KR20200022474A - Photosensitive resin composition and its manufacturing method - Google Patents

Abstract

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), and a photopolymerization initiator Photosensitive resin composition containing (D).

Description

Photosensitive resin composition and its manufacturing method

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

In recent years, from the viewpoint of resource saving and energy saving, photosensitive resin compositions which can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in various coatings, printing, coating materials, adhesives and the like. Moreover, also in the field of electronic materials, such as a printed wiring board, the photosensitive resin composition which can harden | cure by active energy ray is used for a soldering resist, a color filter resist, etc. Moreover, although the required characteristic with respect to the curable photosensitive resin composition is becoming more variously and highly, among them, the short-term curing property which considered productivity, and the low temperature curability which suppresses the thermal damage of the member to apply are calculated | required.

The color filter generally includes a transparent substrate such as a glass substrate, a red (R), green (G), and blue (B) pixel formed on the transparent substrate, a black matrix formed at the boundary of the pixel, a pixel, and It consists of a protective film formed on a black matrix. The color filter which has such a structure is normally manufactured by sequentially forming a black matrix, a pixel, and a protective film on a transparent substrate. Various methods are proposed as a formation method of a pixel and a black matrix (Hereinafter, a pixel and a black matrix are called a "coloring pattern."). Among them, the pigment / dye dispersion method produced by the photolithography method which uses the photosensitive resin composition as a resist and repeats application, exposure, development and baking, has excellent durability and gives a coloring pattern with few defects such as pinholes. Therefore, it is becoming the mainstream of the present.

Generally, the photosensitive resin composition used for the photolithographic method contains alkali-soluble resin, a reactive diluent, a photoinitiator, a coloring agent, and a solvent. In the pigment / dye dispersion method, while having the above-mentioned advantages, in view of the repeated formation of the patterns of the black matrix, R, G, and B, high heat resistance is required and can be used as a colorant capable of withstanding high baking temperatures. It is often problematic that there are limitations such as the kind of colorant being limited.

Patent Literature 1 uses a compound such as an alkali-soluble resin, an ethylenically unsaturated polymerizable compound, a radiation-sensitive polymerization initiator, a colorant, and ethyl 3-aminobenzenesulfonate to enable low-temperature curing and improve storage stability. The coloring composition is disclosed.

Patent document 2 is a photosensitive resin containing the polymer precursor which promotes reaction to a final product by heating with a basic substance or in presence of a basic substance, and the specific base generator which generate | occur | produces a base by irradiation and heating of an electromagnetic wave. Low temperature hardening is enabled by using a composition.

Japanese Unexamined Patent Publication No. 2013-68843 Japanese Laid-Open Patent Publication No. 2014-70148

In recent years, flexible displays, such as electronic paper, have become popular. As a board | substrate of this flexible display, plastic board | substrates, such as a polyethylene terephthalate, are examined. This substrate has the property of elongating or shrinking during baking, and the baking process needs to be lowered. However, the level achieved in Patent Document 1 is insufficient to satisfy the above demand. Moreover, in patent document 2, while low-temperature sclerosis | hardenability was improved, storage stability is low and practical use is difficult.

This invention is made | formed in order to solve the said subject, Comprising: It is an object to provide the photosensitive resin composition which provides the cured coating film excellent in solvent resistance, while being excellent in developability and storage stability, and hardening at low temperature. It is done.

Moreover, an object of this invention is to provide the color filter which has the coloring pattern excellent in solvent resistance, its manufacturing method, and the image display element provided with this color filter.

That is, this invention is shown by the following [1]-[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), a reactive diluent (C), It contains a photoinitiator (D), The photosensitive resin composition characterized by the above-mentioned.

[2] The structural unit (a) having the block isocyanato group is a structural unit derived from the block isocyanato group-containing (meth) acrylate, and the block iso of the block isocyanato group-containing (meth) acrylate The photosensitive resin composition as described in [1] which is 5-99 mass% when the dissociation rate of a cyanato group is heated at 100 degreeC for 30 minutes.

[3] The block agent of the structural unit (a) having the block isocyanato group is one or more selected from the group consisting of diethyl malonate, 3,5-dimethylpyrazole and methylethylketooxime [1] or [ 2] The photosensitive resin composition according to the above.

[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 Photosensitive according to any one of [1] to [3], which is at least one member selected from the group consisting of ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanedimethanol, ethyl lactate and diacetone alcohol Resin composition.

[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 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 [1] ]-The photosensitive resin composition in any one of [5].

[7] The molar ratio of the structural unit (a) having the block isocyanato group in the copolymer (A) and the structural unit (b) having the acid group is from 10:90 to 50:50 [1] ]-The photosensitive resin composition in any one of [6].

[8] The copolymer (A) is a methacrylic acid 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl, methacrylic acid 2- [O- (1'-methylpropylideneamino ) Carboxyamino] 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-propenic acid-2-methyl-2-[[(3,5-dimethyl Phenoxy) carbonyl] amine] ethyl ester, the structural unit (a) derived from at least one selected from the group consisting of; the structural unit (b) derived from (meth) acrylic acid, glycidyl (meth) acrylate, Selected from the group consisting of 2-hydroxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate and methyl (meth) acrylate That even containing a first configuration of the species-derived unit (c) [1] ~ [7] of the photosensitive resin composition according to any one.

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

[10] 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 30 to 1,000 parts by mass of the hydroxyl group-containing organic solvent (B). The part according to [9], wherein the reactive diluent (C) is more than 0 parts by mass to 90 parts by mass, the photopolymerization initiator (D) is contained in an amount of 0.1 to 30 parts by mass, and the colorant (E) is contained in an amount of 5 to 80 parts by mass. Photosensitive resin composition.

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

[12] A color filter comprising a colored pattern comprising 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 comprising applying a photosensitive resin composition according to any one of [9] to [11] to a substrate, exposing and alkali-developing, and baking at a temperature of 160 ° C. or lower to form a colored pattern. The manufacturing method of the color filter characterized by the above-mentioned.

[15] A copolymer (A) is synthesized by copolymerizing a block isocyanato group-containing (meth) acrylate and an unsaturated carboxylic acid in the presence of a hydroxyl group-containing organic solvent (B), followed by a reactive diluent (C) and The manufacturing method of the photosensitive resin composition characterized by including the process of mix | blending a photoinitiator (D).

ADVANTAGE OF THE INVENTION According to this invention, while developability and storage stability are favorable, the photosensitive resin composition which forms the cured coating film excellent in solvent resistance even if it hardens at low temperature can be provided, and its manufacturing method can be provided.

