JPWO2019026547A1 - Photosensitive resin composition and method for producing the same - Google Patents

Abstract

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

Description

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

In recent years, from the viewpoint of resource saving and energy saving, photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron rays have been widely used in the fields of various coatings, printing, paints and adhesives. Also in the field of electronic materials such as printed wiring boards, photosensitive resin compositions curable by active energy rays are used for solder resists, resists for color filters, and the like. Furthermore, the required properties for curable photosensitive resin compositions are becoming increasingly diverse and sophisticated, but among them, short-time curability considering productivity and low-temperature curability that suppresses thermal damage to applied components. Is required.

The color filter generally includes a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, and a black matrix formed at the boundary between the pixels. It is composed of a pixel and a protective film formed on the black matrix. A color filter having such a structure is usually manufactured by sequentially forming a black matrix, pixels and a protective film on a transparent substrate. Various methods have been proposed as a method for forming pixels and a black matrix (hereinafter, the pixels and the black matrix are referred to as “coloring patterns”). Among them, the pigment/dye dispersion method prepared by a photolithography method in which a photosensitive resin composition is used as a resist and repeating coating, exposure, development and baking is excellent in durability and coloring with few defects such as pinholes. It is the current mainstream because it gives patterns.

Generally, 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. The pigment/dye dispersion method has the above-mentioned advantages, but on the other hand, because it repeatedly forms a pattern of black matrix, R, G, and B, high heat resistance is required, and as a colorant capable of withstanding a high baking temperature. However, it is often a problem that there are limitations such as the types of colorants that can be used.

In Patent Document 1, low temperature curing is possible by using a compound 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. A colored composition having improved storage stability is disclosed.

Patent Document 2 discloses a polymer precursor in which a reaction to a final product is promoted by heating with a basic substance or in the presence of a basic substance, and a specific base generation in which a base is generated by irradiation with electromagnetic waves and heating. By using a photosensitive resin composition containing an agent, low temperature curing is possible.

JP, 2013-68843, A JP, 2014-70148, A

In recent years, flexible displays such as electronic paper have become popular. As a substrate for this flexible display, a plastic substrate such as polyethylene terephthalate is under study. This substrate has the property of expanding or contracting during baking, and it is necessary to lower the temperature of the baking process. However, the level achieved in Patent Document 1 is insufficient to satisfy the above requirements. Further, in Patent Document 2, although low-temperature curability is improved, storage stability is low and practical application is difficult.

The present invention has been made in order to solve the above-mentioned problems, and is a photosensitive resin which has a good developability and storage stability and gives a cured coating film excellent in solvent resistance even when cured at a low temperature. It is an object to provide a composition and a method for producing the same.
Another object of the present invention is to provide a color filter having a colored pattern with excellent solvent resistance, a method for producing the same, and an image display device equipped with the color filter.

That is, the present invention is shown in the following [1] to [15].
[1] A copolymer (A) containing a structural unit (a) having a block isocyanato group and a structural unit (b) having an acid group, a hydroxyl group-containing organic solvent (B), and a reactive diluent (C). And a photopolymerization initiator (D).
[2] The structural unit (a) having the block isocyanato group is a structural unit derived from a block isocyanato group-containing (meth)acrylate, and the block isocyanato group of the block isocyanato group-containing (meth)acrylate is dissociated. The photosensitive resin composition according to [1], which has a rate of 5 to 99 mass% when heated at 100° C. for 30 minutes.
[3] The blocking agent of the structural unit (a) having a block isocyanato group is one or more selected from the group consisting of diethyl malonate, 3,5-dimethylpyrazole and methylethylketoxime [1] or [ 2] The photosensitive resin composition as described in [2].
[4] The hydroxyl group-containing organic solvent (B) is 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-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerin monoalkyl ether, glycerin dialkyl ether, methanol, ethanol , Propanol, C _5-6 cycloalkane diol, C _5-6 cycloalkane dimethanol, ethyl lactate and diacetone alcohol, which are one or more selected from [1] to [3]. The photosensitive resin composition of.
[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 copolymer (A) contains 1 to 40 mol% of the structural unit (a) having the block isocyanato group and 1 to 60 mol% of the structural unit (b) having the acid group [ The photosensitive resin composition according to any one of 1] to [5].
[7] The molar ratio of the structural unit (a) having the block isocyanato group to the structural unit (b) having the acid group in the copolymer (A) is 10:90 to 50:50 [ The photosensitive resin composition according to any one of 1] to [6].
[8] The copolymer (A) is 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate, 2-[O-(1′-methylpropylideneamino)carboxaminomethacrylate. ] Ethyl, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid-4-[[[[[2-[ (2-Methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amine]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-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amine]ethyl ester A structural unit (a) derived from at least one selected from the group consisting of, a structural unit (b) derived from (meth)acrylic acid, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dicyclo The photosensitive resin composition according to any one of [1] to [7], containing a structural unit (c) derived from at least one selected from the group consisting of pentanyl (meth)acrylate and methyl (meth)acrylate. object.
[9] The photosensitive resin composition according to any one of [1] to [8], which further contains a colorant (E) and is for a color filter.
[10] 10 to 100 parts by mass of the copolymer (A), 100 parts by mass of the copolymer (A) and the reactive diluent (C), the hydroxyl group-containing organic solvent ( B) is 30 to 1,000 parts by mass, the reactive diluent (C) is more than 0 parts by mass to 90 parts by mass, the photopolymerization initiator (D) is 0.1 to 30 parts by mass, and the colorant ( The photosensitive resin composition according to [9], which contains 5 to 80 parts by mass of E).
[11] The photosensitive resin composition according to [9] or [10], wherein the colorant (E) contains a pigment.

