TWI760534B - Photosensitive resin composition, and method for producing same, color filter, and method for producing same, and image display element - Google Patents

Abstract

A photosensitive resin composition comprising: a copolymer (A) containing a structural unit (a) having a blocked isocyanato group and a structural unit (b) having an acid group, and a hydroxyl-containing organic solvent (B) , reactive diluent (C), and photopolymerization initiator (D).

Description

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

The present invention relates to a photosensitive resin composition and its manufacturing method, a color filter and its manufacturing method, and an image display element.

In recent years, photosensitive resins that can be cured by active energy rays such as ultraviolet rays or electron rays have been widely used in various fields of coating, printing, paint, and adhesives from the viewpoint of saving resources or energy. composition. Moreover, 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 for solder resists, color filter resists, and the like. In addition, the properties required for curable photosensitive resin compositions have gradually become more diversified and advanced, and among them, short-time curability in consideration of productivity and low-temperature curability for suppressing thermal damage to applied members are also required. .

Color filters are generally made of transparent substrates such as glass substrates, It consists of red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed on the boundary of the pixels, and a protective film formed on the pixels and the black matrix. A color filter with such a structure is usually manufactured by sequentially forming a black matrix, a pixel and a protective film on a transparent substrate. Various methods have been proposed as a method of forming a pixel and a black matrix (hereinafter, the pixel and the black matrix are referred to as a "colored pattern"). Among them, the pigment/dye dispersion method produced by the photolithography method of repeated coating, exposure, development and baking using a photosensitive resin composition as a resist can impart excellent durability and prevent pinholes, etc. Coloring patterns with few defects have become the mainstream today.

In general, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant and a solvent. Although the pigment/dye dispersion method has the above advantages, on the other hand, since the pattern of black matrix, R, G, B is repeatedly formed, high heat resistance is required, and it is used as a colorant that can withstand high baking temperature. Restrictions such as limitations on the types of colorants that can be used still often cause problems.

Patent Document 1 discloses that low temperature curing is possible by using compounds such as an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a colorant, and ethyl 3-aminobenzenesulfonate. Moreover, the coloring composition with improved stability is preserved.

Patent Document 2 discloses that low-temperature curing is achieved by using a photosensitive resin composition comprising a A specific base generator that generates a base by irradiating and heating with electromagnetic waves, or a polymer precursor that promotes the reaction toward the final product by heating in the presence of an alkaline substance.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-68843

[Patent Document 2] Japanese Patent Laid-Open No. 2014-70148

In recent years, flexible displays such as electronic paper have become popular. As a substrate of this flexible display, a plastic substrate such as polyethylene terephthalate has been studied. The substrate has the property of stretching or shrinking during baking, so it is necessary to lower the temperature of the baking step. However, the level achieved in Patent Document 1 is insufficient to satisfy the above-mentioned requirements. Moreover, although the low temperature sclerosis|hardenability can be improved in patent document 2, the storage stability is low, and it is difficult to put it into practical use.

The present invention has been made in order to solve the above-mentioned problems, and an object of the present invention is to provide a photosensitive resin composition which is good in developing property and storage stability, and which can provide a cured coating film with excellent solvent resistance even when cured at a low temperature. , and its manufacturing method.

Another object of the present invention is to provide a coloring having excellent solvent resistance A patterned color filter, a method for manufacturing the same, and an image display element provided with the color filter.

That is, the present invention is as shown in the following [1] to [15].

[1] A photosensitive resin composition comprising: a copolymer (A) comprising a structural unit (a) having a blocked isocyanato group and a structural unit (b) having an acid group, a hydroxyl-containing organic Solvent (B), reactive diluent (C), and photopolymerization initiator (D).

[2] The photosensitive resin composition according to [1], wherein the structural unit (a) having a blocked isocyanato group is a structural unit derived from a (meth)acrylate containing a blocked isocyanato group, The dissociation rate of the blocked isocyanato group of the above-mentioned blocked isocyanato group-containing (meth)acrylate is 5 to 99 mass % after heating at 100° C. for 30 minutes.

[3] The photosensitive resin composition according to [1] or [2], wherein the blocking agent of the structural unit (a) having a blocked isocyanato group is selected from the group consisting of diethyl malonate, 3,5 -Dimethylpyrazole and methyl ethyl ketoxime, one or more of the group.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the hydroxyl group-containing organic solvent (B) is selected from the group consisting of ethylene glycol monoalkyl ether and diethylene glycol monoalkyl group Ether, propylene glycol monoalkyl ether, propylene glycol monoaryl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, 3-methoxy-1-butanol, 1,3-propanediol 1,3-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerol monoalkyl ether, glycerol diol One or more of the group consisting of alkyl ether, methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkane dimethanol, ethyl lactate and diacetone alcohol.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid.

[6] The photosensitive resin composition according to any one of [1] to [5], wherein the copolymer (A) contains 1 to 40 mol % of the structural unit (a) having a blocked isocyanato group And the aforementioned structural unit (b) having an acid group is 1 to 60 mol%.

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the structural unit (a) having a blocked isocyanate group and the constituent unit (a) having an acid group in the copolymer (A) The molar ratio of the constituent unit (b) is 10:90 to 50:50.

[8] The photosensitive resin composition according to any one of [1] to [7], wherein the copolymer (A) contains: derived from 2-(3,5-dimethylpyrazole methacrylate) -1-yl)carbonylaminoethyl ester, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate, malonic acid-2-[[[[ [2-Methyl-1-oxy-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, benzoic acid-4-[[[[[2-[ (2-Methyl-1-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-propene Structural unit (a) of at least one of the group of acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl ester, derived from (methyl) Structural unit (b) of acrylic acid, derived from glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dicyclopentyl (meth)acrylate and methyl (meth)acrylate The constituent unit (c) of at least one of the group of acrylates.

[9] The photosensitive resin composition according to any one of [1] to [8], which further contains a colorant (E), and is for color filters.

[10] The photosensitive resin composition according to [9], which contains 10 to 100 parts by mass of the copolymer (A) with respect to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C). parts, 30 to 1,000 parts by mass of the aforementioned hydroxyl-containing organic solvent (B), 0.1 to 30 parts by mass of the aforementioned reactive diluent (C), 0.1 to 30 parts by mass of the aforementioned photopolymerization initiator (D), and the aforementioned Colorant (E) 5-80 parts by mass.

