, and colorant (E) is 5 to 70 parts by mass. Better, preferably the copolymer (A) is 30 to 75 parts by mass, the solvent (B) is 100 to 700 parts by mass, the reactive diluent (C) is 25 to 70 parts by mass, and the photopolymerization initiator (D) The amount is 1 to 15 parts by mass, and the colorant (E) is 10 to 60 parts by mass. If the blending amount is within this range, a photosensitive resin composition with appropriate viscosity will be obtained. Moreover, even in the case of a photosensitive resin composition not containing the colorant (E), the blending of the copolymer (A), solvent (B), reactive diluent (C) and photopolymerization initiator (D) Quantities can also apply to the above numerical range.

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 has alkali developability, and therefore is suitable as a resist. For the curing of the photosensitive resin composition, it is appropriate to select a baking temperature within a range of 250°C or lower. Since the copolymer (A) of the present invention has excellent curing properties at low temperatures, it can be reduced compared to conventional materials. Baking temperature. When a pigment is used as the colorant (E) in the photosensitive resin composition, sufficient curability can be obtained even if the baking temperature is 160°C or lower. The photosensitive resin composition of the present invention is advantageous in terms of energy consumption because the crosslinking reaction can still fully proceed even if the baking temperature is lowered. Furthermore, it becomes possible to use a colorant (E) or a substrate with poor heat resistance, and it becomes possible to obtain the characteristics of the colorant itself, and it can be applied to various substrates. Based on this view, the baking temperature is preferably 210°C or lower, more preferably 180°C or lower, and most preferably 160°C or lower. The lower limit of the baking temperature does not necessarily need to be the same depending on the type of blocked isocyanate group contained in the copolymer (A), but it must be above the dissociation temperature of the blocked isocyanate group, usually above 80°C. , preferably above 90°C, preferably above 100°C. When the baking temperature becomes too low, it becomes difficult to fully improve the solvent resistance of the coating film. 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 a variety of resists, and is particularly suitable as a color filter for the production of solid-state imaging elements incorporated in organic EL displays (for black PDL), liquid crystal display devices, CCDs, CMOS, etc. Resistors used. In addition, the photosensitive resin composition of the present invention can be used in various coatings, adhesives, printing ink adhesives, etc., since it provides a cured coating film with excellent solvent resistance and low-temperature hardening properties.

The photosensitive resin composition of the present invention can form a colored pattern with excellent developability and storage stability, and has excellent solvent resistance even if the baking temperature during pattern formation is lowered, so it is extremely useful as a filter. Photosensitive material for color vessels. In addition, since the photosensitive resin composition of the present invention is accompanied by low-temperature hardening, it can also contribute to the development of flexible displays, reduction of energy consumption in the manufacturing process, and relaxation of restrictions on the colorants used.

<Color filter> Next, a color filter having a color pattern formed by a cured product of the photosensitive resin composition of the present invention is described. The color filter of the present invention has a color pattern formed using the above-mentioned photosensitive resin composition. The color filter is usually composed of a substrate, RGB pixels formed thereon, a black matrix formed on the boundary between individual pixels, and a protective film formed on the pixels and the black matrix. In this structure, except for the pixels and the black matrix (color pattern) formed using the above-mentioned photosensitive resin composition, the other structures can adopt 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 film is irradiated with active energy rays such as ultraviolet rays and excimer laser light through a negative mask to partially expose it. The amount of energy rays to be irradiated can be appropriately selected according to the composition of the photosensitive resin composition. For example, 30 to 2000 mJ/cm ² is preferred. The light source used for exposure is not particularly limited, and low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc. can be used.

The alkaline aqueous solution used for development is not particularly limited, and examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc.; aqueous solutions of p-phenylenediamine 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-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates thereof. Furthermore, defoamers or surfactants may be added to these aqueous solutions as necessary. Furthermore, it is preferred to wash with water and dry the film after developing with the alkaline aqueous solution as described above.