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

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

[14] A step of applying a photosensitive resin composition according to any one of [9] to [11] to a substrate, exposing it to light, developing it with an alkali, and baking it at a temperature of 160° C. or lower to form a colored pattern. A method for producing a color filter, comprising:

[15] A block isocyanato group-containing (meth)acrylate and an unsaturated carboxylic acid are subjected to a copolymerization reaction in the presence of a hydroxyl group-containing organic solvent (B) to synthesize a copolymer (A), and then reactive dilution. A method for producing a photosensitive resin composition, which comprises a step of blending the agent (C) and the photopolymerization initiator (D).

According to the present invention, it is possible to provide a photosensitive resin composition having good developability and storage stability, and forming a cured coating film having excellent solvent resistance even when cured at a low temperature, and a method for producing the same. it can.
Further, according to the present invention, it is possible to provide a color filter having a colored pattern having excellent solvent resistance, a method for producing the same, and an image display device including the color filter.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention comprises a copolymer (A) containing a structural unit (a) having a block isocyanato group and a structural unit (b) having an acid group, and a hydroxyl group-containing organic solvent (B). , A reactive diluent (C) and a photopolymerization initiator (D).

<Copolymer (A)>
<Structural Unit (a) Having Block Isocyanato Group>
The structural unit (a) having a block isocyanato group contained in the copolymer (A) is a structural unit derived from a block isocyanato group-containing monomer. Examples of the monomer include a monomer having an ethylenically unsaturated bond and a blocked isocyanato group, such as a vinyl group in the molecule, an isocyanato group in an isocyanate compound having a (meth)acryloyloxy group, etc., blocked with a blocking agent. Examples of the compound include The reaction between the isocyanate compound and the blocking agent can be carried out regardless of the presence or absence of a solvent. When using a solvent, it is necessary to use a solvent which is inactive to the isocyanato group. In the blocking reaction, organic metal salts of tin, zinc, lead, etc., tertiary amines, etc. may be used as catalysts. The reaction can generally be carried out at -20 to 150°C, preferably 0 to 100°C. Examples of the isocyanate compound include compounds represented by the following formula (1).

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

As the isocyanate compound represented by the above formula (1), specifically, 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, methacryloyl isocyanate and the like can be mentioned. Further, an equimolar (1 mol:1 mol) reaction product of 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, more preferably an ethyl group. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4-(or 2,6-)tolylene 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 and the like can be mentioned.

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 preferable, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are preferable. More preferable.

In addition, what is described as (meth)acrylate in this specification means that either acrylate or methacrylate may be used, and the description of (meth)acrylic acid may be either acrylic acid or methacrylic acid. Means

Examples of the blocking agent that blocks the isocyanato group in the isocyanate compound include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol. , Methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, and other alcohols; phenol, cresol, 2,6-xylenol, 3,5-xylenol, 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, Phenols such as p-chlorophenol; active methylenes such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate and acetylacetone; mercaptans such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan; diphenylamine, phenyl Amines such as naphthylamine, aniline and carbazole; acid amides such as acetanilide, acetanisidide, acetic acid amide and benzamide; acid imides such as succinimide and maleic acid imide; imidazole, 2-methylimidazole, 2-ethylimidazole and the like Imidazole type; pyrazole type such as pyrazole and 3,5-dimethylpyrazole; urea type such as urea, thiourea and ethylene urea; carbamate type such as phenyl N-phenylcarbamate and 2-oxazolidone: ethyleneimine, polyethyleneimine And the like; oximes such as formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime, methylisobutylketoxime and cyclohexanoneoxime; bisulfite such as sodium bisulfite and potassium bisulfite. These blocking agents may be used alone or in combination of two or more.

The blocking agent protects the highly reactive isocyanato group, but the heating dissociates the blocked isocyanato group to regenerate the isocyanato group. In the present invention, the isocyanato group reacts with a reactive functional group contained in the copolymer (A) or the reactive diluent (C), that is, an acid group or a hydroxy group or amino group optionally contained. , To form a cured product having a high crosslinking density.

From the viewpoint of low-temperature curability and storage stability of the photosensitive resin composition described below, it is preferable to use a block isocyanato group-containing (meth)acrylate as the monomer that gives the structural unit (a) having a block isocyanato group. .. A block isocyanato group having a dissociation rate of the block isocyanato group of preferably 5 to 99% by mass, more preferably 8 to 97% by mass, and most preferably 10 to 95% by mass when heat-treated at 100° C. for 30 minutes. It is preferable to use a containing (meth)acrylate. The dissociation rate of the block isocyanato group of the block isocyanato group-containing (meth)acrylate was determined by preparing an n-octanol solution in which the concentration of the block isocyanato group-containing (meth)acrylate was 20% by mass, and adding 1 to the solution. HPLC analysis of the mass reduction ratio of the block isocyanato group-containing (meth)acrylate after heating at 100° C. for 30 minutes after adding dibutyltin laurate of mass% and phenothiazine (polymerization inhibitor) of 3 mass% The value measured by When the block isocyanato group-containing (meth)acrylate having a dissociation rate in the above range is used, the stability of the copolymer at the time of synthesis can be sufficiently ensured, and the baking temperature at the time of producing a cured coating film can be sufficiently increased. It can be lowered, and the solvent resistance of the cured coating film can be sufficiently secured. Examples of the blocking agent of a block isocyanato group-containing (meth)acrylate having such a dissociation rate include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methylethylketoxime, 3,5. -Dimethylpyrazole and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole and methylethylketoxime are more preferable from the viewpoint of low temperature curability.