[11] The photosensitive resin composition according to [9] or [10], wherein the colorant (E) contains a pigment.

[12] A color filter characterized by having a colored pattern composed of a cured product of the photosensitive resin composition according to any one of [9] to [11].

[13] An image display element comprising the color filter according to [12].

[14] A method for manufacturing a color filter, comprising: coating a substrate with the photosensitive resin composition according to any one of [9] to [11], exposing it to light, and performing alkali development at 160° C. The steps of baking at the following temperature to form a colored pattern.

[15] A method for producing a photosensitive resin composition, comprising: in the presence of a hydroxyl-containing organic solvent (B), the (meth)acrylate containing a blocked isocyanato group and an unsaturated carboxyl The acid is subjected to a copolymerization reaction to synthesize a copolymer (A), and then a step of mixing a reactive diluent (C) and a photopolymerization initiator (D).

According to the present invention, it is possible to provide a photosensitive resin composition which is good in developing property and storage stability, and which forms a cured coating film excellent in solvent resistance even when cured at a low temperature, and a method for producing the same. Furthermore, according to the present invention, a color filter having a colored pattern excellent in solvent resistance, a method for producing the same, and an image display element provided with the color filter can be provided.

<Photosensitive resin composition> The photosensitive resin composition of the present invention is characterized by comprising: a copolymer (A) containing a structural unit (a) having a blocked isocyanate group and a structural unit (b) having an acid group. ), a hydroxyl-containing organic solvent (B), a reactive diluent (C), and a photopolymerization initiator (D).

<Copolymer (A)> <Structural unit (a) having a blocked isocyanato group> The structural unit (a) having a blocked isocyanato group contained in the copolymer (A) is derived from the The constituent unit of the monomer of cyano group. As the monomer, a monomer having an ethylenically unsaturated bond and a blocked isocyanato group, etc., for example, isocyanato compounds in isocyanate compounds having a vinyl group, a (meth)acryloyloxy group, etc. in the molecule can be mentioned. Cyanate group is a compound that is capped with a capping agent. The reaction of 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 inert to isocyanato groups. In the capping reaction, organometallic salts such as tin, zinc, and lead, tertiary amines, and the like 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 said isocyanate compound, the compound represented by following formula (1) is mentioned.

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 alkyl group with 2 to 6 carbon atoms, and R ⁵ is an alkyl group with 2 to 12 carbon atoms or an alkyl group with 6 to 6 carbon atoms. 12 of the extended aryl). R ² is preferably -COOR ³ -, and R ³ is preferably an alkylene group having 1 to 4 carbon atoms.

Specific examples of the isocyanate compound represented by the above formula (1) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, Isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl ( Meth)acrylate, 4-isocyanatocyclohexyl(meth)acrylate, methacryloyl isocyanate, and the like. In addition, an equimolar (1 mol:1 mol) reaction product of a 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. As the alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate, an ethyl group or an n-propyl group is preferable, and an ethyl group is preferable. As said diisocyanate compound, for example, hexamethylene diisocyanate, 2,4- (or 2,6-) tolylylene 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, lysine diisocyanate, etc.

Among these isocyanate compounds, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (methyl) Acrylate, 2-Isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanato Acidocyclohexyl (meth)acrylate and methacryloyl isocyanate are preferred, 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate is better.

Moreover, in this specification, what is indicated as (meth)acrylate means that it can be any one of acrylate and methacrylate, and the indication of (meth)acrylic acid means that it can be acrylic acid and methyl acrylate. Either acrylic.

As a blocking agent for blocking the isocyanate group in the isocyanate compound, for example, ε-caprolactam, δ-valerolactam, γ-butyrolactone, and β-propiolactone can be mentioned. Lactamides such as amines; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl Alcohols such as alcohol, cyclohexanol, etc; Phenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, Phenols such as p-nitrophenol and p-chlorophenol; active methylene such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetone acetone, etc. Base series; thiol series such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; amine series such as diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; acetaniline, methoxy Acetanisidide (Acetanisidide), Acetamide, Benzylamide and other acid amides; succinic acid amides, maleic acid amides and other acid amides; imidazole, 2-methylimidazole, Imidazole series such as 2-ethylimidazole; Pyrazole series such as pyrazole and 3,5-dimethylpyrazole; Urea series such as urea, thiourea, vinyl urea, etc.; Phenyl N-phenylcarbamate, Amine formate series such as 2-oxazolidinone: imine series such as ethyleneimine, polyethyleneimine, etc.; formaldehyde oxime, acetaldoxime, acetaldoxime, methyl ethyl ketoxime, methyl isobutyl Oxime series such as ketoxime, cyclohexanone oxime, etc.; bisulfite series such as sodium bisulfite, potassium bisulfite, etc. These terminal blocking agents may be used alone or in combination of two or more.

The blocking agent protects the highly reactive isocyanato group, but the blocked isocyanato group is dissociated by heating to regenerate the isocyanato group. In the present invention, the isocyanate group is reacted 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. contained in the desired reaction, A hardened product with high crosslink density is formed.

From the viewpoint of low-temperature curability and storage stability of the photosensitive resin composition to be described later, as the monomer for imparting the structural unit (a) having a blocked isocyanato group, (a) containing a blocked isocyanato group is used. Meth)acrylates are preferred. The dissociation rate of the blocked isocyanato group after heat treatment at 100°C for 30 minutes is preferably 5 to 99 mass %, preferably 8 to 97 mass %, and most preferably 10 to 95 mass % The isocyanato-blocked (meth)acrylates are preferred. In addition, the dissociation rate of the blocked isocyanato group of the blocked isocyanato group-containing (meth)acrylate was measured by HPLC analysis to prepare the blocked isocyanato group-containing (meth)acrylic acid. An n-octanol solution with an ester concentration of 20% by mass was added to this solution by adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor), and heated at 100°C for 30 The value obtained by the ratio of the mass reduction of the blocked isocyanate group-containing (meth)acrylate after separation. When a (meth)acrylate containing a blocked isocyanate group with a dissociation rate in the above range is used, the stability of the copolymer during synthesis can be sufficiently ensured, the baking temperature during the production of the hardened coating film can be sufficiently lowered, and The solvent resistance of the hardened coating film can be fully ensured. As a blocking agent containing a blocked isocyanate group-containing (meth)acrylate having such a dissociation rate, for example, γ-butyrolactam, 1-methoxy-2-propanol, 2 , 6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, 3,5-dimethylpyrazole and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole and methyl ethyl ketoxime are preferable from the viewpoint of low-temperature curability.