Moreover, according to this invention, the color filter which has the coloring pattern excellent in solvent resistance, its manufacturing method, and the image display element provided with this color filter can be provided.

<Photosensitive resin composition>

The photosensitive resin composition of this invention is a copolymer (A) containing the structural unit (a) which has a block isocyanato group, and the structural unit (b) which has an acidic group, a hydroxyl-containing organic solvent (B), and a reactive diluent. (C) and a photoinitiator (D) are contained, It is characterized by the above-mentioned.

<Copolymer (A)>

<Structural unit (a) having a block isocyanato group>

The structural unit (a) which has the block isocyanato group which a copolymer (A) contains is a structural unit derived from a block isocyanato group containing monomer. As the monomer, for example, a monomer having an ethylenically unsaturated bond and a block isocyanato group, for example, an isocyanato group in an isocyanate compound having a vinyl group, a (meth) acryloyloxy group, etc. in a molecule, The compound blocked by the blocking agent is mentioned. Reaction of an isocyanate compound and a blocking agent can be performed regardless of the presence or absence of a solvent. When using a solvent, it is necessary to use the solvent inactive with respect to an isocyanato group. At the time of blocking reaction, organometallic salts, such as tin, zinc, and lead, tertiary amine, etc. may be used as a catalyst. Although reaction can be generally performed at -20-150 degreeC, it is preferable to carry out at 0-100 degreeC. As an example of the said isocyanate compound, the compound represented by following formula (1) is mentioned.

[Formula 1]

In the formula ^(1), R 1 is a hydrogen atom or a methyl group, R ² is, -CO-, -COOR ³ - (wherein, R ³ is a carbon atom number of 1-6 alkylene group) 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 an alkylene group having 2 to 12 carbon atoms or 6 to 6 carbon atoms which may have a substituent; 12 arylene group). R ² is preferably -COOR ^3- , where R ³ is preferably an alkylene group having 1 to 4 carbon atoms.

Specifically as an isocyanate compound represented by the said Formula (1), 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acryl Late, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate, meta Cryloyl isocyanate etc. are mentioned. Moreover, the equimolar (1 mol: 1 mol) reaction product of 2-hydroxyalkyl (meth) acrylate and a diisocyanate compound can also be used. As an alkyl group of the said 2-hydroxyalkyl (meth) acrylate, an ethyl group or n-propyl group is preferable and an ethyl group is more preferable. As said diisocyanate compound, For example, 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 And lysine diisocyanate.

Among these isocyanate compounds, 2-isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, and 2-isocyanato-1-methyl Ethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate and methacryloyl isocyanate are preferable, and 2-iso More preferred are cyanatoethyl (meth) acrylate and 2-isocyanatopropyl (meth) acrylate.

In addition, in this specification, what was described as (meth) acrylate means that any of acrylate and methacrylate may be sufficient, and the description of (meth) acrylic acid may be any of acrylic acid and methacrylic acid. It means to be.

As a block agent which blocks the isocyanato group in the said isocyanate compound, For example, lactam systems, such as (epsilon) -caprolactam, (delta) -valerolactam, (gamma) -butyrolactam, (beta) -propiolactam; Alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol and cyclohexanol; Butylphenol, p-tert-octylphenol, nonylphenol, such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, Phenols such as dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; Active methylene compounds such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; Mercaptans such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; Amines such as diphenylamine, phenylnaphthylamine, aniline and carbazole; Acid amides such as acetanilide, acetanisidide, amide acetate and benzamide; Acid imides such as succinic acid imide and maleic acid imide; Imidazoles such as imidazole, 2-methylimidazole and 2-ethylimidazole; Pyrazole systems such as pyrazole and 3,5-dimethylpyrazole; Urea system, such as urea, thiourea, and ethylene urea; Carbamate salts such as phenyl N-phenylcarbamate and 2-oxazolidone: imine salts such as ethyleneimine and polyethyleneimine; Oximes such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl keto oxime, methyl isobutyl keto oxime and cyclohexanone oxime; And bisulfite-based compounds such as sodium bisulfite and potassium bisulfite. These blocking agents may be used independently or may be used in combination of 2 or more type.

Although the blocking agent protects the highly reactive isocyanato group, the block isocyanato group dissociates by heating 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, a hydroxyl group or an amino group included as desired, and has a high crosslinking density. To form a cured product.

It is preferable to use block isocyanato-group containing (meth) acrylate as a monomer which gives the structural unit (a) which has a block isocyanato group from a low temperature curability and storage stability of the photosensitive resin composition mentioned later. Do. Preferably the dissociation rate of the block isocyanato group in the case of heat-processing at 100 degreeC for 30 minutes becomes 5-99 mass%, More preferably, it is 8-97 mass%, Most preferably, it becomes 10-95 mass% It is preferable to use block isocyanato-group containing (meth) acrylate. In addition, the dissociation rate of the block isocyanato group of block isocyanato-group containing (meth) acrylate prepares n-octanol solution whose density | concentration of the block isocyanato group containing (meth) acrylate is 20 mass%. After adding 1 mass% equivalent dibutyltin laurate and 3 mass% phenothiazine (antipolymerization agent) to this solution, the block isocyanato group containing after heating at 100 degreeC for 30 minutes (meth The mass reduction ratio of the acrylate is taken as the value measured by HPLC analysis. By using a block isocyanato group-containing (meth) acrylate having a dissociation rate in the above range, it is possible to sufficiently secure the stability of the copolymer at the time of synthesis, to sufficiently lower the baking temperature at the time of preparing the cured coating film, Solvent resistance can also be sufficiently secured. As a block agent of the block isocyanato group containing (meth) acrylate which has such a dissociation rate, (gamma) -butyrolactam, 1-methoxy- 2-propanol, 2, 6- dimethylphenol, diisopropylamine, methyl Ethyl ketooxime, 3,5-dimethylpyrazole and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole and methylethylketooxime are more preferable from the viewpoint of low temperature curability.