It is also preferable to use a block isocyanato group-containing (meth)acrylate having a block isocyanato group dissociation temperature of 80°C or higher in the block isocyanato group-containing (meth)acrylate. When a block isocyanato group-containing (meth)acrylate having a dissociation temperature of 80° C. or higher is used, the stability of the copolymer at the time of synthesis can be sufficiently ensured, and unintended crosslinking at the time of the modification reaction described later The reaction can be reduced. On the other hand, when the dissociation temperature of the block isocyanato 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. The dissociation temperature of the block isocyanato group of the block isocyanato group-containing (meth)acrylate was determined by preparing an n-octanol solution having a concentration of the block isocyanato group-containing (meth)acrylate of 20% by mass, and adding 1 to the solution. After the addition of dibutyltin laurate in an amount of 3% by mass and phenothiazine (a polymerization inhibitor) in an amount of 3% by mass, the mixture is heated at a predetermined temperature and the mass reduction ratio of the block isocyanato group-containing (meth)acrylate after 30 minutes. Is determined by HPLC analysis, and the temperature at which the mass reduction rate is 80% by mass or more is defined as the dissociation temperature of the block isocyanato group.

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

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

<Structural 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 an acid group-containing monomer (provided that the structural unit (a) having a block isocyanato group is except). Examples of the acid group include a carboxyl group, a sulfo group, a phospho group and the like, and among these, the carboxyl group is preferable from the viewpoint of easy availability. Examples of the monomer that provides the structural unit (b) having an acid group include a monomer having a polymerizable unsaturated bond and an acid group, such as unsaturated carboxylic acid or its anhydride, unsaturated sulfonic acid, and unsaturated phosphonic acid. Can be mentioned. Specific examples of preferable monomers include (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid. , Unsaturated carboxylic acids such as maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; -Unsaturated sulfonic acids such as -methyl propane sulfonic acid, tert-butyl acrylamide sulfonic acid and p-styrene sulfonic acid; unsaturated phosphonic acids such as vinyl phosphonic acid; These monomers may be used alone or in combination of two or more. Among these, unsaturated carboxylic acids are preferable, and (meth)acrylic acid is more preferable, from the viewpoints of excellent alkali developability and easy availability.

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

The proportion of the structural unit (b) having an acid group contained in the copolymer (A) is not particularly limited, but is preferably 1 to 60 mol%, more preferably 10 to 50 mol%, and most preferably 15 to It is 40 mol %. When the proportion of the structural unit (b) having an acid group is from 1 to 60 mol %, an appropriate alkali development rate can be obtained and a fine pattern can be formed.

In the copolymer (A), the molar ratio of the structural unit (a) having a block isocyanato group and the structural unit (b) having an acid group can be, for example, 1:99 to 99:1, From the viewpoint of solvent resistance of the cured coating film and storage stability of the copolymer (A), it is more preferably 5:95 to 75:25, most preferably 10:90 to 50:50.

<Other structural units (c)>
In the present invention, the constitutional unit contained in the copolymer (A) is a constitutional unit (a) having a block isocyanato group and a constitutional unit (b) having an acid group, and other constitutions copolymerizable therewith. The unit (c) may be contained (excluding those corresponding to the structural unit (a) having the block isocyanato group and the structural unit (b) having the acid group). Specific examples of the other structural unit (c) include a structural unit (c-1) having an epoxy group, a structural unit (c-2) having a hydroxyl group, and a constitution other than (c-1) and (c-2). A unit (c-3) etc. are mentioned. The proportion of the other structural unit (c) contained in the copolymer (A) is not particularly limited, but is preferably 0 to 80 mol%, more preferably 0 to 70 mol%, and most preferably 0 to 60 mol. %.

As a monomer used for introducing the structural unit (c-1) having an epoxy group, a monomer having a polymerizable unsaturated bond and an epoxy group, for example, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2- Methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (Meth)acrylic ester derivative containing an epoxy group such as (meth)acrylate; 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl) ) 3,4-epoxycyclohexane such as ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate Examples thereof include (meth)acrylic acid ester derivatives containing an epoxy group-containing alicyclic carbon ring such as a ring; vinyl ether compounds containing an epoxy group; and allyl ether compounds containing an epoxy group. These monomers may be used alone or in combination of two or more. Among these, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl Epoxy group-containing (meth)acrylates such as (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, and glycidyloxyphenyl (meth)acrylate are preferable, and glycidyl (meth)acrylate is more preferable.

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 constitutional unit (c-1) having an epoxy group is introduced into the copolymer (A), the proportion of the constitutional unit (c-1) having an epoxy group is not particularly limited, but preferably more than 0 mol%. -60 mol%, more preferably more than 0 mol% to 50 mol%, most preferably more than 0 mol% to 40 mol%.

The monomer used for introducing the structural unit (c-2) having a hydroxyl group is a monomer having a polymerizable unsaturated bond and a hydroxyl group, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth). Acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 4-hydroxybutyl acrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyl Examples thereof include oxyethylhexahydrophthalic acid, 2-acryloyloxyethylphthalic acid and 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid. These monomers 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, 2-hydroxy-3-phenoxypropyl. A (meth)acrylic acid ester derivative containing a hydroxyl group such as acrylate or 4-hydroxybutyl acrylate is preferable, and 2-hydroxyethyl (meth)acrylate is more preferable.

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, but preferably more than 0 mol% to 50. Mol%, more preferably more than 0 mol% to 40 mol%, most preferably more than 0 mol% to 30 mol%.

