KR20220066187A - Photosensitive resin composition and method for manufacturing 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), and a photopolymerization initiator (D) The photosensitive resin composition containing.

Description

A photosensitive resin composition and its manufacturing method TECHNICAL FIELD

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

In recent years, from the viewpoint of resource saving and energy saving, in the fields of various coatings, printing, paints, adhesives, etc., the photosensitive resin composition curable by active energy rays, such as an ultraviolet-ray or an electron beam, is widely used. Moreover, also in the field of electronic materials, such as a printed wiring board, the photosensitive resin composition which can be hardened|cured with an active energy ray is used for a soldering resist, the resist for color filters, etc. In addition, the properties required for the curable photosensitive resin composition are becoming more and more diverse and advanced, and among them, short-time curability in consideration of productivity and low-temperature curability that suppresses thermal damage to the member to be applied are required.

A 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, a black matrix formed at the boundary between the pixels, a pixel and It consists of a protective film formed on a black matrix. A color filter having 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 "coloring pattern."). Among them, a pigment/dye dispersion method produced by a photolithography method that uses a 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. Because of this, it has become the mainstream at present.

Generally, the photosensitive resin composition used for a photolithography 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 advantages, high heat resistance is required in that the black matrix, R, G, and B patterns are repeatedly formed, and can be used as a colorant that can withstand high baking temperatures. It is often a problem that there are restrictions such as the type of colorant being limited.

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

Patent Document 2 discloses a photosensitive resin comprising a polymer precursor whose reaction to a final product is accelerated by heating with a basic substance or in the presence of a basic substance, and a specific base generator that generates a base by irradiation and heating with electromagnetic waves. By using the composition, low-temperature curing is possible.

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

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

The present invention has been made in order to solve the above problems, and it is an object of the present invention to provide a photosensitive resin composition which provides a cured coating film having good developability and storage stability and excellent solvent resistance even when cured at a low temperature, and a method for producing the same do it with

Moreover, an object of this invention is to provide the color filter which has a 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), and a reactive diluent (C); A photoinitiator (D) is contained, The photosensitive resin composition characterized by the above-mentioned.

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

[3] The blocking agent of the structural unit (a) having a blocked isocyanato group is at least one selected from the group consisting of diethyl malonate, 3,5-dimethylpyrazole and methylethylketoxime [1] or [ 2] The photosensitive resin composition as described in.

[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 cycloalkanediol, C _5-6 cycloalkanedimethanol, ethyl lactate, and at least one selected from the group consisting of diacetone alcohol The photosensitivity according to any one of [1] to [3]. 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 an unsaturated carboxylic acid.

[6] [1] wherein the copolymer (A) contains 1 to 40 mol% of the structural unit (a) having a block isocyanato group and 1 to 60 mol% of the structural unit (b) having an acid group ] - The photosensitive resin composition in any one of [5].

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

[8] The 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-propenoic acid-2-methyl-2-[[(3,5-dimethyl A structural unit (a) derived from at least one selected from the group consisting of phenoxy) carbonyl] amine] ethyl ester, a structural unit (b) derived from (meth) acrylic acid, and glycidyl (meth) acrylate; [1] to [1] containing a structural unit (c) derived from at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate and methyl (meth) acrylate 7] The photosensitive resin composition as described in any one of.

[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] 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) part, the reactive diluent (C) is contained in an amount of from more than 0 parts by mass to 90 parts by mass, the photoinitiator (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. A photosensitive resin composition.

[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 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] Applying the photosensitive resin composition according to any one of [9] to [11] on a substrate, exposing, alkali development, and baking at a temperature of 160 ° C. or less to form a colored pattern. A method of manufacturing a color filter, characterized in that

[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 process of mix|blending a photoinitiator (D) is included, The manufacturing method of the photosensitive resin composition characterized by the above-mentioned.