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 a photosensitive resin composition for a black matrix and a photosensitive resin composition for red, green, and blue pixels, and repeating the above-mentioned coating, exposure, development, and baking in sequence, a desired coloring pattern can be formed. Moreover, the above describes a method for forming a coloring pattern formed by photocuring, but if a photosensitive resin composition formed by combining a curing accelerator and a known epoxy resin is used instead of a photopolymerization initiator (D), the desired coloring pattern can also be formed by heating after coating by an inkjet method. Next, a protective film is formed on the coloring pattern (RGB pixels and black matrix). There is no particular limitation on the protective film, and it can be formed by using a known one.

The color filter manufactured by this operation is manufactured using a photosensitive resin composition that can impart a coloring pattern with excellent sensitivity and developability, can be cured at a low temperature, and has excellent solvent resistance, so it has an excellent coloring pattern with little color change.

＜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] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 257.3 g of diethylene glycol methyl ethyl ether was placed, nitrogen substitution was performed and stirring was performed at the same time, and the temperature was raised to 78°C. Next, a monomer mixture composed of 110.0 g of dicyclopentyl methacrylate, 17.0 g of glycidyl methacrylate, 28.4 g of methacrylic acid and 12.1 g of 2-[O-(1'-methylpropyleneamino)carboxylamino]ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko Co., Ltd., dissociation rate of blocked isocyanate group: 18% by mass) and 13.4 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) was added to 78.7 g of diethylene glycol methyl ethyl ether and dissolved, and the mixture was dropped into the flask from a dropping funnel. After the dripping was completed, the copolymerization reaction was carried out by stirring at 78°C for 3 hours to generate a copolymer and obtain the polymer composition of sample No. 1 (the concentration of components other than the solvent was 40% by mass). The weight average molecular weight of the copolymer in the obtained polymer composition was 7,500, and the acid value was 102.3 KOHmg/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 developability The photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 were spin-coated so that the thickness after exposure became 2.5 μm. After placing on a 5 cm square glass substrate (alkali-free glass substrate), the solvent was volatilized by heating at 90°C for 3 minutes. Next, a distance of 100 μm from the coating film is set to a prescribed pattern mask, and the coating film is exposed through this mask (exposure amount: 150 mJ/cm ² ), thereby photohardening the exposed part. Next, an aqueous solution containing 0.1% by mass sodium carbonate was sprayed at a temperature of 23°C and a pressure of 0.3MPa to dissolve the unexposed portion and developed, and then baked at 100°C for 20 minutes. 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-tech Co., Ltd. The basis for this evaluation is as follows. ○: No residue ×: There is residue. Table 4 shows the evaluation results of alkali developability.

(2) Evaluation of Solvent Resistance The photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 were spin-coated on a 5 cm square glass substrate (without After placing it on an alkali glass substrate, it was heated at 90°C for 3 minutes to evaporate the solvent. Next, the coating film is exposed by irradiating light with a wavelength of 365 nm, and after photohardening the exposed part, it is placed in a desiccator with a baking temperature of 100° C. for 20 minutes to form a hardened coating film. Put 200 mL of propylene glycol monomethyl ether acetate into a 500 mL capped glass bottle and let it stand at 80°C. After the above-mentioned test piece with the hardened coating film was immersed in it, it was left to stand for 5 minutes while maintaining it at 80°C. The color change (ΔE ^* ab) before and after the test piece was immersed 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 1.5 or less, 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 weighed in equal amounts and placed in glass containers, and the openings were sealed with aluminum foil to prevent dust from entering. Next, 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%, the storage stability of the copolymer can be considered to be 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 Sample Nos. 1 to 12 are both good in 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 containing it, it can be seen from the results in Table 5 that the implementation of the polymer composition using sample Nos. 1 to 12 is The photosensitive resin compositions of Examples 13 to 24 can also be said to be good in terms of storage stability. On the other hand, although the storage stability of the photosensitive resin compositions of Comparative Examples 4 to 6 using the polymer compositions of Sample Nos. 13 to 15 was good, the solvent resistance was not sufficient, and in Comparative Example 6 The photosensitive resin composition also has insufficient alkali developability.