In addition, it is also preferable to use a blocked isocyanato group-containing (meth)acrylate whose dissociation temperature of the blocked isocyanato group is 80°C or higher. . When a (meth)acrylate containing a blocked isocyanate group with a dissociation temperature of 80°C or higher is used, the stability of the copolymer during synthesis can be sufficiently ensured, and unwanted crosslinking 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 lowered, and the solvent resistance of the cured coating film can be sufficiently secured. Furthermore, the dissociation temperature of the blocked isocyanato group of the blocked isocyanato group-containing (meth)acrylate was measured by HPLC analysis to prepare the blocked isocyanato group-containing (meth)acrylic acid. An n-octanol solution having an ester concentration of 20% by mass was heated at a predetermined temperature after adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to this solution After 30 minutes, the mass reduction ratio of the blocked isocyanato group-containing (meth)acrylate, and the temperature at which the mass reduction ratio becomes 80% by mass or more was used as the dissociation temperature of the blocked isocyanato group.

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

The ratio of the constituent unit (a) with blocked isocyanate groups contained in the copolymer (A) is not particularly limited, and is preferably 1-40 mol %, preferably 2-30 mol %, and the best It is 3~25 mol%. When the ratio of the structural unit (a) having a blocked isocyanate group is 1 to 40 mol %, the solvent resistance of the hardened coating film is improved, and the storage stability of the copolymer (A) is also maintained.

<Constituent unit (b) having an acid group> The constituent unit (b) having an acid group contained in the copolymer (A) is a constituent unit derived from an acid group-containing monomer (however, it is equivalent to the above-mentioned structural unit having a terminal block Except for the constituent unit (a) of the cyano group). Examples of the acid group include a carboxyl group, a sulfonic acid group, a phosphonium group (phospho), and the like, and among these, a carboxyl group is preferred in terms of easy availability. Examples of the monomer that imparts the structural unit (b) having an acid group include monomers having a polymerizable unsaturated bond and an acid group, for example, unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, and unsaturated phosphonic acids. Wait. Specific examples of preferable monomers include (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl (meth)acrylic acid, crotonic acid, propyolic acid, cinnamic acid, α- Cyanocinnamic acid, maleic acid, maleic acid anhydrous, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic acid anhydrous, citrate Unsaturated carboxylic acids or their anhydrides such as citraconic acid, anhydrous citraconic acid, etc.; Saturated sulfonic acid; unsaturated phosphonic acid such as vinylphosphonic acid, etc. These single systems may be used alone or in combination of two or more. Among these, unsaturated carboxylic acid is preferable, and (meth)acrylic acid is preferable from the viewpoint of excellent alkali developability and availability.

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

The ratio of the constituent unit (b) with an acid group contained in the copolymer (A) is not particularly limited, and is preferably 1-60 mol %, preferably 10-50 mol %, and most preferably 15-40 mol %. Mol%. When the ratio of the constituent unit (b) having an acid group is 1 to 60 mol %, the speed of alkali image development is suitable, and a fine pattern can be formed.

In the copolymer (A), the molar ratio of the structural unit (a) having a blocked isocyanato group to the structural unit (b) having an acid group can be, for example, 1:99 to 99:1, from the hardened coating film. From the viewpoint of the solvent resistance and the storage stability of the copolymer (A), 5:95~75:25 is preferable, and 10:90~50:50 is the best.

<Other structural unit (c)> In the present invention, as the structural unit contained in the copolymer (A), in addition to the structural unit (a) having a blocked isocyanate group and the structural unit (b) having an acid group, It may also contain other constituent units (c) which can be copolymerized with these (however, this is except for the aforementioned constituent unit (a) having a blocked isocyanate group and the aforementioned constituent unit (b) having an acid group) . Specific examples of the other structural unit (c) include, for example, a structural unit (c-1) having an epoxy group, a structural unit (c-2) having a hydroxyl group, (c-1), and (c-2) Other constituent units (c-3), etc. The proportion of other constituent units (c) contained in the copolymer (A) is not particularly limited, and is preferably 0-80 mol %, preferably 0-70 mol %, and most preferably 0-60 mol % .

As the monomer used to introduce the structural unit (c-1) having an epoxy group, for example, a monomer having a polymerizable unsaturated bond and an epoxy group, for example, ethylene oxide (meth)acrylic acid can be mentioned. Esters, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranyl Ethyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3-glycidoxypropyl (meth)acrylate, glycidoxyphenyl (meth)acrylate (meth)acrylate derivatives containing epoxy groups such as acrylates; 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (methyl) ) acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, 2-(3,4-epoxycyclohexylmethoxy)ethyl(meth)acrylate , 3-(3,4-epoxycyclohexylmethoxy)propyl (meth)acrylate, etc. containing alicyclic carbon containing epoxy groups such as 3,4-epoxycyclohexane ring (meth)acrylate derivatives of rings; vinyl ether compounds containing epoxy groups; allyl ether compounds containing epoxy groups, and the like. These single systems may be used alone or in combination of two or more. Among these, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethyl epoxy Propyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3-glycidoxypropyl Epoxy-containing (meth)acrylates such as (meth)acrylates and glycidoxyphenyl (meth)acrylates are preferred, and glycidyl (meth)acrylates are preferred .

By including the structural unit (c-1) having an epoxy group in the copolymer (A), the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

When the constituent unit (c-1) having an epoxy group is introduced into the copolymer (A), the ratio of the constituent unit (c-1) having an epoxy group is not particularly limited, and the ratio of the constituent unit (c-1) having an epoxy group is more than 0 mol % to 60 mol %. Ear% is better, preferably more than 0 mol% to 50 mol%, and the best is more than 0 mol% to 40 mol%.

As the monomer used to introduce the structural unit (c-2) having a hydroxyl group, for example, a monomer having a polymerizable unsaturated bond and a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropylacrylate , 4-hydroxybutyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl phthalate Ethyl-2-hydroxyethyl-phthalic acid, etc. These single systems may be used alone or in combination of two or more. Among these, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (Meth)acrylate derivatives containing hydroxyl groups such as (meth)acrylate, 2-hydroxy-3-phenoxypropylacrylate, and 4-hydroxybutylacrylate are preferred, and 2-hydroxyethyl acrylate is preferred. (Meth)acrylates are preferred.