Moreover, it is also preferable to use the block isocyanato group containing (meth) acrylate whose dissociation temperature of the block isocyanato group of block isocyanato group containing (meth) acrylate is 80 degreeC or more. By using a block isocyanato group-containing (meth) acrylate having a dissociation temperature of 80 ° C. or more, it is possible to sufficiently secure the stability of the copolymer during synthesis and to reduce an unintended crosslinking reaction during the modification reaction described later. have. On the other hand, if the dissociation temperature of a block isocyanato group is 160 degrees C or less, baking temperature can fully be lowered and solvent resistance of a cured coating film can also be ensured enough. Moreover, the dissociation temperature of the block isocyanato group of block isocyanato-group containing (meth) acrylate prepares the n-octanol solution whose density | concentration of the block isocyanato group containing (meth) acrylate is 20 mass%. 1 mass% of dibutyltin laurate and 3 mass% of phenothiazine (polymerization inhibitor) were added to the solution, and then heated at a predetermined temperature, and the block isocyanato group contained after 30 minutes. The mass reduction ratio of the (meth) acrylate is measured by HPLC analysis, and the temperature at which the mass reduction ratio is 80 mass% or more is taken as the dissociation temperature of the block isocyanato group.

Examples of the block isocyanate group-containing (meth) acrylate include Karenz (registered trademark) MOI-DEM (reaction product of methacryloyloxyethyl isocyanate and diethyl malonate) represented by the following formula (2), Showa Dissolution temperature of a block isocyanate group, manufactured by Electro Electric Co., Ltd .: 90 ° C., dissociation rate: 90 mass%), and Karenz MOI-BP (methacryloyloxyethyl isocyanate and 3,5-dimethyl represented by the following formula (3): Pyazole reaction product, Showa Denko Co., Ltd. dissociation temperature of block isocyanato group: 110 degreeC, dissociation rate: 70 mass%), Karenz MOI-BM (methacryloyloxy represented by following formula (4)) Methacrylates such as reaction products of ethyl isocyanate and methyl ethyl ketooxime, manufactured by Showa Denko Co., Ltd., dissociation temperature of block isocyanato group: 130 ° C, dissociation rate: 18% by mass), and acrylates corresponding thereto; Lifted All. These block isocyanato group containing (meth) acrylates may be used independently, and may be used in combination of 2 or more type.

[Formula 2]

[Formula 3]

[Formula 4]

Although the ratio of the structural unit (a) which has the block isocyanato group which a copolymer (A) contains does not have a restriction | limiting in particular, Preferably it is 1-40 mol%, More preferably, it is 2-30 mol%, Most preferably Preferably it is 3-25 mol%. When the ratio of the structural unit (a) which has a block isocyanato group is 1-40 mol%, the solvent resistance of a cured coating film improves and the storage stability of a copolymer (A) is also maintained.

<Structural Unit (b) Having an Acid Group>

The structural unit (b) which has an acidic radical which a copolymer (A) contains is a structural unit derived from an acidic radical containing monomer (however, it corresponds to the structural unit (a) which has the said block isocyanato group is excluded). As an acid group, a carboxyl group, a sulfo group, a phospho group, etc. are mentioned, Among these, a carboxyl group is preferable at the point of availability. As a monomer which provides the structural unit (b) which has an acidic radical, the monomer which has a polymerizable unsaturated bond and an acidic radical, for example, unsaturated carboxylic acid or its anhydride, unsaturated sulfonic acid, unsaturated phosphonic acid, etc. are mentioned. Specific examples of preferred 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 and maleic anhydride. Unsaturated carboxylic acids such as acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride or its anhydrides; Unsaturated sulfonic acids such as 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid and p-styrenesulfonic acid; Unsaturated phosphonic acids such as vinyl phosphonic acid; Etc. can be mentioned. These monomers may be used independently and may be used in combination of 2 or more type. Among these, unsaturated carboxylic acid is preferable and (meth) acrylic acid is more preferable from a viewpoint which is excellent in alkali developability, and the availability.

In this invention, alkali developability at the time of using a copolymer (A) as a photosensitive material is greatly improved because the structural unit (b) which has an acidic radical is included in a copolymer (A).

There is no restriction | limiting in particular in the ratio of the structural unit (b) which has an acidic radical which a copolymer (A) contains, Preferably it is 1-60 mol%, More preferably, it is 10-50 mol%, Most preferably, 15- 40 mol%. If the ratio of the structural unit (b) which has an acidic radical is 1-60 mol%, it will become a suitable speed of alkali image development and the formation of a precise pattern will be attained.

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 may be, for example, 1:99 to 99: 1 and may be cured. From the viewpoint of solvent resistance of the coating film and storage stability of the copolymer (A), more preferably 5:95 to 75:25, and most preferably 10:90 to 50:50.

<Other structural unit (c)>

In the present invention, as the structural unit contained in the copolymer (A), together with the structural unit (a) having a block isocyanato group and the structural unit (b) having an acid group, other structural units copolymerizable with these ( c) may be contained (except the structural unit (a) which has the said block isocyanato group, and the structural unit (b) which has the said acidic radical is excluded). As a specific example of another structural unit (c), structural units other than the structural unit (c-1) which has an epoxy group, the structural unit (c-2) which has a hydroxyl group, (c-1), and (c-2) (c-3) etc. are mentioned. Although the ratio of the other structural unit (c) which a copolymer (A) contains does not have a restriction | limiting in particular, Preferably it is 0-80 mol%, More preferably, it is 0-70 mol%, Most preferably, 0-60 Mol%.

As a monomer used for introducing the structural unit (c-1) which has an epoxy group, the monomer which has a polymerizable unsaturated bond and an epoxy group, for example, oxiranyl (meth) acrylate and glycidyl (meth) acrylate , 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-oxyranylethyl (meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3 (Meth) acrylic acid ester derivatives containing epoxy groups such as glycidyloxypropyl (meth) acrylate and glycidyloxyphenyl (meth) acrylate; 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2- (3,4-epoxycyclohexyl) ethyl (meth) acrylate, 2- (3, Epoxy-group containing alicyclic types, such as 3, 4- epoxy cyclohexane ring, such as 4-epoxy cyclohexyl methyloxy) ethyl (meth) acrylate and 3- (3, 4- epoxy cyclohexyl methyloxy) propyl (meth) acrylate (Meth) acrylic acid ester derivative containing a carbon ring; Vinyl ether compound containing an epoxy group; And allyl ether compounds containing an epoxy group. These monomers may be used independently and may be used in combination of 2 or more type. Among these, oxiranyl (meth) acrylate, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 2-ethylglycidyl (meth) acrylate, 2-oxyranylethyl ( Epoxy-group-containing (meth) acrylates, such as meth) acrylate, 2-glycidyloxyethyl (meth) acrylate, 3-glycidyloxypropyl (meth) acrylate, and glycidyloxyphenyl (meth) acrylate Is preferable, and glycidyl (meth) acrylate is more preferable.