Specific examples of the monomer used to introduce the structural unit (c-3) other than the structural unit (c-1) having an epoxy group and the structural unit (c-2) having a hydroxyl group are styrene and α- Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p- Aromatic vinyl compounds such as nitrostyrene, p-cyanostyrene, p-acetylaminostyrene; 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 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]deca-8-ene, tricyclo[5.2.1.0 ^2,6 ]deca-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 ]dodec-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 . 0 ^1,6 ]dodeca-3-ene, 8-ethylidene tetracyclo[4.4.0.1 ^2,5 . 1 ^7,12 ] Dodeca-3-ene, 8-ethylidenetetracyclo[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] pentadeca-4-ene, pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] pentadeca-3-ring having a norbornene structure such as ene-olefin; butadiene, isoprene, dienes such as 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, pentyl (meth)acrylate, neopentyl (meth) Acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth) Acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (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, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate isobornyl (meth)acrylate, adamantyl (meth)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, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth) (Meth)acrylic acid ester such as acrylate, phenoxy polyethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate; ) Acrylic amide, (meth)acrylic acid N,N-di Methylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenylamide, etc. (Meth)acrylic acid amide; (meth)acrylic acid anilide, (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 citraconic acid, diethyl maleic acid, diethyl fumarate, and itaconic acid diethyl; N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl) Monomaleimides such as maleimide; and the like. Among these, (meth)acrylic acid ester is preferable, and methyl (meth)acrylate and dicyclopentanyl (meth)acrylate are particularly preferable. These monomers may be used alone or in combination of two or more.

<Method for producing copolymer (A)>
The ratio of the block isocyanato group-containing monomer (a0) and the acid group-containing monomer (b0) used in the production of the copolymer (A) is not particularly limited, but preferably (a0) 1 to 40 mol%. And (b0) 1 to 60 mol%, more preferably (a0) 2 to 30 mol% and (b0) 10 to 50 mol%, and most preferably (a0) 3 to 25 mol% and (b0) 15 to. It is 40 mol %. When the copolymer (A) further contains another structural unit (c), the block isocyanato group-containing monomer (a0), the acid group-containing monomer (b0), and the acid group-containing monomer used in the production of the copolymer (A). The proportion of the other monomer (c0) is preferably (a0) 1 to 40 mol%, (b0) 1 to 60 mol% and (c0) more than 0 mol% to 80 mol%, more preferably (a0). 2 to 30 mol%, (b0) 10 to 50 mol% and (c0) more than 0 mol% to 70 mol%, most preferably (a0) 3 to 25 mol%, (b0) 15 to 40 mol% and ( c0) It is more than 0 mol% to 60 mol %.

The copolymerization reaction of the block isocyanato group-containing monomer (a0), the acid group-containing monomer (b0) and the other monomer (c0) can be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. Although it can be carried out, it is preferably carried out in the presence of a hydroxyl group-containing organic solvent (B) described later, from the viewpoint that abnormal polymerization can be prevented and the polymerization reaction can be carried out stably. By carrying out the copolymerization reaction in the presence of the hydroxyl group-containing organic solvent (B), the isocyanato group reacts with the hydroxyl group of the hydroxyl group-containing organic solvent (B) even if the block isocyanato group is dissociated to form an isocyanato group. Abnormal polymerization is prevented. In the copolymer (A) thus obtained, it is considered that a part of the blocking agent that blocked the isocyanato group was replaced with the hydroxyl group-containing organic solvent (B). For example, these monomers may be dissolved in the hydroxyl group-containing organic solvent (B), a polymerization initiator may be added to the solution, and the polymerization reaction may be performed at 50 to 100° C. for 1 to 20 hours. At this time, when the polymerization reaction is performed at a temperature at which the block isocyanato group of the block isocyanato group-containing monomer (a0) dissociates, the isocyanato group generated by the dissociation of the block isocyanato group reacts with the acid group to form a gel. It is preferable to carry out the polymerization at a temperature lower than the dissociation temperature of the block isocyanato group, preferably about 20 to 50° C. lower than the dissociation temperature of the block isocyanato group.

The polymerization initiator that can be used in this copolymerization reaction is not particularly limited, but for example, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2- Examples include ethyl hexanoate. These polymerization initiators may be used alone or in combination of two or more kinds. The amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, when the total amount of the monomers charged is 100 parts by mass.

The polystyrene-equivalent weight average molecular weight of the copolymer (A) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 3,000 to 40,000 by the production method described above. It is possible to obtain a copolymer (A) having When the weight average molecular weight of the copolymer (A) is 1,000 or more, the colored pattern is less likely to be chipped 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 developing time becomes appropriate and the practicality is secured.

Further, the acid value (JIS K6901 5.3) of the copolymer (A) can be appropriately selected, but when blended in the photosensitive resin composition, it is preferably 20 to 300 KOHmg/g, more preferably 30 to 300 KOHmg/g. It is in the range of 200 KOHmg/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 good. On the other hand, when the acid value of the copolymer (A) is 300 KOHmg/g or less, the exposed portion (photocured portion) is difficult to dissolve in the alkali developing solution, and the pattern shape becomes good.

In the present invention, the copolymer (A) contains a block isocyanato group in the molecule. The content of the block isocyanato group may be appropriately selected, but it is usually selected in the range such that the block isocyanato group equivalent is 400 to 6,000, preferably 1,000 to 5,000. The block isocyanato group equivalent is the mass of the polymer per 1 mol of the block isocyanato group contained in the polymer, and is determined by dividing the mass of the polymer by the number of moles of the block isocyanato group contained in the polymer. It is possible (g/mol). In the present invention, the block isocyanato group equivalent is a theoretical value calculated from the charged amount of the block isocyanato group-containing monomer.

<Hydroxyl group-containing organic solvent (B)>
The hydroxyl group-containing organic solvent (B) may be any organic solvent containing a hydroxyl group, and examples thereof include ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, propylene glycol monoaryl ether, and dipropylene glycol monoalkyl ether. Ether, tripropylene glycol monoalkyl ether, 3-methoxy-1-butanol, 1,3-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerin monoalkyl Examples thereof include ether, glycerin dialkyl ether, methanol, ethanol, propanol, C _5-6 cycloalkane diol, C _5-6 cycloalkane dimethanol, ethyl lactate and diacetone alcohol. Among these, ethyl lactate, diacetone alcohol, 3-methoxy-1-butanol and propylene glycol monomethyl ether are preferable, and propylene glycol monomethyl ether is particularly preferable, from the viewpoint of film formability during production of a cured coating film and easy availability. preferable. These hydroxyl group-containing organic solvents (B) may be used alone or in combination of two or more.