By including the structural unit (c-2) having a hydroxyl group in the copolymer (A), the solvent resistance when the copolymer (A) is used as a photosensitive material is greatly improved.

When the structural unit (c-2) having a hydroxyl group is introduced into the copolymer (A), the ratio of the structural unit (c-2) having a hydroxyl group is not particularly limited, and it is preferable to exceed 0 mol % to 50 mol % , preferably more than 0 mol% to 40 mol%, and the best is more than 0 mol% to 30 mol%.

Specific examples of monomers used to introduce structural units (c-3) other than the structural unit (c-1) having an epoxy group and the structural unit (c-2) having a hydroxyl group include styrene, for example. , α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxybenzene Aromatic vinyl compounds of ethylene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostyrene, p-acetylaminostyrene, etc.; Camphene (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 ] Dodec-3-ene, 8-ethyl Tetracyclo[4.4.0.1 ^{2,5.1 7,10} ]dodec-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[ ^{4.4.0.12,5.17,10.01,6} ] ^dodec -3-ene, 8-methyltetracyclo[ ^{4.4.0.12 , 5.1 7,10.0 1,6} ] Dodec-3-ene, 8-ethylenetetracyclo[4.4.0.1 ^{2,5.1 7,12} ] Dodec-3-ene, 8-ethylene base tetracyclo[4.4.0.1 ^{2,5.1 7,10.0 1,6} ] dodec-3-ene, pentacyclo[6.5.1.1 ^{3,6.0 2,7.0 9,13} ] fifteen Cyclic olefins with norbornene structure such as -4-ene, pentacyclo[7.4.0.1 ^{2,5.1 9,12.0 8,13} ]pentadec-3-ene; butadiene, isoprene Dienes of alkene, chloroprene, etc.; 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, pentyl (methyl) ) acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Acrylates, Lauryl (meth)acrylate, Dodecyl (meth)acrylate, Cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, Methylcyclohexyl (meth)acrylate ester, ethylcyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono(meth)propene acid ester, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methyl norbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dimethicone Cyclopentenyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate Acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl ( Meth)acrylate, perfluoro-isopropyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate Acrylate, Phenyl (meth)acrylate, Cumyl (meth)acrylate, 4-Phenoxyphenyl (meth)acrylate, Phenoxyethyl (meth)acrylate, Benzene Oxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylic acid (Meth)acrylates of esters, anthracene (meth)acrylates, etc.; (meth)acrylate amide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N- Diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylate anthrylamide, etc. ( Acrylic acid amide; (meth) acrylate benzene, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidine Vinyl compounds of ketone, vinyl pyridine, vinyl acetate, vinyl toluene, etc.; unsaturation of diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl iconate, etc. Dicarboxylic acid diesters; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide Monomaleimide and so on. Among these, (meth)acrylates are preferred, and methyl (meth)acrylates and dicyclopentyl (meth)acrylates are particularly preferred. These single systems may be used alone or in combination of two or more.

<The production method of the copolymer (A)> The ratio of the blocked isocyanate group-containing monomer (a0) and the acid group-containing monomer (b0) used in the production of the copolymer (A) is not particularly limited , preferably (a0) 1~40 mol% and (b0) 1~60 mol%, preferably (a0) 2~30 mol% and (b0) 10~50 mol%, the best is (a0) 3~25 mol% and (b0) 15~40 mol%. When the copolymer (A) further contains other constituent units (c), the blocked isocyanate group-containing monomer (a0) and the acid group-containing monomer (b0) used in the production of the copolymer (A) And the ratio of other monomers (c0) is preferably (a0) 1~40 mol%, (b0) 1~60 mol% and (c0) more than 0 mol%~80 mol%, preferably (a0) 2~30 mol%, (b0) 10~50 mol% and (c0) more than 0~70 mol%, the best is (a0) 3~25 mol%, (b0) 15~40 mol% and (c0) more than 0 mol%~60 mol%.

The copolymerization reaction of the blocked isocyanate group-containing monomer (a0), the acid group-containing monomer (b0), and the other monomers (c0) can be carried out according to the free radical polymerization method well-known in the technical field. It may be performed in the presence or absence of a solvent, but it is preferably performed in the presence of a hydroxyl group-containing organic solvent (B) described later, from the viewpoint of preventing abnormal polymerization and stably advancing the polymerization reaction. By carrying out the copolymerization reaction in the presence of the hydroxyl group-containing organic solvent (B), even if the blocked isocyanato group is dissociated to generate an isocyanato group, the isocyanato group and the hydroxyl group of the hydroxyl group-containing organic solvent (B) will proceed. reaction to prevent abnormal aggregation. In the copolymer (A) thus obtained, a part of the blocking agent for blocking the isocyanato group is considered to be substituted with the hydroxyl group-containing organic solvent (B). For example, after dissolving these monomers in the hydroxyl-containing organic solvent (B), a polymerization initiator may be added to the solution, and a polymerization reaction may be carried out at 50 to 100° C. for 1 to 20 hours. On this occasion, when the polymerization reaction is carried out at a temperature at which the blocked isocyanato group of the blocked isocyanato group-containing monomer (a0) dissociates, the isocyanide generated by the dissociation of the blocked isocyanato group is The acid group will react with the acid group to generate a gel, so the temperature should be lower than the dissociation temperature of the blocked isocyanato group, preferably the dissociation temperature of the blocked isocyanato group should be lower than the dissociation temperature of the blocked isocyanato group by 20~50℃ The polymerization is preferably carried out at temperature.

Moreover, it does not specifically limit as a polymerization initiator which can be used for this copolymerization reaction, For example, azobisisobutyronitrile, azobisisovaleronitrile, peracid benzyl group, t-butyl group is mentioned. Peroxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more. The usage amount of the polymerization initiator is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, when the total input amount of the monomers is 100 parts by mass.

The weight average molecular weight in terms of polystyrene of the copolymer (A) is not particularly limited, and by the above-mentioned production method, a copolymer (A) having a weight average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 40,000 can be obtained ). When the weight average molecular weight of the copolymer (A) is 1,000 or more, it becomes difficult to produce a color pattern defect 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 suitable, and practicality can be ensured.