By containing the structural unit (c-1) which has an epoxy group in a copolymer (A), the solvent resistance at the time of using a copolymer (A) as a photosensitive material improves significantly.

When introducing the structural unit (c-1) which has an epoxy group into a copolymer (A), although the ratio of the structural unit (c-1) which has an epoxy group does not have a restriction | limiting in particular, Preferably it is more than 0 mol%-60 mol %, More preferably, it is more than 0 mol%-50 mol%, Most preferably, it is more than 0 mol%-40 mol%.

As a monomer used for introducing the structural unit (c-2) which has a hydroxyl group, the monomer which has 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 acryl Acrylate, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, etc. are mentioned. Can be. These monomers may be used independently and may be used in combination of 2 or more type. Among these, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, (Meth) acrylic acid ester derivative containing hydroxyl groups, such as 2-hydroxy-3- phenoxypropyl acrylate and 4-hydroxybutyl acrylate, is preferable, and 2-hydroxyethyl (meth) acrylate is more preferable. .

When the structural unit (c-2) which has a hydroxyl group is contained in a copolymer (A), the solvent resistance at the time of using a copolymer (A) as a photosensitive material improves significantly.

When introducing the structural unit (c-2) having a hydroxyl group into the copolymer (A), the ratio of the structural unit (c-2) having a hydroxyl group is not particularly limited, but is preferably more than 0 mol% to 50 mol %, More preferably, it is more than 0 mol%-40 mol%, Most preferably, it is more than 0 mol%-30 mol%.

As a specific example of the monomer used to introduce structural unit (c-3) other than the structural unit (c-1) which has an epoxy group mentioned above, and the structural unit (c-2) which has a hydroxyl group, styrene and (alpha) -methyl Styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, aromatic vinyl compounds such as p-nitrostyrene, p-cyanostyrene, and 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 ] dodeca-3-ene, 8-ethyl Tetracyclo [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 ] undeca-9-ene, tricyclo [6.2.1.0 ^{1 , 8} ] undeca-4-ene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 .0 ^1,6 ] dodeca-3-ene, 8-ethylidenetetracyclo [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 ] dodeca-3-ene, pentacyclo [6.5.1.1 ^3,6 .0 ^2,7 .0 ^9,13 ] ^pentadeca -4-ene , penta-cyclo [7.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] norbornyl, such as penta-deca-3-ene Cyclic olefin having a norbornene structure; Dienes such as butadiene, isoprene and chloroprene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 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-methylnor Boryl (meth) acrylate, 5-ethylnorbor Neyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyloxyethyl acrylate isobornyl (meth) acrylate, adamantyl (meth) acrylic 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) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene glycol mono (meth) acrylate, biphenyloxyethyl ( Meth) acrylate, naph (Meth) acrylic acid esters such as alkylene (meth) acrylate, anthracene (meth) acrylate; (Meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di (Meth) acrylic acid amides such as isopropylamide and anthracenyl amide (meth) acrylate; Vinyl compounds such as (meth) acrylic acid acrylate, (meth) acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate and vinyltoluene; Unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate and diethyl itaconic acid; Monomaleimide, such as N-phenylmaleimide, N-cyclohexyl maleimide, N-lauryl maleimide, and N- (4-hydroxyphenyl) maleimide; Etc. can be mentioned. Among these, (meth) acrylic acid ester is preferable and methyl (meth) acrylate and dicyclopentanyl (meth) acrylate are especially preferable. These monomers may be used independently and may be used in combination of 2 or more type.

<Method for producing copolymer (A)>

Although the ratio of the block isocyanato group containing monomer (a0) and the acid group containing monomer (b0) used at the time of manufacture of a copolymer (A) does not have a restriction | limiting in particular, Preferably it is (a0) 1-40 mol% and (b0) 1-60 mol%, More preferably, (a0) 2-30 mol% and (b0) 10-50 mol%, Most preferably, (a0) 3-25 mol% and (b0) 15 It is-40 mol%. When the copolymer (A) further contains other structural units (c), the block isocyanato group-containing monomer (a0), the acid group-containing monomer (b0), and the like, which are used in the production of the copolymer (A) The ratio of the other monomer (c0) is preferably 1 to 40 mol% (a0), 1 to 60 mol% (b0) and more than 0 mol% to 80 mol% (c0), more preferably (a0). 2-30 mol%, (b0) 10-50 mol% and (c0) more than 0 mol%-70 mol%, Most preferably, (a0) 3-25 mol%, (b0) 15-40 mol% And (c0) more than 0 mol%-60 mol%.

The copolymerization reaction of the block isocyanato group-containing monomer (a0), the acid group-containing monomer (b0) and the other monomer (c0) is carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. Although it can carry out, it is preferable to perform in presence of the hydroxyl-containing organic solvent (B) mentioned later from a viewpoint of preventing abnormal superposition | polymerization and carrying out a polymerization reaction stably. By carrying out the copolymerization reaction in the presence of the hydroxyl group-containing organic solvent (B), even if the block isocyanato group dissociates and generates an isocyanato group, the hydroxyl group of the isocyanato group and the hydroxyl group-containing organic solvent (B) reacts and is abnormal. Polymerization is prevented. In the copolymer (A) obtained in this way, it is thought that a part of the blocking agent which blocked the isocyanato group is substituted by the hydroxyl group containing organic solvent (B). For example, after dissolving these monomers in the hydroxyl-containing organic solvent (B), a polymerization initiator is added to this solution, and what is necessary is just to perform a polymerization reaction at 50-100 degreeC over 1 to 20 hours. At this time, if the polymerization reaction is carried out at a temperature at which the block isocyanato group of the block isocyanato group-containing monomer (a0) dissociates, the isocyanate group generated by dissociation of the block isocyanato group reacts with an acid group to form a gel. Since this occurs, it is preferable to perform polymerization at a temperature below the dissociation temperature of the block isocyanato group, preferably at a temperature below the dissociation temperature of the block isocyanato group about 20 to 50 ° C.

Moreover, it does not specifically limit as a polymerization initiator which can be used for this copolymerization reaction, For example, Azobisisobutyronitrile, Azobisisovaleronitrile, benzoyl peroxide, t-butylperoxy-2-ethyl Hexanoate etc. are mentioned. These polymerization initiators may be used independently and may be used in combination of 2 or more type. The amount of the polymerization initiator to be used is generally 0.5 to 20 parts by mass, and preferably 1.0 to 10 parts by mass when the total amount of the monomer is 100 parts by mass.