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

Moreover, according to this invention, the color filter which has a 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 radical, 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 a block isocyanato group which a copolymer (A) contains 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, for example, an isocyanato group in an isocyanate compound having a vinyl group, a (meth)acryloyloxy group, etc. in the molecule; The compound which blocked with the blocking agent is mentioned. Reaction of an isocyanate compound and a blocking agent can be performed irrespective 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. In the case of blocking reaction, you may use organometallic salts, such as tin, zinc, and lead, a tertiary amine, etc. as a catalyst. Although reaction can generally be implemented 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 said formula (1), R< ¹ > represents a hydrogen atom or a methyl group, R< ² > is -CO-, -COOR ³ - (here, R< ³ > is a C1-C6 alkylene group) or -COO. -R ⁴ O-CONH-R ⁵ - (Here, R ⁴ is an alkylene group having 2 to 6 carbon atoms, and R ⁵ is an optionally substituted alkylene group having 2 to 12 carbon atoms or an alkylene group having 6 to 6 carbon atoms. 12 is an arylene group). R ² is preferably -COOR ³ -, wherein R ³ is preferably an alkylene group having 1 to 4 carbon atoms.

Specifically, as an isocyanate compound represented by said Formula (1), 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acryl Rate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, meth Acryloyl isocyanate etc. are mentioned. Moreover, an 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. 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-isocyanatomethylcyclohexylisocyanate (IPDI), m- (or p-) xylenediisocyanate, 1,3- (or 1,4-) bis(isocyanatomethyl)cyclohexane , lysine diisocyanate, and the like.

Among these isocyanate compounds, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 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-isocyanato Cyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferable.

In addition, the description of (meth)acrylate in this specification means that any of acrylate and methacrylate may be sufficient, and the description of (meth)acrylic acid may be either acrylic acid or methacrylic acid. it means to be

As a blocking agent which blocks the isocyanato group in the said isocyanate compound, For example, Lactam types, 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 such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol; phenols such as dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; Active methylene type|system|groups, 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, acetate amide, and benzamide; Acid imide type, such as succinimide and maleic acid imide; imidazole systems such as imidazole, 2-methylimidazole and 2-ethylimidazole; pyrazoles such as pyrazole and 3,5-dimethylpyrazole; Urea type, such as urea, thiourea, and ethylene urea; Carbamid acid salt types, such as N-phenylcarbamate phenyl and 2-oxazolidone: Imine types, such as ethyleneimine and polyethyleneimine; Oxime systems, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; Bisulfite types, such as sodium bisulfite and potassium bisulfite, etc. are mentioned. These blocking agents may be used independently and may be used in combination of 2 or more type.

Although the blocking agent protects the highly reactive isocyanato group, the blocked isocyanato group dissociates by heating, and the isocyanato group is regenerated. 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 contained as desired, and the crosslinking density is high form a cured product.

It is preferable to use a block isocyanato group containing (meth)acrylate as a monomer which provides the structural unit (a) which has a block isocyanato group from a viewpoint of low-temperature curability and storage stability of the photosensitive resin composition mentioned later. Do. The dissociation rate of the blocked isocyanato group when heat-treated at 100°C for 30 minutes is preferably 5 to 99 mass%, more preferably 8 to 97 mass%, and most preferably 10 to 95 mass%. It is preferable to use a block isocyanato group containing (meth)acrylate. In addition, the dissociation rate of the blocked isocyanato group of the 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 % After adding dibutyltin laurate equivalent to 1 mass % and phenothiazine (polymerization inhibitor) equivalent to 3 mass % to the solution, the block isocyanato group containing (method) after heating at 100°C for 30 minutes ) Let the mass reduction ratio of acrylate be the value measured by HPLC analysis. When the block isocyanato group-containing (meth)acrylate having a dissociation rate in the above range is used, the stability of the copolymer during synthesis can be sufficiently ensured, and the baking temperature at the time of preparing a cured coating film can be sufficiently lowered, and the cured coating film Solvent resistance can also be sufficiently secured. Examples of the blocking agent for the blocked isocyanato group-containing (meth)acrylate having such a dissociation rate include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, 3,5-dimethylpyrazole, and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, and methyl ethyl ketoxime are 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. When the block isocyanato group-containing (meth)acrylate having a dissociation temperature of 80 ° C. or higher is used, the stability of the copolymer during synthesis can be sufficiently ensured, and unintended crosslinking reaction can be reduced during the denaturation reaction described later. there is. On the other hand, when the dissociation temperature of the blocked isocyanato group is 160°C or less, the baking temperature can be sufficiently lowered and the solvent resistance of the cured coating film can be sufficiently secured. In addition, the dissociation temperature of the blocked isocyanato group of the blocked isocyanato group-containing (meth)acrylate prepares an n-octanol solution in which the concentration of the blocked isocyanato group-containing (meth)acrylate is 20% by mass. After adding dibutyltin laurate equivalent to 1 mass % and phenothiazine (polymerization inhibitor) equivalent to 3 mass % to the solution, heating at a predetermined temperature and containing the blocked isocyanato group after 30 minutes The mass reduction ratio of (meth)acrylate is measured by HPLC analysis, and let the temperature at which the mass reduction ratio becomes 80 mass % or more be the dissociation temperature of a blocked isocyanato group.