In addition, the acid value (JIS K6901 5.3) of the copolymer (A) can be appropriately selected, and when it is blended into the photosensitive resin composition, it is preferably 20 to 300 KOHmg/g, more preferably 30 to 200 KOH mg/g. . 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 favorable. On the other hand, when the acid value of the copolymer (A) is 300 KOHmg/g or less, the exposed portion (photocured portion) of the alkali developing solution is not easily dissolved, so that the pattern shape becomes favorable.

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

<Hydroxy-containing organic solvent (B)> The hydroxyl-containing organic solvent (B) should just be a hydroxyl-containing organic solvent, and examples thereof include ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, Propylene glycol monoalkyl ether, propylene glycol monoaryl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, 3-methoxy-1-butanol, 1,3-propylene glycol monoalkyl ether, 1,3 -Butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerol monoalkyl ether, glycerol dialkyl ether, methanol, ethanol, propanol, C _5-6 cycloalkane Diol, C _5-6 cycloalkane dimethanol, ethyl lactate and diacetone alcohol, etc. Among them, ethyl lactate, diacetone alcohol, 3-methoxy-1-butanol, and propylene glycol monomethyl ether are preferred from the viewpoint of film formability and easy availability during the production of the cured coating film. , propylene glycol monomethyl ether is particularly preferred. These hydroxyl-containing organic solvents (B) may be used alone or in combination of two or more.

In the present invention, by using together a copolymer (A) containing a structural unit (a) having a blocked isocyanate group and a structural unit (b) having an acid group, and a hydroxyl-containing organic solvent (B), The storage stability of the photosensitive resin composition is improved.

Moreover, in the photosensitive resin composition of this invention, the solvent other than the hydroxyl-containing organic solvent (B) may be used together.

<Reactive diluent (C)> 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 a plurality of polymerizable functional groups . By using such a reactive diluent (C) in combination with the copolymer (A), the viscosity can be adjusted, and the strength of the formed cured product or the adhesion to the substrate can be improved.

Examples of the monofunctional monomer used as the reactive diluent (C) include (meth)acrylamide, methylol (meth)acrylamide, and methoxymethyl (meth)propylene. amide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (methyl) ) 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)acryloyloxy-2 -Hydroxypropyl phthalate, glycerol mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylates such as bis(meth)acrylate, 2,2,3,3-tetrafluoropropyl(meth)acrylate, hemi(meth)acrylate of phthalic acid derivatives; benzene Aromatic vinyl compounds such as ethylene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, etc.; carboxylic acid esters such as vinyl acetate, vinyl propionate, etc. In addition, these single systems may be used alone or in combination of two or more.

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, butanediol 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 base) acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acrylooxydiethoxyphenyl)propane, 2,2-Bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol Alcohol Diglycidyl Ether Di(meth)acrylate, Diethylene Glycol Diglycidyl Ether Di(meth)acrylate, Diglycidyl Phthalate Di(meth)acrylate, Propylene Triol triacrylate, glycerol polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (ie, tolylylene diisocyanate), trimethylhexamethylene The reaction products of bis(hydroxyethyl) diisocyanate, hexamethylene diisocyanate, etc. with 2-hydroxyethyl (meth)acrylate, tris(meth)acrylate of bis(hydroxyethyl) isocyanurate, etc. ( Meth) acrylates; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, diallyl phenylphosphonate, etc.; dicarboxylates such as divinyl adipate; Triallyl cyanurate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, polyvalent alcohols and N-methylol (meth) acrylamide The condensate, etc. These single systems may be used alone or in combination of two or more.

<Photopolymerization initiator (D)> 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-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl yl)acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, 2-benzyl-2-dimethylamino- Acetophenones such as 1-(4-morpholinylphenyl)butanone-1; 2-methylanthraquinone, 2-pentylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone Anthraquinones such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, etc. thioxanthone; Ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone, 4-(1-t-butyldioxy-1-methylethyl)dibenzyl Ketones, benzophenones such as 3,3',4,4'-tetra(t-butyldioxycarbonyl) benzophenone; acylphosphine oxides, etc. These photopolymerization initiators (D) may be used alone or in combination of two or more.

The photosensitive resin composition of the present invention may contain known additives such as known coupling agents, leveling agents, and thermal polymerization inhibitors in order to impart predetermined properties in addition to the aforementioned components. The compounding quantity of these additives will not be specifically limited if it is a range which does not inhibit the effect of this invention.

<Photosensitive resin composition for color filters> In addition, the photosensitive resin composition of the present invention may further contain a colorant (E) to prepare a photosensitive resin composition for color filters.

The colorant (E) is not particularly limited as long as it dissolves or disperses in the hydroxyl group-containing organic solvent (B), and examples thereof include dyes, pigments, and the like. As the dye, from the viewpoints of solubility in the hydroxyl group-containing organic solvent (B) or alkali developing solution, interaction with other components in the photosensitive resin composition, heat resistance, etc., those having carboxylic acid or sulfonic acid are used. Preferred are acid dyes of acidic groups such as acids, salts of acid dyes and nitrogen compounds, and sulfonamides of acid dyes.

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 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; edible yellow 3 and their derivatives, etc. Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more depending on the color system of the target pixel.

Examples of pigments include 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 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51 , 55, 59, 61, 64, 65, 71, 73, etc. orange pigments; C.I. 215, 216, 224, 242, 254, 255, 264, 265, etc. red pigments; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. blue pigments; C.I. Pigment Violet 1, 19 , 23, 29, 32, 36, 38, etc. violet pigment; C.I. Pigment Green 7, 36, 58, 59, etc. green pigment; C.I. Pigment brown 23, 25, etc. brown pigment; C.I. Pigment black 1, 7, carbon Black pigments such as black, titanium black, iron oxide, etc.

These colorants (E) may be used alone or in combination of two or more depending on the color system of the intended pixel. Furthermore, the above-mentioned dyes and pigments may be used in combination according to the color of the target pixel.

When a pigment is used as the colorant (E), from the viewpoint of improving the dispersibility of the pigment, a known dispersant may be blended into the photosensitive resin composition. As the dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, Rowandan aliphatic ester-based dispersant, aliphatic modified ester-based dispersant, etc. As such a polymer dispersant, for example, EFKA (manufactured by EFKA chemicals BV (EFKA), Inc.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), Disparlon (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.) can also be used. system) and other commercially available products. The blending amount of the dispersant may be appropriately set according to the type of the pigment to be used.