From the above results, it can be seen that the present invention can provide a photosensitive resin composition having good developing properties, excellent solvent resistance and storage stability. In addition, the present invention can provide a copolymer used in 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 (17)

A photosensitive resin composition, characterized by containing a copolymer (A), a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D), wherein, relative to 100 parts by weight of the total amount of the copolymer (A) and the reactive diluent (C), the copolymer (A) contains 10 to less than 100 parts by weight, the solvent (B) contains 30 to 1,000 parts by weight, the reactive diluent (C) contains more than 0 to 90 parts by weight, and the photopolymerization initiator (D) contains 0.1 to 30 parts by weight, the copolymer (A) contains: 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, The copolymer (A) contains 1 to 40 mol% of the constituent unit (a) having a blocked isocyanate group, 1 to 60 mol% of the constituent unit (b) having an acid group, 1 to 70 mol% of the constituent unit (c) having an epoxy group, and more than 0 mol% to 50 mol% of the constituent unit (d) having a hydroxyl group. The constituent unit (a) having a blocked isocyanate group is 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-[[[[ At least one constituent unit of the group consisting of 2-[(2-methyl-1-oxo-2-propene-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl-1-oxo-2-propene-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl ester, the acid value of the above copolymer (A) is 20~300 KOHmg/g. In the photosensitive resin composition of claim 1, the molar ratio of the structural unit (a) having a blocked isocyanate group to the structural unit (c) having an epoxy group in the copolymer (A) is 10 :90~75:25. The photosensitive resin composition of claim 1, wherein the 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 composition derived from glycidyl (meth)acrylate Unit (c), and constituent unit (d) derived from 2-hydroxyethyl methacrylate. The photosensitive resin composition of claim 1, wherein the 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 composition derived from glycidyl (meth)acrylate Unit (c), constituent unit (d) derived from 2-hydroxyethyl methacrylate, and derived from the group consisting of dicyclopentyl (meth)acrylate and methyl (meth)acrylate At least one of the constituent units (e). The photosensitive resin composition of claim 3, 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). The photosensitive resin composition of claim 3, 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, and 2-hydroxyethyl methacrylate Its constituent unit (d). A photosensitive resin composition as claimed in claim 6, 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 3, 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 aforementioned copolymer (A) further contains the aforementioned constitutional unit (e) other than the aforementioned constitutional units (a) to (d), and the aforementioned copolymer (A) contains the aforementioned constitutional unit ( e) Exceeding 0 mol%~80 mol%. The photosensitive resin composition of claim 1, wherein the aforementioned copolymer (A) further contains a constituent unit (e) other than the aforementioned constituent units (a) to (d), and the aforementioned copolymer (A) contains: the aforementioned sealing unit The structural unit of terminal isocyanate group (a) is 3~20 mol%, the aforementioned structural unit having acid group (b) is 20~50 mol%, and the aforementioned structural unit having epoxy group (c) is 20~40 mol%. %, the aforementioned structural unit (d) having a hydroxyl group exceeds 0 to 20 mol% and the aforementioned structural unit (e) exceeds 20 to 40 mol%. The photosensitive resin composition of claim 1 further comprises a colorant (E). The photosensitive resin composition of claim 11, 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 11, wherein the solvent (B) includes: a hydroxyl-containing organic solvent. The photosensitive resin composition according to claim 11, 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 11. An image display element is characterized by having a color filter as claimed in claim 15. A method for manufacturing a color filter, characterized by comprising the steps of applying a photosensitive resin composition as claimed in claim 11 on a substrate, exposing it to light, alkaline developing it, and then baking it at a temperature below 160°C to form a colored pattern.