As an example of the block isocyanato group-containing (meth)acrylate, Karenz (registered trademark) MOI-DEM (reaction product of methacryloyloxyethyl isocyanate and diethyl malonate, Showa Dissociation temperature of a block isocyanato group: 90 degreeC, dissociation rate: 90 mass %), Carenz MOI-BP (methacryloyloxyethyl isocyanate and 3,5-dimethyl represented by the following formula (3)), manufactured by Denko Co., Ltd. A reaction product of pyrazole, manufactured by Showa Denko Co., Ltd., dissociation temperature of block isocyanato group: 110° C., dissociation rate: 70 mass%), Karenz MOI-BM (methacryloyloxy) represented by the following formula (4) A reaction product of ethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Denko Co., Ltd., dissociation temperature of a block isocyanato group: 130° C., dissociation rate: 18 mass%) and methacrylates and acrylates corresponding to these can be heard 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]

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 preferably 3 to 25 mol%. The solvent resistance of a cured coating film improves that the ratio of the structural unit (a) which has a block isocyanato group is 1-40 mol%, and the storage stability of a copolymer (A) is also maintained.

<Structural unit having an acid group (b)>

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

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

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 40 mol%. When the ratio of the structural unit (b) having an acid group is 1 to 60 mol%, an appropriate alkali development rate is achieved, and a precise 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 may be, for example, 1:99 to 99:1, and cured From a viewpoint of the solvent resistance of a coating film and the storage stability of a copolymer (A), More preferably, it is 5:95-75:25, Most preferably, it is 10:90-50:50.

<Other structural units (c)>

In the present invention, as a 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 (however, the thing corresponding to 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 there is no restriction|limiting in particular as for the ratio of the other structural unit (c) which a copolymer (A) contains, Preferably it is 0-80 mol%, More preferably, it is 0-70 mol%, Most preferably, it is 0-60 mol%. is mol%.

As a monomer used to introduce 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-methyl glycidyl (meth) acrylate, 2-ethyl glycidyl (meth) acrylate, 2-oxiranyl ethyl (meth) acrylate, 2-glycidyl oxyethyl (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 alicyclics such as 3,4-epoxycyclohexane ring, such as 4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate (meth)acrylic acid ester derivative containing a carbon ring; vinyl ether compound containing an epoxy group; An allyl ether compound containing an epoxy group, etc. are mentioned. 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-oxiranylethyl ( 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.

When the structural unit (c-1) having an epoxy group is contained in the copolymer (A), the solvent resistance at the time of using the copolymer (A) as a photosensitive material is greatly improved.

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

As the monomer used to introduce the structural unit (c-2) having a hydroxyl group, 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-hydroxybutylacrylic Late, 2-acryloyloxyethyl-succinic acid, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxyethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, etc. are mentioned. can 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 derivatives containing hydroxyl groups, such as 2-hydroxy-3-phenoxypropyl acrylate and 4-hydroxybutyl acrylate, are preferable, and 2-hydroxyethyl (meth)acrylate is more preferable. .