The compounding amounts of the copolymer (A), the hydroxyl-containing organic solvent (B), the reactive diluent (C), the photopolymerization initiator (D) and the coloring agent (E) in the photosensitive resin composition for color filters With respect to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C) in the photosensitive resin composition for color filters, the amount of the copolymer (A) is 10 to 100 parts by mass, a hydroxyl group-containing The organic solvent (B) is 30 to 1,000 parts by mass, 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, and the colorant (E) is 5 to 80 parts by mass, 20 to 80 parts by mass of the copolymer (A), 50 to 800 parts by mass of the hydroxyl-containing organic solvent (B), 20 to 80 parts by mass of the reactive diluent (C), and photopolymerization The initiator (D) is preferably 0.5 to 20 parts by mass, the colorant (E) is preferably 5 to 70 parts by mass, preferably the copolymer (A) is 30 to 75 parts by mass, and the hydroxyl-containing organic solvent (B) It is 100-700 mass parts, reactive diluent (C) is 25-70 mass parts, photopolymerization initiator (D) is 1-15 mass parts, and coloring agent (E) is 10-60 mass parts. In the compounding quantity of this range, it will become the photosensitive resin composition for color filters which has an appropriate viscosity. Moreover, even in the case of a photosensitive resin composition that does not contain a colorant (E), the copolymer (A), the hydroxyl-containing organic solvent (B), the reactive diluent (C), and the photopolymerization initiator ( The compounding amount of D) can also be applied to the above numerical range.

<Production of Photosensitive Resin Composition> The photosensitive resin composition of the present invention can be produced by mixing the above-mentioned components using a known mixing device. Moreover, in the presence of a hydroxyl group-containing organic solvent (B), it is also possible to prepare a copolymer containing a blocked isocyanato group by subjecting a (meth)acrylate containing a blocked isocyanato group to a copolymerization reaction with an unsaturated carboxylic acid. After the composition of (A) and the hydroxyl group-containing organic solvent (B), the reactive diluent (C), the photopolymerization initiator (D), and the coloring agent (E) as an optional component are mixed and produced.

Since the photosensitive resin composition obtained by the said operation has alkali developability, it is suitable as a resist. For curing of the photosensitive resin composition, the baking temperature can be appropriately selected in the range of 250° C. or lower. The copolymer (A) of the present invention has excellent curability at low temperature, so compared with the conventional materials, it can reduce the 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 proceed sufficiently even if the baking temperature is lowered. Moreover, even if it is a coloring agent (E) or a board|substrate which is inferior in heat resistance, it becomes possible to acquire the characteristic of a coloring agent itself, and it becomes applicable to various board|substrates. Based on such knowledge, the baking temperature is preferably 160°C or lower, more preferably 150°C or lower. The lower limit of the baking temperature is not necessarily the same depending on the type of blocked isocyanato group contained in the copolymer (A), but it must be above the dissociation temperature of the blocked isocyanato group, usually above 80°C , preferably 90°C or higher, preferably 100°C or higher. When the baking temperature becomes too low, it becomes difficult to sufficiently improve the solvent resistance of the coating film. In addition, the baking time can be appropriately selected, and is 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, especially suitable as a color filter to be incorporated in an organic EL display (for black PDL), a liquid crystal display device, a solid-state imaging element such as CCD or CMOS, etc. Resistant used. Furthermore, since the photosensitive resin composition of the present invention provides a cured coating film excellent in solvent resistance and curing properties at low temperatures, it can also be used for various coatings, adhesives, binders for printing inks, and the like.

The photosensitive resin composition of the present invention has good developing properties and good storage stability, and can form colored patterns with excellent solvent resistance even if the baking temperature during pattern formation is lowered, so it is extremely useful. Photosensitive materials for color filters. In addition, since the photosensitive resin composition of the present invention is accompanied by low-temperature curing, it can contribute to the development of flexible displays, reduction of energy consumption in manufacturing steps, and relaxation of restrictions on colorants 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 this invention has the coloring pattern formed using the said photosensitive resin composition for color filters. A color filter is generally composed of a substrate, RGB pixels formed thereon, a black matrix formed on the boundaries of the individual pixels, and a protective film formed over the pixels and the black matrix. In this structure, except that the pixel and the black matrix (colored pattern) are formed using the above-mentioned photosensitive resin composition, the other structures can be all known.

Next, one embodiment of a method of manufacturing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, the black matrix and the RGB pixels are sequentially formed on the substrate. The material of the substrate is not particularly limited, such as glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, polyamide substrate, polyamide imide substrate, polyimide substrate, aluminum substrate can be suitably used , printed wiring substrates, array substrates, etc.

Shading patterns can be formed by photolithography. Specifically, after applying the above-mentioned photosensitive resin composition on a substrate to form a coating film, the coating film is exposed through a mask of a predetermined pattern, and the exposed part is photocured. After that, after developing the unexposed portion with an alkaline aqueous solution, a predetermined color pattern can be formed by performing baking.

It does not specifically limit as a coating method of the photosensitive resin composition, For example, a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, etc. are used. Moreover, after apply|coating the photosensitive resin composition, you may volatilize the organic solvent (B) containing a hydroxyl group by heating by heating means, such as a circulating oven, an infrared heater, a hotplate, etc. as needed. The heating conditions are not particularly limited, and may be appropriately set according to the type of the photosensitive resin composition to be used. Generally, it can be heated at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

Next, the formed coating film is partially exposed by irradiating active energy rays such as ultraviolet rays and excimer laser light through a negative mask. The amount of irradiated energy rays can be appropriately selected according to the composition of the photosensitive resin composition, for example, 30 to 2000 mJ/cm ² is preferred. It does not specifically limit as a light source used for exposure, For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used.

There is no particular limitation on the alkaline aqueous solution used for development, 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-beta-methanesulfonamidoethylaniline, 3-Methyl-4-amino-N-ethyl-N- β-Methoxyethylaniline and aqueous solutions of p-phenylenediamine-based compounds such as sulfate, hydrochloride, or p-toluenesulfonate. Furthermore, antifoaming agents or surfactants may be added to these aqueous solutions as necessary. In addition, it is preferable to wash with water and to dry it after the above-mentioned development with an aqueous alkali solution.