In the present invention, by using the copolymer (A) containing the structural unit (a) having a block isocyanato group and the structural unit (b) having an acid group in combination with the hydroxyl group-containing organic solvent (B), The storage stability of the resin composition is improved.

Further, in the photosensitive resin composition of the present invention, a solvent other than the hydroxyl group-containing organic solvent (B) may be used in combination.

<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 among them, a compound having a plurality of polymerizable functional groups is preferable. By using such a reactive diluent (C) in combination with the copolymer (A), the viscosity can be adjusted, and the strength of the cured product to be formed and 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, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxy. Methyl (meth)acrylamide, methyl (meth)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, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth ) Acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, phthalic acid derivative half (meth)acrylate, etc. (Meth)acrylates; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene and vinyltoluene; carboxylic acid esters such as vinyl acetate and vinyl propionate. Further, these monomers may be used alone or in combination of two or more kinds.

Examples of the polyfunctional 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, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth) Acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydi Ethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycidyl ether di(meth) Acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (that is, tolylene diisocyanate), Reaction products of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and the like with 2-vidroxyethyl (meth)acrylate, (meth)acrylates such as tri(meth)acrylate of tris(hydroxyethyl)isocyanurate; divinylbenzene, diallyl phthalate, diallyl Aromatic vinyl compounds such as benzenephosphonate; Dicarboxylic acid esters such as divinyl adipate; Triallyl cyanurate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, polyhydric alcohol and N-methylol(meth)acrylamide And the like. These monomers may be used alone or in combination of two or more.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) is not particularly limited, but for example, benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1 -Dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-benzyl-2 -Acetophenones such as dimethylamino-1-(4-morpholinophenyl)butanone-1; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; xanthone, thioxanthone, Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-(1-t-butyldioxy-1-methylethyl) ) Benzophenones such as benzophenone and 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone; acylphosphine oxides; and the like. These photopolymerization initiators (D) may be used alone or in combination of two or more.

In addition to the above components, 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. Good. The blending amount of these additives is not particularly limited as long as the effects of the present invention are not impaired.

<Photosensitive resin composition for color filter>
Further, the photosensitive resin composition of the present invention can further contain a colorant (E) to give a photosensitive resin composition for a color filter.

The colorant (E) is not particularly limited as long as it can be dissolved or dispersed in the hydroxyl group-containing organic solvent (B), and examples thereof include dyes and pigments. As the dye, from the viewpoint of solubility in a hydroxyl group-containing organic solvent (B) or an alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., an acidic group such as carboxylic acid or sulfonic acid is used. It is preferable to use an acidic dye having a salt, a salt of the acidic dye with a nitrogen compound, a sulfonamide body of the acidic dye, or the like.

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 chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73. , 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216. , 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof. Among these, azo, xanthene, anthraquinone or phthalocyanine acid dyes are preferable. These dyes may be used alone or in combination of two or more, depending on the intended color of the pixel.

Examples of pigments include C.I. 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, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; C.I. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like; I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and the like; C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments; C.I. I. Pigment Green 7, 36, 58, 59 and other green pigments; C.I. I. Pigment Brown 23, 25 and other brown pigments; C.I. I. Pigment Black 1 and 7, black pigments such as carbon black, titanium black and iron oxide.

These colorants (E) may be used alone or in combination of two or more, depending on the intended color of the pixel. The above dyes and pigments may be used in combination depending on the intended color of the pixel.

When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. As the dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. Examples include a system dispersant. As such a polymer dispersant, EFKA (manufactured by EFKA CHEMICALS BV (EFKA)), Disperbyk (manufactured by Big Chemie), DISPARON (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Zeneca) are commercially available. You may use what has been. The blending amount of the dispersant may be appropriately set according to the type of pigment or the like used.

The blending amounts of the copolymer (A), the hydroxyl group-containing organic solvent (B), the reactive diluent (C), the photopolymerization initiator (D) and the colorant (E) in the photosensitive resin composition for color filters are as follows: 10-100 parts by mass of the copolymer (A) and a hydroxyl group-containing group based on 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C) in the photosensitive resin composition for a color filter. The organic solvent (B) is 30 to 1,000 parts by mass, the reactive diluent (C) is more than 0 parts by mass 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, preferably 20 to 80 parts by mass of the copolymer (A), 50 to 800 parts by mass of the hydroxyl group-containing organic solvent (B), and 20 of the reactive diluent (C). To 80 parts by mass, the photopolymerization initiator (D) is 0.5 to 20 parts by mass, the colorant (E) is 5 to 70 parts by mass, and more preferably the copolymer (A) is 30 to 75 parts by mass. Parts, the hydroxyl group-containing organic solvent (B) is 100 to 700 parts by mass, the reactive diluent (C) is 25 to 70 parts by mass, the photopolymerization initiator (D) is 1 to 15 parts by mass, and the colorant (E) is 10 to 60 parts by mass. If it is the compounding quantity of this range, it will be a photosensitive resin composition for color filters which has suitable viscosity. Even in the case of a photosensitive resin composition containing no colorant (E), the copolymer (A), the hydroxyl group-containing organic solvent (B), the reactive diluent (C) and the photopolymerization initiator (D) The above numerical range can be applied to the compounding amount.

<Production of photosensitive resin composition>
The photosensitive resin composition of the present invention can be produced by mixing the above components using a known mixing device. Further, by copolymerizing the block isocyanato group-containing (meth)acrylate and the unsaturated carboxylic acid in the presence of the hydroxyl group-containing organic solvent (B), the copolymer (A) and the hydroxyl group-containing organic solvent (B) are obtained. It is also possible to prepare a composition containing the above by mixing the reactive diluent (C), the photopolymerization initiator (D) and the colorant (E) which is an optional component.