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

When the structural unit (c-2) having a hydroxyl group is introduced into the copolymer (A), the proportion 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%, and 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 include styrene, α-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-nitro styrene, p-cyano styrene, and p-acetylamino styrene; 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 ]undeca-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 , cyclic olefins having a norbornene structure, such as pentacyclo[7.4.0.1 ^2,5 .1 ^{9,12.0 8,13} ]pentadeca-3-ene; dienes such as butadiene, isoprene and chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, Iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, 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 Bornyl (meth) acrylate, 5-ethyl norbornyl (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) acrylic Rate, phenyl (meth) acrylate, cumyl (meth) acrylate, 4-phenoxyphenyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, nonylphenoxy polyethylene (meth)acrylic acid esters, such as glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, and 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 (meth)acrylic acid anthracenylamide; (meth)acrylic acid anilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl pyridine, vinyl acetate, vinyl toluene, such as vinyl compounds; unsaturated dicarboxylic acid diesters such as diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconic acid; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; and the like. 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.

<The manufacturing method of a 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%, most preferably (a0) 3 to 25 mol% and (b0) 15 -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 its monomers (a0) used in the production of the copolymer (A) The proportion of the external 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) greater than 0 mol% to 60 mol%.

The copolymerization reaction of the block isocyanato group-containing monomer (a0), the acid group-containing monomer (b0) and other monomers (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 be carried out, it is preferable to carry out in presence of the hydroxyl-containing organic solvent (B) mentioned later from a viewpoint that abnormal polymerization can be prevented and a polymerization reaction can be performed stably. Even if a blocked isocyanato group dissociates and an isocyanato group is generated by performing a copolymerization reaction in the presence of the hydroxyl group-containing organic solvent (B), the isocyanato group and the hydroxyl group of the hydroxyl group-containing organic solvent (B) react and abnormal polymerization is prevented. In the copolymer (A) obtained in this way, it is thought that a part of the blocking agent which had blocked the isocyanato group is substituted by the hydroxyl-containing organic solvent (B). For example, after dissolving these monomers in the hydroxyl-containing organic solvent (B), a polymerization initiator is added to the solution, and what is necessary is just to perform a polymerization reaction at 50-100 degreeC over 1 to 20 hours. At this time, when the polymerization reaction is carried out at a temperature at which the blocked isocyanato group of the blocked isocyanato group-containing monomer (a0) dissociates, the isocyanato group generated by dissociating the blocked isocyanato group reacts with the acid group to form a gel. Since this occurs, polymerization is preferably carried out at a temperature lower than the dissociation temperature of the blocked isocyanato group, preferably at a temperature lower than the dissociation temperature of the blocked isocyanato group by about 20 to 50°C.

Moreover, it is although 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 usage-amount of a polymerization initiator is 0.5-20 mass parts generally, when the total injection amount of a monomer makes 100 mass parts, Preferably it is 1.0-10 mass parts.

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 loss of a coloring pattern becomes difficult to generate|occur|produce after alkali image 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, image development time becomes suitable and practicality is ensured.

Moreover, although the acid value (JIS K6901 5.3) of a copolymer (A) can select suitably, when mix|blending with the photosensitive resin composition, Preferably it is 20-300KOHmg/g, More preferably, it is 30-200KOHmg/g. is the range of Alkali developability at the time of using as the acid value of a copolymer (A) being 20 KOHmg/g or more as a photosensitive resin composition becomes favorable. On the other hand, if the acid value of a copolymer (A) is 300 KOHmg/g or less, since it is hard to melt|dissolve an exposed part (photocured part) with respect to alkaline developing solution, a pattern shape becomes favorable.

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

<Hydroxy group-containing organic solvent (B)>

The hydroxyl group-containing organic solvent (B) may be an 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, and the like. 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 viewpoints of film forming properties and availability at the time of preparing a cured coating film. Do. These hydroxyl-containing organic solvents (B) may be used independently and may be used in combination of 2 or more type.