The conditions of the baking are not particularly limited, and the heat treatment may be performed according to the type of the photosensitive resin composition to be used. If the baking temperature of the conventional photosensitive resin composition is 200°C or lower, the solvent resistance of the colored pattern will be insufficient, but the photosensitive resin composition for color filter of the present invention is baked at a temperature of 120°C or lower. When baked, a tinted pattern showing adequate solvent resistance is still formed. Therefore, the baking temperature can be lowered, and the processing time can be shortened when baking at a high temperature, which is a great advantage in terms of production. Based on this knowledge, the baking temperature is usually set at 210°C or lower, preferably 160°C or lower, preferably 120°C or lower, and the baking time is usually set at 10 minutes to 4 hours, preferably 20 minutes to 20 minutes. 2 hours to do it.

By using the photosensitive resin composition for black matrix and the photosensitive resin composition for red, green, and blue pixels, and repeating the above-mentioned coating, exposure, development and baking in sequence, it can be formed. Color the pattern as you want. Furthermore, the method for forming the colored pattern by photohardening has been described above, but instead of the photopolymerization initiator (D), a photosensitive resin composition containing a hardening accelerator and a known epoxy resin is used. , After coating by the inkjet method, the desired color pattern can also be formed by heating. Next, a protective film is formed on the color pattern (each pixel of RGB and black matrix). It does not specifically limit as a protective film, What is necessary is just to form using a well-known thing.

The color filter produced by this operation is produced by using a photosensitive resin composition that imparts a color pattern that is excellent in sensitivity and developability, can be cured at a low temperature, and is excellent in solvent resistance, so it has Excellent shading pattern with little color change.

<Image display element> The image display element of the present invention is an image display element provided with the above-mentioned color filter, and specific examples thereof include a liquid crystal display element, an organic EL display element, a CCD element, or a CMOS element. Solid-state imaging elements, etc. The production of the image display element of the present invention may be carried out according to a conventional method, except that the above-mentioned color filter is used. For example, in the case of manufacturing a liquid crystal display element, the above-described color filter is formed on a substrate, and then electrodes, spacers, and the like are formed in this order. Moreover, electrodes etc. are formed on the other board|substrate, the two are bonded together, a predetermined amount of liquid crystal is injected, and what is necessary is just to seal. [Example]

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

[Synthesis Example 1] After placing 149.3 g of propylene glycol monomethyl ether in 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, 22.4 g of dicyclopentyl methacrylate, 17.2 g of methacrylic acid and 50.2 g of methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl A monomer mixture consisting of ester (Karenz MOI-BP, manufactured by Showa Denko Co., Ltd., dissociation rate of blocked isocyanato group: 70% by mass), and 11.2 g of 2,2'-azobis(2, 4-dimethylvaleronitrile) (polymerization initiator) was added to 62.8 g of propylene glycol monomethyl ether acetate and dissolved, and each was dropped into the flask from the dropping funnel. After completion of the dropping, the copolymerization reaction was performed by stirring at 78° C. for 3 hours to form a copolymer, and the polymer composition (component concentration other than the solvent: 35% by mass) of Sample No. 1 was obtained. The weight average molecular weight of the copolymer in the obtained polymer composition was 9,100, and the acid value was 121.5 KOHmg/g.

[Synthesis Examples 2 to 9 and Comparative Synthesis Examples 1 to 2] Except that the raw materials described in Tables 1 and 2 were used, the copolymerization reaction was carried out under the same conditions as in Synthesis Example 1, and the samples No. 2 to 11 were obtained. Polymer composition (component concentration other than solvent: 35% by mass). The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Tables 1 and 2. In addition, in Tables 1 and 2, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate is Karenz MOI-BM manufactured by Showa Denko Co., Ltd. Dissociation rate of cyano group: 18% by mass), malonic acid-2-[[[[[2-methyl-1-oxy-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- Dissociation rate of blocked isocyanato group of methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester: 40% by mass, benzoin Termination of acid-2-[[[[2-[(2-methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester Dissociation rate of isocyanato group: 75% by mass, blocked isocyanide of 2-acrylic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amino]ethyl ester The dissociation rate of the acid group: 28% by mass.

[Examples 1 to 9 and Comparative Examples 1 to 2]

<Preparation of photosensitive resin composition (pigment type)>

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 Japan Co., Ltd.) Disperbyk-161, manufactured by Co., Ltd., 25 parts by mass, and mixed with a paint shaker for 2 hours to disperse to prepare a green pigment dispersion.

This green pigment dispersion liquid was mixed with other compounding components (ie, polymer composition, reactive diluent, photopolymerization initiator, and solvent) shown in Table 3 to prepare a photosensitive resin composition. The compounding amounts of individual components are shown in Table 3. Furthermore, the photosensitive resin compositions of Examples 1 to 9 were prepared using the polymer compositions of Sample Nos. 1 to 9, respectively, and the photosensitive resin compositions of Comparative Examples 1 to 2 were prepared using Sample Nos. 10 to 11, respectively. The polymer composition was prepared. 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 a compounding component.

<Evaluation of Photosensitive Resin Compositions> (1) Alkali Developability The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 2 were spin-coated so that the thickness after exposure might be 2.5 μm. After placing it on a glass substrate (alkali-free glass substrate) of 5 cm square, the solvent was volatilized by heating at 90° C. for 3 minutes. Next, a distance of 100 μm from the coating film was set to a predetermined pattern mask, the coating film was exposed through the mask (exposure amount: 150 mJ/cm ² ), and the exposed part was photocured. Next, by spraying an aqueous solution containing 0.1% by mass of sodium carbonate at a temperature of 23°C and a pressure of 0.3 MPa, the unexposed part was dissolved and developed, and then baked at 100°C for 20 minutes. Form the prescribed pattern. The residue after alkali imaging was confirmed by observing the pattern after alkali imaging using an electron microscope S-3400 manufactured by Hitachi High-Tech Co., Ltd. The criteria for this evaluation are as follows. ○: No residue × : Residue is present Table 4 shows the evaluation results of alkali developability.

(2) Evaluation of Solvent Resistance The photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 2 were spin-coated on a 5 cm square glass substrate (without a thickness of 2.5 μm after baking), respectively. After being placed on an alkali glass substrate), the solvent was volatilized by heating at 90° C. for 3 minutes. Next, the coating film was exposed to light with a wavelength of 365 nm, and after the exposure part was photo-hardened, it was placed in a dryer with a baking temperature of 100° C. for 20 minutes to prepare a hardened coating film. Put 200 mL of propylene glycol monomethyl ether acetate into a capped glass bottle with a capacity of 500 mL, and let it stand at 80°C. After immersing the above-mentioned test piece with a hardened coating film therein, it was left to stand for 5 minutes in a state maintained 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. When 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 Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 2 were respectively put into glass containers in equal amounts, and the mouths were closed with aluminum foil so that dust would not enter. Next, these samples were left to stand in a thermostat maintained at 23° C., respectively, and the weight-average molecular weight (Mw) of the samples after one month was measured. The change rate of Mw after 1 month is shown in Table 5. If the change rate of Mw after 1 month is within 20%, it can be said that the copolymer has excellent storage stability.