Although the weight average molecular weight in terms of polystyrene of the copolymer (A) is not particularly limited, the copolymer (A) having a weight average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 40,000, by the above-described production method. Can be obtained. When the weight average molecular weight of a copolymer (A) is 1,000 or more, the defect of a coloring pattern will not generate | occur | produce well after alkali development at the time of using as a photosensitive resin composition. On the other hand, when the weight average molecular weight of a copolymer (A) is 50,000 or less, developing time is appropriate and practicality is ensured.

Moreover, although the acid value (JIS K6901 5.3) of a copolymer (A) can be selected suitably, when mix | blending with the photosensitive resin composition, Preferably it is 20-300 KOHmg / g, More preferably, it is 30-200 KOHmg / g Range. When the acid value of the copolymer (A) is 20 KOHmg / g or more, alkali developability at the time of using it 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, since the exposed portion (photocured portion) is less likely to be dissolved in the alkaline developer, the pattern shape is good.

In the present invention, the copolymer (A) contains a block isocyanato group in the molecule. Although content of a block isocyanato group may be selected suitably, normally, the block isocyanato group equivalent is selected in the range which becomes 400-6,000, Preferably it is 1,000-5,000. Block isocyanato group equivalent is the mass of a polymer per mol of block isocyanato groups contained in a polymer, and can be calculated | required by dividing the mass of a polymer by the number of moles of block isocyanato groups contained in a polymer (g / mol ). In the present invention, the block isocyanato group equivalent is a theoretical value calculated from the injection amount of the block isocyanato group-containing monomer.

<Hydroxy group-containing organic solvent (B)>

The hydroxyl group-containing organic solvent (B) may be any organic solvent containing a hydroxyl group. For example, 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 mono Alkyl ether, glycerin dialkyl ether, methanol, ethanol, propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanedimethanol, ethyl lactate, diacetone alcohol, etc. are mentioned. 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 the film forming property and the availability at the time of preparing a cured coating film. Do. These hydroxyl group containing organic solvents (B) may be used independently and may be used in combination of 2 or more type.

In this invention, preservation of the photosensitive resin composition is carried out by using together the copolymer (A) and the hydroxyl-containing organic solvent (B) containing the structural unit (a) which has a block isocyanato group, and the structural unit (b) which has an acidic group. Stability is improved.

Moreover, in the photosensitive resin composition of this invention, you may use together solvents other than a hydroxyl-containing organic solvent (B).

<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 these, a compound having a plurality of polymerizable functional groups is preferable. By using together such a reactive diluent (C) with a copolymer (A), a viscosity can be adjusted, the intensity | strength of the hardened | cured material formed, and adhesiveness with respect to a base material can be improved.

As a monofunctional monomer used as a reactive diluent (C), (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl ( Meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxy 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-tetrafluoro Peel (meth) acrylate, a half (meth) acrylate such as (meth) acrylates of phthalic acid derivatives; Aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; Carboxylic acid esters, such as vinyl acetate and a vinyl propionate, etc. are mentioned. Moreover, these monomers may be used independently and may be used in combination of 2 or more type.

As a polyfunctional monomer used as a reactive diluent (C), ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (meth) acryl Rate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tree ( 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) acryloxydiethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3 -(Meth) acryloyloxy Lofil (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 (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. and 2-hydroxyethyl (meth) (Meth) acrylates, such as a acrylate reactant and a tri (meth) acrylate of tris (hydroxyethyl) isocyanurate; Aromatic vinyl compounds such as divinylbenzene, diallyl phthalate and diallylbenzene phosphonate; Dicarboxylic acid esters such as adipic divinyl; Triallyl cyanurate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, a condensate of a polyhydric alcohol and N-methylol (meth) acrylamide, and the like. These monomers may be used independently and may be used in combination of 2 or more type.

<Photoinitiator (D)>

Although it does not specifically limit as a photoinitiator (D), For example, Benzoin, 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- [ Acetophenones, such as 4- (methylthio) phenyl] -2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1; Anthraquinones such as 2-methylanthraquinone, 2-amyl anthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones, such as xanthone, thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro thioxanthone; Ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone ; Acyl phosphine oxides; Etc. can be mentioned. These photoinitiators (D) may be used independently and may be used in combination of 2 or more type.

In addition to said component, the photosensitive resin composition of this invention may mix | blend well-known additives, such as a well-known coupling agent, a leveling agent, and a thermal polymerization inhibitor, in order to provide a predetermined characteristic. The compounding quantity of these additives will not be specifically limited if it is a range which does not impair the effect of this invention.

<Photosensitive resin composition for color filters>

Moreover, the photosensitive resin composition of this invention can further contain a coloring agent (E), and it can be set as the photosensitive resin composition for color filters.

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

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, acidic dyes of azo, xanthene, anthraquinone or phthalocyanine are preferable. These dyes may be used alone or in combination of two or more kinds, depending on the color 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 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 194, and 214; C.I. Orange pigments such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like; C.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, etc. ; C.I. Blue pigments such as pigment blue 15, 15: 3, 15: 4, 15: 6 and 60; C.I. Violet pigments such as pigment violet 1, 19, 23, 29, 32, 36 and 38; C.I. Green pigments such as pigment green 7, 36, 58 and 59; C.I. Brown pigments such as pigment brown 23 and 25; C.I. Pigment black 1, 7, black pigments, such as carbon black, titanium black, iron oxide, etc. are mentioned.

These coloring agents (E) may be used independently or may be used in combination of 2 or more type according to the color of the pixel made into the objective. Moreover, according to the color of the pixel made into the objective, you may use combining said dye and pigment.

When using a pigment as a coloring agent (E), you may mix | blend a well-known dispersing agent with the photosensitive resin composition from a viewpoint of improving the dispersibility of a pigment. As the dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of the polymer dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, aliphatic modified ester dispersants, and the like. As such a polymeric dispersant, it is marketed under brand names, such as EFKA (made by Efka Chemicals Viv (EFKA)), Disperbyk (made by Bikchem), Disparon (made by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (made by Geneca). You can use what you have. What is necessary is just to set the compounding quantity of a dispersing agent suitably according to the kind of pigment etc. to be used.