The photosensitive resin composition obtained as described above has alkali developability and is therefore suitable as a resist. To cure the photosensitive resin composition, the baking temperature may be appropriately selected within the range of 250° C. or lower. However, since the copolymer (A) used in the present invention has excellent curability at low temperatures, conventional materials can be used. The baking temperature can be lowered as compared with. When a pigment is used as the colorant (E) in the photosensitive resin composition, sufficient curability can be obtained even at a baking temperature of 160°C or lower. The photosensitive resin composition of the present invention is advantageous in terms of energy consumption because the crosslinking reaction sufficiently proceeds even if the baking temperature is lowered. Further, it becomes possible to use even a colorant (E) or a substrate having poor heat resistance, the original characteristics of the colorant can be obtained, and application to various substrates becomes possible. From this viewpoint, 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 uniform depending on the type of block isocyanato group contained in the copolymer (A), but it is necessary that the lower limit is not less than the dissociation temperature of the block isocyanato group, and usually 80°C. Or higher, preferably 90° C. or higher, more 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. The baking time can be appropriately selected, but is usually 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

INDUSTRIAL APPLICABILITY The photosensitive resin composition of the present invention is used for producing various types of resists, particularly color filters incorporated in organic EL displays (for black PDL), liquid crystal display devices, solid-state imaging devices such as CCD and CMOS, and the like. Is suitable as Further, since the photosensitive resin composition of the present invention gives a cured coating film having excellent solvent resistance and curing characteristics at low temperatures, it can be used for various coatings, adhesives, binders for printing inks and the like.

The photosensitive resin composition of the present invention has good developability and storage stability, and can form a colored pattern having excellent solvent resistance even when the baking temperature during pattern formation is lowered, It is extremely useful as a photosensitive material for filters. In addition, the photosensitive resin composition of the present invention can contribute to the development of flexible displays, the reduction of energy consumption in the manufacturing process, and the relaxation of the restriction of the coloring agent to be used with the low temperature curing.

<Color filter>
Next, a color filter having a colored pattern made of a cured product of the photosensitive resin composition for a color filter of the present invention will be described. The color filter of the present invention has a colored pattern formed by using the above-described photosensitive resin composition for a color filter. The color filter is usually composed of a substrate, RGB pixels formed on the substrate, a black matrix formed at the boundaries of the respective pixels, and a protective film formed on the pixels and the black matrix. In this structure, a known structure can be adopted as the other structure except that the pixel and the black matrix (coloring pattern) are formed by using the above-described photosensitive resin composition for color filter.

Next, an embodiment of a method of manufacturing a color filter will be described. First, a colored pattern is formed on the 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 polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate, or the like can be used as appropriate. it can.

The colored pattern can be formed by a photolithography method. Specifically, after coating the above-mentioned photosensitive resin composition on a substrate to form a coating film, the coating film is exposed through a photomask having a predetermined pattern to photo-cur the exposed portion. Then, the unexposed portion is developed with an alkaline aqueous solution and then baked to form a predetermined colored pattern.

The method for applying the photosensitive resin composition is not particularly limited, but a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method or the like can be used. Further, after the application of the photosensitive resin composition, the hydroxyl group-containing organic solvent (B) may be volatilized by heating with a heating means such as a circulation oven, an infrared heater or a hot plate, if necessary. The heating conditions are not particularly limited and may be appropriately set depending on the type of photosensitive resin composition used. Generally, heating may be performed at a temperature of 50° C. to 120° C. for 30 seconds to 30 minutes.

Then, the formed coating film is partially exposed by irradiating it with an active energy ray such as ultraviolet rays or excimer laser light through a negative mask. The energy dose for irradiation may be appropriately selected according to the composition of the photosensitive resin composition, and is preferably 30 to 2000 mJ/cm ² , for example. The light source used for the exposure is not particularly limited, but a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp and the like can be used.

The alkaline aqueous solution used for the development is not particularly limited, but an aqueous solution of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide or the like; an aqueous solution of an amine compound such as ethylamine, diethylamine or dimethylethanolamine; tetra. Methylammonium, 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 p-phenylenediamine such as sulfate, hydrochloride or p-toluenesulfonate thereof An aqueous solution of a system compound can be used. In addition, an antifoaming agent or a surfactant may be added to these aqueous solutions, if necessary. Further, it is preferable to wash with water and dry after the development with the above alkaline aqueous solution.

The baking conditions are not particularly limited, and heat treatment may be performed depending on the type of the photosensitive resin composition used. In the conventional photosensitive resin composition, when the baking temperature is 200° C. or lower, the solvent resistance of the colored pattern is insufficient, but in the photosensitive resin composition for a color filter of the present invention, when baking is performed at a temperature of 120° C. or lower. Even in this case, a colored pattern exhibiting sufficient solvent resistance can be 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 manufacturing. From this viewpoint, the baking temperature is usually 210° C. or lower, preferably 160° C. or lower, more preferably 120° C. or lower, and the baking time is usually 10 minutes to 4 hours, preferably 20 minutes to 2 hours. Done.

Application, exposure, development and baking as described above are sequentially repeated using the photosensitive resin composition for black matrix and the photosensitive resin composition for red, green and blue pixels to obtain a desired coloring pattern. Can be formed. In the above, the method for forming a colored pattern by photocuring has been described, but if a photosensitive resin composition containing a curing accelerator and a known epoxy resin is used instead of the photopolymerization initiator (D), an inkjet method is used. It is also possible to form a desired colored pattern by applying the coating method and then heating. Next, a protective film is formed on the colored pattern (each pixel of RGB and the black matrix). The protective film is not particularly limited, and a known film may be used.