In this invention, the photosensitive resin composition is preserved by using together the copolymer (A) containing the structural unit (a) which has a block isocyanato group, and the structural unit (b) which has an acidic radical, and the hydroxyl-containing organic solvent (B). 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 such a reactive diluent (C) together with a copolymer (A), a viscosity can be adjusted, the intensity|strength of the hardened|cured material formed, and adhesiveness to a base material 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, butoxymethoxymethyl (meth) acrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydr Roxyethyl (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)acrylates such as (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylate of a phthalic acid derivative; 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.

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, 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 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)acryloxydiethoxyphenyl)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 (ie, tolylene diisocyanate), trimethylhexamethylene diisocyanate and hexamethylene diisocyanate, etc. (meth)acrylates, such as a reaction product of 2-hydroxyethyl (meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl) isocyanurate; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, a condensate of a polyhydric alcohol and N-methylol(meth)acrylamide, etc. are mentioned. 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, 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-[ 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-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthone, such as xanthone, thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone ; Acyl phosphine oxides; and the like. These photoinitiators (D) may be used independently and may be used in combination of 2 or more type.

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 addition to said component, in order to provide predetermined|prescribed 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 be made to contain a coloring agent (E) further, and it can be set as the photosensitive resin composition for color filters.

The coloring agent (E) will not be specifically limited as long as it melt|dissolves or disperse|distributes in the hydroxyl-containing organic solvent (B), For example, dye, a pigment, etc. are mentioned. As the dye, from the viewpoint of solubility in hydroxyl group-containing organic solvent (B) or alkali developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., acid dye having an acid group such as carboxylic acid or sulfonic acid, acid dye It is preferable to use a salt with a nitrogen compound of

Examples of such a dye 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, and the like. Among these, the acid dye of an azo type, a xanthene type, an anthraquinone type, or a phthalocyanine type is preferable. According to the color of the pixel made into the objective, these dyes may be used independently and may be used in combination of 2 or more type.

Examples of pigments include C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194, 214 yellow pigments; C.I. Orange pigments, such as pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 ; C.I. Blue pigments, such as pigment blue 15, 15:3, 15:4, 15:6, 60; C.I. Violet pigments, such as pigment violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments, such as Pigment Green 7, 36, 58, 59; C.I. Brown pigments, such as Pigment Brown 23 and 25; C.I. Black pigments, such as pigment black 1 and 7, carbon black, a titanium black, and iron oxide, etc. are mentioned.

These coloring agents (E) may be used independently according to the color of the pixel made into object, and may be used in combination of 2 or more type. Moreover, according to the color of the pixel made into the objective, you may use combining said dye and a 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 dispersing agent, it is preferable to use a polymer dispersing agent excellent in dispersion stability over time. Examples of the polymer dispersant include a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, and an aliphatic modified ester-based dispersant. As such a polymer dispersing agent, EFKA (manufactured by EFKA Corporation), Disperbyk (manufactured by Big Chemi Corporation), Disparon (manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (manufactured by Zeneca Corporation) are marketed under trade names. 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) in the photosensitive resin composition for color filters, a hydroxyl-containing organic solvent (B), a reactive diluent (C), a photoinitiator (D), and a coloring agent (E) is the photosensitive resin composition for color filters With respect to 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C) in the copolymer (A), 10 to 100 parts by mass, 30 to 1,000 parts by mass of the hydroxyl group-containing organic solvent (B), and the reactive diluent (C) ) is more than 0 mass parts - 90 mass parts, 0.1-30 mass parts of a photoinitiator (D), 5-80 mass parts of a coloring agent (E), Preferably, a copolymer (A) is 20-80 mass 50-800 mass parts of parts, hydroxyl-containing organic solvent (B), 20-80 mass parts of reactive diluents (C), 0.5-20 mass parts of photoinitiators (D), 5-70 masses of coloring agents (E) part, more preferably 30 to 75 parts by mass of the copolymer (A), 100 to 700 parts by mass of the hydroxyl group-containing organic solvent (B), 25 to 70 parts by mass of the reactive diluent (C), and a photopolymerization initiator ( D) is 1-15 mass parts, and a coloring agent (E) is 10-60 mass parts. If it is a compounding quantity of this range, it will become the photosensitive resin composition for color filters which has an appropriate 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 group 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 photopolymerization initiator (D), and the colorant (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 preferable as a resist. For curing of the photosensitive resin composition, the baking temperature may be appropriately selected within the range of 250° C. or less, but since the copolymer (A) used in the present invention has excellent curability at low temperatures, the baking temperature is lower than that of conventional materials. can be made lower In the photosensitive resin composition, when a pigment is used as a coloring agent (E), sufficient sclerosis|hardenability is acquired also in baking temperature 160 degreeC or less. The photosensitive resin composition of this invention is advantageous from the point of energy consumption, since a crosslinking reaction fully advances even if baking temperature is low. Moreover, it becomes possible to use even if it is a coloring agent (E) and a board|substrate which are inferior in heat resistance, the characteristic characteristic of a colorant is acquired, and application to various board|substrates also becomes possible. From such a standpoint, the baking temperature is preferably 160°C or lower, more preferably 150°C or lower. Although the lower limit of the baking temperature is not necessarily constant depending on the type of block isocyanato group contained in the copolymer (A), it needs to be equal to or higher than the dissociation temperature of the block isocyanato group, and is usually 80° C. or higher, preferably is 90°C or higher, more preferably 100°C or higher. When the 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, Usually, it is 10 minutes - 4 hours, Preferably they are 20 minutes - 2 hours.