The compounding quantity of the copolymer (A), the hydroxyl group containing organic solvent (B), the reactive diluent (C), the photoinitiator (D), and the coloring agent (E) in the photosensitive resin composition for color filters is the photosensitive resin composition for color filters 10-100 mass parts of copolymers (A), 30-1,000 mass parts of hydroxyl-containing organic solvents (B), and reactive diluent (C) with respect to 100 mass parts of total amounts of the copolymer (A) and reactive diluent (C) in the inside. ) 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, and preferably the copolymer (A) is 20 to 80 parts by mass. 50-800 mass parts of hydroxyl-containing organic solvents (B), 20-80 mass parts of reactive diluents (C), 0.5-20 mass parts of photoinitiators (D), and 5-70 mass of coloring agents (E) Part, More preferably, 30-75 mass parts of copolymers (A) and 100-700 mass parts of hydroxyl-containing organic solvents (B) are 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 a compounding quantity of this range, it will become the photosensitive resin composition for color filters which has a suitable viscosity. Moreover, also in the case of the photosensitive resin composition which does not contain a coloring agent (E), the compounding quantity of a copolymer (A), a hydroxyl-containing organic solvent (B), a reactive diluent (C), and a photoinitiator (D) is said numerical value. Range is applicable.

<Production of Photosensitive Resin Composition>

The photosensitive resin composition of this invention can be manufactured by mixing said component using a well-known mixing apparatus. Moreover, the composition containing a copolymer (A) and a hydroxyl-containing organic solvent (B) by copolymerizing a block isocyanato-group-containing (meth) acrylate and unsaturated carboxylic acid in presence of a hydroxyl-containing organic solvent (B). After preparing, the reactive diluent (C), the photoinitiator (D), and the coloring agent (E) which is an optional component can also be mixed and manufactured.

Since the photosensitive resin composition obtained by making it above has alkali developability, it is suitable as a resist. Although the curing temperature of the photosensitive resin composition should just select a baking temperature suitably in the range of 250 degrees C or less, since the copolymer (A) used by this invention is excellent in sclerosis | hardenability at low temperature, baking temperature is compared with the conventional material. Can be lowered. When a pigment is used as a coloring agent (E) in the photosensitive resin composition, sufficient curing property is obtained even if baking temperature is 160 degrees C or less. Since the crosslinking reaction fully advances even if the baking temperature is low, the photosensitive resin composition of this invention is advantageous at the point of energy consumption. Moreover, even if it is a colorant (E) and a board | substrate which are inferior in heat resistance, it becomes possible to use, the original characteristic of a colorant is acquired, and the application to various board | substrates becomes also possible. In view of the above, 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 constant depending on the type of the block isocyanato group contained in the copolymer (A), but it is required to be at least the dissociation temperature of the block isocyanato group, and usually 80 ° C. or higher, preferably Is 90 degreeC or more, More preferably, it is 100 degreeC or more. When baking temperature becomes too low, it will become difficult to fully improve the solvent resistance of a coating film. Moreover, although baking time can be selected suitably, it is 10 minutes-4 hours normally, Preferably it is 20 minutes-2 hours.

The photosensitive resin composition of this invention is suitable as various resist, especially resist used in order to manufacture the color filter inserted in solid-state image sensors, such as organic electroluminescent display (for black PDL), a liquid crystal display device, CCD, CMOS, etc. Moreover, since the photosensitive resin composition of this invention gives the cured coating film excellent in solvent resistance, the hardening characteristic at low temperature, etc., it can also be used for various coatings, adhesives, binders for printing ink, etc.

The photosensitive resin composition of the present invention is very useful as a photosensitive material for color filters because it has good developability and storage stability and can form a colored pattern excellent in solvent resistance even if the baking temperature at the time of pattern formation is low. Do. Moreover, the photosensitive resin composition of this invention can contribute also to power generation of a flexible display, reduction of energy consumption in a manufacturing process, and restriction | limiting relaxation of the coloring agent to be used with low temperature hardening.

<Color filter>

Next, the color filter which has a coloring pattern which consists of hardened | cured material of the photosensitive resin composition for color filters of this invention is demonstrated. The color filter of this invention has the coloring pattern formed using said photosensitive resin composition for color filters. A color filter is usually comprised with a board | substrate, the pixel of RGB formed on it, the black matrix formed in the boundary of each pixel, and the protective film formed on the pixel and black matrix. In this structure, a well-known thing can be employ | adopted except the pixel and black matrix (coloring pattern) formed using the photosensitive resin composition for color filters mentioned above.

Next, one Embodiment of the manufacturing method of a color filter is described. First, a coloring pattern is formed on a board | substrate. Specifically, black matrix and RGB pixels are sequentially formed on the substrate. The material of a board | substrate is not specifically limited, A glass substrate, a silicon substrate, a polycarbonate board | substrate, a polyester board | substrate, a polyamide board | substrate, a polyamideimide board | substrate, a polyimide board | substrate, an aluminum board | substrate, a printed wiring board, an array board | substrate, etc. suitably Can be used

A coloring pattern can be formed by the photolithographic method. Specifically, after apply | coating said photosensitive resin composition on a board | substrate and forming a coating film, a coating film is exposed through the photomask of a predetermined pattern, and an exposure part is photocured. And after developing an unexposed part with aqueous alkali solution, baking can form a predetermined coloring pattern.

Although it does not specifically limit as a coating method of the photosensitive resin composition, The screen printing method, the roll coat method, the curtain coat method, the spray coat method, the spin coat method, etc. can be used. Moreover, after application | coating of the photosensitive resin composition, you may volatilize a hydroxyl-containing organic solvent (B) by heating using heating means, such as a circulating oven, an infrared heater, and a hotplate, as needed. Heating conditions are not specifically limited, What is necessary is just to set suitably according to the kind of photosensitive resin composition to be used. Generally, what is necessary is just to heat 30 second-30 minutes at the temperature of 50 degreeC-120 degreeC.

Subsequently, active energy rays, such as an ultraviolet-ray and an excimer laser beam, are irradiated and partially exposed through the negative mask to the formed coating film. What is necessary is just to select the energy dose to irradiate suitably according to the composition of the photosensitive resin composition, For example, it is preferable that it is 30-2000 mJ / cm <2>. Although it does not specifically limit as a light source used for exposure, 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.

Although it does not specifically limit as aqueous alkali solution used for image development, aqueous solution, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; Aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; Tetramethylammonium, 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N P-phenyl such as -ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof The aqueous solution of a rendiamine type compound, etc. can be used. Moreover, you may add an antifoamer and surfactant to these aqueous solutions as needed. Moreover, it is preferable to wash with water and to dry after image development by said aqueous alkali solution.