As is clear from the results in Table 4, the photosensitive resin compositions of Examples 1 to 9 using the polymer compositions of Sample Nos. 1 to 9 were 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 mixed with it, it can be seen from the results in Table 5 that the implementation of the polymer compositions using Sample Nos. 1 to 9 is used. The photosensitive resin compositions of Examples 1 to 9 are also good in terms of storage stability. On the other hand, although the storage stability of the photosensitive resin compositions of Comparative Examples 1 to 2 using the polymer compositions of Sample No. 10 to 11 was good, the comparative examples of the polymer compositions of Sample No. 10 were used The solvent resistance of the photosensitive resin composition of 1 was insufficient, and the alkali developability and solvent resistance of the photosensitive resin composition of Comparative Example 2 using the polymer composition of Sample No. 11 were insufficient.

From the above results, it was found that according to the present invention, a photosensitive resin composition having good developability and excellent solvent resistance and storage stability can be provided.

Furthermore, the present international application claims priority based on Japanese Patent Application No. 2017-150502 filed on August 3, 2017, and the entire contents of the Japanese Patent Application are cited in the present international application .

Claims (13)

A photosensitive resin composition, characterized by comprising: a copolymer (A) comprising a structural unit (a) having a blocked isocyanato group, a structural unit (b) having an acid group, and other structural units (c), Hydroxyl-containing organic solvent (B), reactive diluent (C), and photopolymerization initiator (D); the aforementioned other constituent unit (c) contains a hydroxyl group-containing constituent unit (c-2), which is relative to the aforementioned The total amount of the copolymer (A) and the reactive diluent (C) is 100 parts by mass, containing 10 to less than 100 parts by mass of the copolymer (A) and 30 to 1,000 parts by mass of the hydroxyl-containing organic solvent (B) , the above-mentioned reactive diluent (C) exceeds 0 to 90 parts by mass, the above-mentioned photopolymerization initiator (D) is 0.1 to 30 parts by mass, and the above-mentioned structural unit (a) having a blocked isocyanato group is derived from The structural unit of the (meth)acrylate containing blocked isocyanato group, the dissociation rate of the block isocyanato group of the aforementioned (meth)acrylate containing blocked isocyanato group was heated at 100°C for 30 minutes The latter is 5 to 99 mass %. According to the photosensitive resin composition of claim 1, the blocking agent having the structural unit (a) of blocked isocyanate group is selected from the group consisting of diethyl malonate, One or more of the group consisting of 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate and 3,5-stubble phenol. The photosensitive resin composition according to claim 1, wherein the aforementioned hydroxyl-containing organic solvent (B) is selected from the group consisting of ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, and propylene glycol monoalkyl ether. ether), propylene glycol monoaryl ether, dipropylene glycol monoalkyl ether, tripropylene glycol monoalkyl ether, 3-methoxy-1-butanol, 1,3-propanediol monoalkyl ether ether), 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerol monoalkyl ether, glycerol dialkyl ether, methanol, ethanol, propanol, One or more of the group consisting of C _5-6 cycloalkanediol, C _5-6 cycloalkane dimethanol, ethyl lactate and diacetone alcohol. The photosensitive resin composition according to claim 1 or 2, wherein the structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid. The photosensitive resin composition according to claim 1 or 2, wherein the copolymer (A) contains 1 to 40 mol % of the aforementioned constituent unit (a) having a blocked isocyanate group and the aforementioned constituent unit having an acid group ( b) 1~60 mol%. The photosensitive resin composition according to claim 1 or 2, wherein the molar ratio of the structural unit (a) having a blocked isocyanate group to the structural unit (b) having an acid group in the copolymer (A) 10:90~50:50. The photosensitive resin composition according to claim 1 or 2, wherein the copolymer (A) contains: derived from methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methyl ester, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate, malonic acid-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-oxo yl-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-acrylic acid-2-methyl-2-[[(3,5-dimethylbenzene The constituent unit (a) of at least one of the group consisting of oxy)carbonyl]amino]ethyl ester, the constituent unit (b) derived from (meth)acrylic acid, and the constituent unit (b) derived from glycidyl (methyl) ) Composition of at least one of acrylate, 2-hydroxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate (dicyclopentanyl (meth)acrylate) and methyl (meth)acrylate group Unit (c). The photosensitive resin composition according to claim 1 or 2, wherein relative to the aforementioned The total amount of the copolymer (A) and the reactive diluent (C) is 100 parts by mass, and it contains 5 to 80 parts by mass of the colorant (E), and is for color filters. The photosensitive resin composition according to claim 8, 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 of claim 8 or 9. An image display element is characterized by having the color filter as claimed in claim 10. A method for manufacturing a color filter, characterized by comprising: coating the photosensitive resin composition as claimed in claim 8 or 9 on a substrate, exposing it to light, and after alkali developing, baking at a temperature below 160° C. The steps of forming a shaded pattern. A method for producing a photosensitive resin composition, comprising: in the presence of a hydroxyl-containing organic solvent (B), a (meth)acrylate containing a blocked isocyanato group, and an unsaturated carboxylic acid, with polymerizable unsaturated Bond and hydroxyl monomers are copolymerized to synthesize copolymer (A), and secondly, the step of coordinating reactive diluent (C) and photopolymerization initiator (D); The total amount of the reactive diluent (C) is 100 parts by mass, containing 10 to less than 100 parts by mass of the copolymer (A), 30 to 1,000 parts by mass of the hydroxyl-containing organic solvent (B), and the reactive diluent (C) more than 0 to 90 parts by mass, 0.1 to 30 parts by mass of the above-mentioned photopolymerization initiator (D), and 0.1 to 30 parts by mass of the above-mentioned blocked isocyanato group-containing (meth)acrylate The dissociation rate was 5 to 99 mass % after heating at 100° C. for 30 minutes.