The color filter produced in this manner has excellent sensitivity and developability, and is produced using a photosensitive resin composition that can be cured at a low temperature and gives a colored pattern having excellent solvent resistance. It has an excellent coloring pattern with little color change.

<Image display device>
The image display device of the present invention is an image display device provided with the color filter described above, and specific examples thereof include a liquid crystal display device, an organic EL display device, a solid-state imaging device such as a CCD device or a CMOS device, and the like. The image display device of the present invention may be manufactured by a conventional method except that the above color filter is used. For example, in the case of manufacturing a liquid crystal display element, the color filter is formed on a substrate, and then electrodes, spacers and the like are sequentially formed. Then, an electrode or the like may be formed on the other substrate, and the two may be attached to each other to inject and seal a predetermined amount of liquid crystal.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In this example, all parts and percentages are based on mass unless otherwise specified. The methods for measuring the acid value and the weight average molecular weight are as follows.
(1) Acid value: Acid value of the copolymer (A) measured according to JIS K6901 5.3, and water required to neutralize the acidic component contained in 1 g of the copolymer (A). It means the number of mg of potassium oxide.
(2) The weight average molecular weight (Mw) means a standard polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC) under the following conditions.
Column: Showdex (registered trademark) LF-804+LF-804 (Showa Denko KK)
Column temperature: 40°C
Sample: 0.2% solution of copolymer in tetrahydrofuran Developing solvent: Tetrahydrofuran Detector: Differential refractometer (Showdex RI-71S) (Showa Denko KK)
Flow rate: 1 mL/min

[Synthesis example 1]
149.3 g of propylene glycol monomethyl ether was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, and the mixture was stirred while substituting with nitrogen and heated to 78°C. Next, 22.4 g of dicyclopentanyl methacrylate, 17.2 g of methacrylic acid and 50.2 g of 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate (Karenz MOI-BP, Showa, Japan). Denko Corporation, dissociation rate of block isocyanato group: 70 mass%) and 11.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) What was added and dissolved in 62.8 g of propylene glycol monomethyl ether acetate was dropped into the flask from the dropping funnel. After completion of dropping, the mixture was stirred at 78° C. for 3 hours to carry out a copolymerization reaction to produce a copolymer, and the sample No. Polymer composition 1 (concentration of components other than solvent: 35% by mass) 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 2-9 and Comparative Synthesis Examples 1-2]
A copolymerization reaction was performed under the same conditions as in Synthesis Example 1 except that the raw materials shown in Tables 1 and 2 were used, and Sample No. Polymer compositions 2 to 11 (concentration of components other than solvent: 35% by mass) were obtained. The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Tables 1 and 2. In Tables 1 and 2, 2-[O-(1′-methylproprideneamino)carboxyamino]ethyl methacrylate was produced by Showa Denko KK, Karenz MOI-BM, and the dissociation rate of block isocyanato groups: 18% by mass), and malonate-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester is produced by Showa Denko K.K. MOI-DEM, dissociation rate of block isocyanato group: 90% by mass, and 4-[[[[[2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl benzoate. ]Amine]carbonyl]oxy]methyl ester has a dissociation ratio of the block isocyanato group: 40% by mass, and is benzoic acid-2-[[[[[2-[(2-methyl-1-oxy-2-propene- 1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester has a dissociation rate of the block isocyanato group: 75% by mass, and is 2-propenoic acid-2-methyl-2-[[(3,5- Dimethylphenoxy)carbonyl]amine]ethyl ester has a dissociation rate of the block isocyanato group of 28% by mass.

[Examples 1-9 and Comparative Examples 1-2]
<Preparation of photosensitive resin composition (pigment type)>
In a stainless steel container filled with 200 g of zirconia beads having a diameter of 0.5 mm, C.I. 100 parts by mass of I Pigment Green 36 (coloring agent), 44.98 parts by mass of propylene glycol monomethyl ether acetate, and 25 parts by mass of a dispersant (Disperbyk-161 manufactured by Big Chemie Japan Co., Ltd.) were added, and 2 with a paint shaker. A green pigment dispersion was prepared by mixing and dispersing for a period of time.
This green pigment dispersion was mixed with the other compounding ingredients shown in Table 3 (that is, the polymer composition, the reactive diluent, the photopolymerization initiator and the solvent) to prepare a photosensitive resin composition. The compounding ratio of each component is as shown in Table 3. The photosensitive resin compositions of Examples 1 to 9 were sample No. Sample Nos. 1 to 9 were used to prepare the photosensitive resin compositions of Comparative Examples 1 and 2. Prepared using each of 10-11 polymer compositions. Further, 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 Each of the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2 was applied onto a 5 cm square glass substrate (alkali-free glass substrate) with a thickness after exposure of 2.5 μm. After spin-coating so as to be formed, the solvent was volatilized by heating at 90° C. for 3 minutes. Next, a photomask having a predetermined pattern was arranged at a distance of 100 μm from the coating film, and the coating film was exposed (exposure amount 150 mJ/cm ² ) through the photomask to photo-cur the exposed portion. Then, an unexposed portion was dissolved and developed 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, and then baked at 100° C. for 20 minutes. A predetermined pattern was formed. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation. The criteria for this evaluation are as follows.
◯: No residue X: Residue is shown in Table 4 below.