The conditions of baking are not specifically limited, What is necessary is just to heat-process according to the kind of photosensitive resin composition to be used. In the conventional photosensitive resin composition, when baking temperature becomes 200 degrees C or less, the solvent resistance of a coloring pattern is lacking, but in the photosensitive resin composition for color filters of this invention, even if it bakes at the temperature of 120 degrees C or less, it shows sufficient solvent resistance. A coloring pattern can be formed. Therefore, baking temperature can be made low, and when baking at high temperature, processing time can be shortened and it is a big advantage in manufacture. In view of this, 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 It is implemented as 2 hours.

The desired coloring pattern can be formed by repeating application | coating, exposure, image development, and baking as above using the photosensitive resin composition for black matrices, and the photosensitive resin composition for pixels of red, green, and blue one by one. In addition, although the formation method of the coloring pattern by photocuring was demonstrated above, when the photosensitive resin composition which mix | blended a hardening accelerator and a well-known epoxy resin was used instead of a photoinitiator (D), it applied by the inkjet method. After that, a desired coloring pattern can also be formed by heating. Next, a protective film is formed on a coloring 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.

Since the color filter manufactured in this way is manufactured using the photosensitive resin composition which is excellent in a sensitivity and developability, hardening at low temperature, and providing a coloring pattern excellent in solvent resistance, it is excellent in few color changes. It has a coloring pattern.

<Image display element>

The image display element of this invention is an image display element provided with said color filter, As a specific example, solid-state imaging elements, such as a liquid crystal display element, an organic electroluminescence display element, a CCD element, and a CMOS element, etc. are mentioned. Manufacture of the image display element of this invention may be performed in accordance with a conventional method other than using said color filter. For example, when manufacturing a liquid crystal display element, the said color filter is formed on a board | substrate, and then an electrode, a spacer, etc. are formed one by one. Then, an electrode or the like may be formed on another substrate, the two may be bonded together, and a predetermined amount of liquid crystal may be injected and sealed.

Example

Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited by these Examples. In addition, in this Example, all of parts and percentages are mass references | standards unless there is particular notice. In addition, the measuring method of an acid value and a weight average molecular weight is as follows.

(1) Acid value: As an acid value of the copolymer (A) measured according to JISK6901 5.3, it means the mg number of potassium hydroxide required in order to neutralize the acidic component contained in 1 g of this copolymer (A).

(2) Weight average molecular weight (Mw) means the standard polystyrene conversion weight average molecular weight measured on condition of the following using gel permeation chromatography (GPC).

Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)

Column temperature: 40 ℃

Sample: 0.2% tetrahydrofuran solution of copolymer

Developing Solvent: Tetrahydrofuran

Detector: parallax refractometer (Showdex RI-71S) (manufactured by Showa Denko Co., Ltd.)

Flow rate: 1 ml / min

Synthesis Example 1

After putting 149.3 g of propylene glycol monomethyl ether into the flask provided with the stirring apparatus, the dropping funnel, the condenser, the thermometer, and the gas inlet tube, it stirred while nitrogen-substituting and heated up at 78 degreeC. Next, 22.4 g of dicyclopentanyl methacrylate, 17.2 g of methacrylic acid and 50.2 g of methacrylic acid 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl (Carenz MOI- BP, the monomer mixture consisting of Showa Denko Co., Ltd., dissociation rate of block isocyanato group: 70 mass%), and 11.2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) ) Were added to 62.8 g of propylene glycol monomethyl ether acetate and dissolved in the flask from the dropping funnel. After completion of the dropwise addition, the mixture was stirred at 78 ° C. for 3 hours to carry out a copolymerization reaction to produce a copolymer, thereby obtaining a polymer composition (component concentration 35 mass% other than the solvent) of Sample No. 1. 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]

Except using the raw material of Table 1 and 2, copolymerization reaction was performed on the conditions similar to the synthesis example 1, and the polymer composition (35 mass% of component concentrations other than a solvent) of Sample No. 2-11 was 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, methacrylic acid 2- [O- (1'-methylpropylideneamino) carboxyamino] ethyl is produced by Showa Electric Co., Ltd., Carens MOI-BM, and block isocyanato group. Dissociation ratio: 18 mass%, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl] oxy] ethyl] amino] carbonyl] -1,3 diethyl ester is Showa Electric The disassociation rate of Carens MOI-DEM and a block isocyanato group manufactured by KK Co., Ltd .: 90 mass%, and benzoic acid-4-[[[[2-[(2-methyl-1-oxo-2-propene-1-) I) oxy] ethyl] amine] carbonyl] oxy] methyl ester dissociation rate of a block isocyanato group: 40 mass%, benzoic acid-2- [[[[[2- [(2-methyl-1-oxy) -2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester has a dissociation ratio of block isocyanato group: 75 mass%, 2-propenic acid-2-methyl-2- [[(3,5-dimethylphenoxy) carbonyl] amine] ethyl ester has a dissociation rate of a block isocyanato group: 28% by mass or less All.

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

<Preparation of the photosensitive resin composition (pigment type)>

In a stainless steel container filled with 200 g of zirconia beads having a diameter of 0.5 mm, 100 parts by mass of CI pigment green 36 (coloring agent), 44.98 parts by mass of propylene glycol monomethyl ether acetate, and a dispersant (Bicchemy Japan Co., Ltd. Disperbyk- 25 parts by mass of 161 was added, and a green pigment dispersion liquid was prepared by mixing and dispersing with a paint shaker for 2 hours.

This green pigment dispersion liquid was mixed with the other compounding components (that is, a polymer composition, a reactive diluent, a photoinitiator, and a solvent) shown in Table 3, and the photosensitive resin composition was prepared. The mixing | blending ratio of each component is as showing in Table 3. In addition, the photosensitive resin composition of Examples 1-9 is prepared using each of the polymer compositions of Sample Nos. 1-9, and the photosensitive resin composition of Comparative Examples 1-2 is each the polymer composition of Samples No. 10-11, respectively. It was prepared using. Moreover, the quantity of a polymer composition contains the solvent contained at the time of completion | finish of copolymerization reaction, and the quantity of the solvent contained in each sample is also summed in the solvent as a compounding component.

<Evaluation of the photosensitive resin composition>

(1) alkali developability

Each of the photosensitive resin compositions of Examples 1-9 and Comparative Examples 1-2 was spin-coated so that the thickness after exposure might be set to 2.5 micrometers on the glass substrate (alkali-free glass substrate) of 5 cm in width, and at 90 degreeC The solvent was volatilized by heating for 3 minutes. Next, the photomask of a predetermined pattern was arrange | positioned at the distance of 100 micrometers from a coating film, the coating film was exposed (exposure amount 150mJ / cm <2>) through this photomask, and the exposure part was photocured. Next, 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 a predetermined pattern was formed by baking at 100 ° C. for 20 minutes. The residue after alkali image development was confirmed by observing the pattern after alkali image development using the electron microscope S-3400 by Hitachi High Technologies. The criteria of this evaluation are as follows.

○: no residue

×: residue

Table 4 shows the evaluation results of alkali developability.

(2) Evaluation of solvent resistance

After spin coating each of the photosensitive resin compositions of Examples 1-9 and Comparative Examples 1-2 on the glass substrate (alkali-free glass substrate) of 5 cm in width so that the thickness after baking may be set to 2.5 micrometers, it is 90 degreeC The solvent was volatilized by heating for 3 minutes. Next, after exposing light of wavelength 365nm to a coating film and photocuring an exposed part, it left for 20 minutes in the drying machine of baking temperature 100 degreeC, and produced the cured coating film. 200 ml of propylene glycol monomethyl ether acetate was put into the glass bottle with a cap of 500 ml of capacity, and it was left still on 80 degreeC conditions. After immersing the said test piece with a cured coating film in it, it stood still for 5 minutes in the state maintained at 80 degreeC. Color change (ΔE * ab) before and after the test piece was immersed in propylene glycol monomethyl ether acetate was measured by a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). Table 4 shows the measurement results of ΔE * ab. It can be said that solvent resistance is excellent when (DELTA) E * ab is 1.5 or less.

(3) evaluation of storage stability

The copolymers of Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 to 2 were weighed into the glass containers in equal amounts, and the inlet was closed with aluminum foil so that dust and the like did not enter. Next, these samples were left still in the thermostat maintained at 23 degreeC, respectively, and the weight average molecular weight (Mw) after one month of samples was measured. The change rate of Mw after one month is shown in Table 5. When the rate of change of Mw after one 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 photosensitive resin compositions of Examples 1 to 9 using the polymer compositions of Samples Nos. 1 to 9 had good alkali developability and solvent resistance. In addition, since the storage stability of a copolymer has a correlation with the storage stability of the photosensitive resin composition which mix | blended it, from the result of Table 5, the photosensitive resin composition of Examples 1-9 which used the polymer composition of samples No. 1-9. Silver storage stability can also be said to be favorable. On the other hand, although the storage stability of the photosensitive resin compositions of Comparative Examples 1-2 using the polymer compositions of Sample No. 10-11 is favorable, the photosensitive resin composition of Comparative Example 1 using the polymer composition of Sample No. 10 is The solvent resistance was not sufficient, and the photosensitive resin composition of Comparative Example 2 using the polymer composition of Sample No. 11 was not sufficient in 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 good developability and excellent solvent resistance and storage stability.

In addition, this international application claims the priority based on Japanese Patent Application No. 2017-150502 for which it applied on August 3, 2017, and uses the whole content of this Japanese patent application for this international application.

Claims (15)

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), and a photopolymerization initiator (D) is contained, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The structural unit (a) which has the said block isocyanato group is a structural unit derived from a block isocyanato group containing (meth) acrylate, and the block isocyanato group of the said block isocyanato group containing (meth) acrylate The photosensitive resin composition which is 5-99 mass% when the dissociation rate of is heated at 100 degreeC for 30 minutes. The method according to claim 1 or 2,
The block agent of the structural unit (a) which has the said block isocyanato group is diethyl malonate, 3, 5- dimethyl pyrazole and methyl ethyl ketooxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate, and 3, Photosensitive resin composition which is 1 or more types chosen from the group which consists of 5- xylenol. The method according to any one of claims 1 to 3,
The said 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, At least one photosensitive resin composition selected from the group consisting of propanol, C _5-6 cycloalkanediol, C _5-6 cycloalkanedimethanol, ethyl lactate and diacetone alcohol. The method according to any one of claims 1 to 4,
The photosensitive resin composition whose structural unit (b) which has the said acidic radical is a structural unit derived from unsaturated carboxylic acid. The method according to any one of claims 1 to 5,
The said photosensitive resin composition in which the said copolymer (A) contains 1-40 mol% of structural units (a) which has the said block isocyanato group, and the structural unit (b) which has the said acidic group. The method according to any one of claims 1 to 6,
The photosensitive resin composition whose molar ratio of the structural unit (a) which has the said block isocyanato group in the said copolymer (A) and the structural unit (b) which has the said acidic group is 10: 90-50: 50. The method according to any one of claims 1 to 7,
The said copolymer (A) is methacrylic acid 2- (3,5-dimethylpyrazol-1-yl) carbonylaminoethyl, methacrylic acid 2- [O- (1'-methylpropylideneamino) carboxyamino ] 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-propenic acid-2-methyl-2-[[(3,5-dimethylphenoxy) carb Structural unit (a) derived from at least 1 sort (s) chosen from the group which consists of a carbonyl] amine] ethyl ester, the structural unit (b) derived from (meth) acrylic acid, glycidyl (meth) acrylate, and 2-hydroxy At least one selected from the group consisting of ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate and methyl (meth) acrylate 1 kinds of photosensitive resin composition containing a structural unit (c) derived from. The method according to any one of claims 1 to 8,
The photosensitive resin composition which further contains a coloring agent (E) and is for color filters. The method of claim 9,
10-100 mass parts of said copolymers (A), 30-1,000 mass parts of said hydroxyl group containing organic solvents (B) with respect to 100 mass parts of total amounts of the said copolymer (A) and the said reactive diluent (C), The photosensitive resin composition in which a reactive diluent (C) exceeds 0-90 mass parts, the said photoinitiator (D) contains 0.1-30 mass parts, and the said coloring agent (E) 5-80 mass parts. The method according to claim 9 or 10,
The photosensitive resin composition in which the said coloring agent (E) contains a pigment. It has a coloring pattern which consists of hardened | cured material of the photosensitive resin composition of any one of Claims 9-11, The color filter characterized by the above-mentioned. An image display element comprising the color filter according to claim 12. The process of apply | coating the photosensitive resin composition of any one of Claims 9-11 to a board | substrate, exposing, alkali-developing, baking at the temperature of 160 degrees C or less, and forming a coloring pattern, It characterized by The manufacturing method of the color filter to make. Copolymerization of the block isocyanato group-containing (meth) acrylate and an unsaturated carboxylic acid in the presence of a hydroxyl group-containing organic solvent (B) to synthesize a copolymer (A), followed by a reactive diluent (C) and a photopolymerization initiator The manufacturing method of the photosensitive resin composition characterized by including the process of mix | blending (D).