(2) Evaluation of solvent resistance Each of the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 and 2 had a thickness after baking of 2 on a 5 cm square glass substrate (alkali-free glass substrate). After spin coating so as to have a thickness of 5 μm, the solvent was volatilized by heating at 90° C. for 3 minutes. Next, the coating film was exposed to light having a wavelength of 365 nm to photo-cure the exposed portion, and then left in a dryer at a baking temperature of 100° C. for 20 minutes to prepare a cured coating film. 200 mL of propylene glycol monomethyl ether acetate was placed in a glass bottle with a lid having a capacity of 500 mL, and the glass bottle was left standing at 80° C. The test piece with the cured coating film was immersed therein, and then allowed to stand for 5 minutes while being maintained at 80°C. The color change (ΔE ^* ab) before and after the test piece was dipped in propylene glycol monomethyl ether acetate was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Table 4 shows the measurement results of ΔE ^* ab. 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 Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 and 2 were weighed in equal amounts in a glass container, and the mouth was closed with an aluminum foil so as to prevent dust from entering. Next, each of these samples was allowed to stand in a thermostat kept at 23° C., and the weight average molecular weight (Mw) of the sample after one month was measured. Table 5 shows the change rate of Mw after one month. If the change rate of Mw after 1 month is within 20%, it can be said that the storage stability of the copolymer is excellent.

As can be seen from the results in Table 4, the sample No. The photosensitive resin compositions of Examples 1 to 9 using the polymer compositions of 1 to 9 had good alkali developability and solvent resistance. Furthermore, since the storage stability of the copolymer has a correlation with the storage stability of the photosensitive resin composition containing the copolymer, the results of Table 5 show that the sample No. It can be said that the photosensitive resin compositions of Examples 1 to 9 using the polymer compositions of 1 to 9 also have good storage stability. On the other hand, sample No. The photosensitive resin compositions of Comparative Examples 1 and 2 using the polymer compositions of 10 to 11 have good storage stability, but Sample No. The photosensitive resin composition of Comparative Example 1 using the polymer composition of Example 10 did not have sufficient solvent resistance, and Sample No. The photosensitive resin composition of Comparative Example 2 using the polymer composition of Example 11 had insufficient alkali developability and solvent resistance.

As can be seen from the above results, according to the present invention, it is possible to provide a photosensitive resin composition having excellent developability, solvent resistance and storage stability.

This international application claims priority based on Japanese Patent Application No. 2017-150502 filed on August 3, 2017, and the entire contents of this Japanese patent application are incorporated into this international application. To do.

Claims (15)

A copolymer (A) containing a structural unit (a) having a block isocyanato group and a structural unit (b) having an acid group, a hydroxyl group-containing organic solvent (B), a reactive diluent (C), A photosensitive resin composition comprising a photopolymerization initiator (D). The structural unit (a) having the block isocyanato group is a structural unit derived from a block isocyanato group-containing (meth)acrylate, and the block isocyanato group dissociation rate of the block isocyanato group-containing (meth)acrylate is 100. The photosensitive resin composition according to claim 1, which is 5 to 99 mass% when heated at 30° C. for 30 minutes. The blocking agent of the structural unit (a) having a blocked isocyanato group is diethyl malonate, 3,5-dimethylpyrazole and methylethylketoxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate and 3,5-xylenol. The photosensitive resin composition according to claim 1 or 2, which is one or more selected from the group consisting of: The hydroxyl group-containing organic solvent (B) is 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-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerin monoalkyl ether, glycerin dialkyl ether, methanol, ethanol, propanol, The photosensitivity according to any one of claims 1 to 3, which is at least one selected from the group consisting of C _5-6 cycloalkane diol, C _5-6 cycloalkane dimethanol, ethyl lactate and diacetone alcohol. Resin composition. The photosensitive resin composition according to any one of claims 1 to 4, wherein the structural unit (b) having the acid group is a structural unit derived from an unsaturated carboxylic acid. The copolymer (A) contains 1 to 40 mol% of the structural unit (a) having the block isocyanato group and 1 to 60 mol% of the structural unit (b) having the acid group. 5. The photosensitive resin composition according to any one of 5 above. The molar ratio of the structural unit (a) having the block isocyanato group to the structural unit (b) having the acid group in the copolymer (A) is 10:90 to 50:50. 7. The photosensitive resin composition according to any one of 6 above. The copolymer (A) is 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate, 2-[O-(1′-methylpropylideneamino)carboxyamino]ethyl methacrylate, Malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, benzoic acid-4-[[[[2-[(2- Methyl-1-oxo-2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl-1-oxy-2- From the group consisting of propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carbonyl]amine]ethyl ester. The structural unit (a) derived from at least one selected, the structural unit (b) derived from (meth)acrylic acid, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, dicyclopentanyl (meth ) The photosensitive resin composition according to any one of claims 1 to 7, further comprising a structural unit (c) derived from at least one selected from the group consisting of acrylate and methyl (meth)acrylate. The photosensitive resin composition according to any one of claims 1 to 8, which further contains a colorant (E) and is for a color filter. With respect to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C), 10 to 100 parts by mass of the copolymer (A) and the hydroxyl group-containing organic solvent (B) are contained. 30 to 1,000 parts by mass, the reactive diluent (C) is more than 0 parts by mass to 90 parts by mass, the photopolymerization initiator (D) is 0.1 to 30 parts by mass, and the colorant (E) is The photosensitive resin composition according to claim 9, which is contained in an amount of 5 to 80 parts by mass. The photosensitive resin composition according to claim 9 or 10, wherein the colorant (E) contains a pigment. A color filter having a colored pattern made of a cured product of the photosensitive resin composition according to claim 9. An image display device comprising the color filter according to claim 12. A step of applying a photosensitive resin composition according to any one of claims 9 to 11 to a substrate, exposing it to light, performing alkali development, and then baking at a temperature of 160°C or lower to form a colored pattern. And a method for manufacturing a color filter. A block isocyanato group-containing (meth)acrylate and an unsaturated carboxylic acid are subjected to a copolymerization reaction in the presence of a hydroxyl group-containing organic solvent (B) to synthesize a copolymer (A), and then a reactive diluent (C ) And a photopolymerization initiator (D) are included in the photosensitive resin composition.