The photosensitive resin composition of the present invention is suitable as a resist used for manufacturing various resists, particularly color filters to be inserted into organic EL displays (for black PDL), liquid crystal displays, solid-state imaging devices such as CCD and CMOS, and the like. Moreover, since the photosensitive resin composition of this invention provides the cured coating film excellent in solvent resistance, hardening characteristic at low temperature, etc., it can also be used for various coatings, adhesives, binders for printing inks, etc.

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

<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 a coloring pattern formed using said photosensitive resin composition for color filters. A color filter is normally comprised from a board|substrate, the RGB pixel formed thereon, the black matrix formed in the boundary of each pixel, and the protective film formed on the pixel and the black matrix. This structure WHEREIN: A well-known thing can be employ|adopted for other structures except that a pixel and a black matrix (coloring pattern) are formed using the photosensitive resin composition for color filters mentioned above.

Next, one Embodiment of the manufacturing method of a color filter is demonstrated. First, a coloring pattern is formed on a substrate. Specifically, a black matrix and RGB pixels are sequentially formed on a substrate. The material of the substrate is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed wiring boards, array substrates, etc. are appropriately selected. can be used

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

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 the hydroxyl-containing organic solvent (B) by heating using heating means, such as a circulation 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 at the temperature of 50 degreeC - 120 degreeC for 30 second - 30 minutes.

Next, the formed coating film is partially exposed by irradiating active energy rays such as ultraviolet rays or excimer laser beams through a negative mask. 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 solutions, 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 -ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and p-phenyls such as sulfate, hydrochloride or p-toluenesulfonate salts thereof An aqueous solution of a rendiamine-based compound or the like may be used. In addition, 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 the baking temperature is 200 ° C. or less, the solvent resistance of the coloring pattern is insufficient, but in the photosensitive resin composition for a color filter of the present invention, even when baked at a temperature of 120 ° C. or less, sufficient solvent resistance is shown. A coloring pattern can be formed. Therefore, baking temperature can be made low, and when baking at high temperature, a processing time can be shortened, and it becomes a great advantage in manufacturing. From such a 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 It is carried out in 2 hours.

A desired coloring pattern can be formed by repeating the above application|coating, exposure, image development, and baking one by one using the photosensitive resin composition for black matrices, and the photosensitive resin composition for red, green, and blue pixels. In addition, in the above, although the formation method of the coloring pattern by photocuring was demonstrated, when the photosensitive resin composition which mix|blended the hardening accelerator and a well-known epoxy resin is used instead of the photoinitiator (D), the inkjet method applied Then, a desired coloring pattern can also be formed by heating. Next, a protective film is formed on the coloring pattern (each pixel of RGB and a black matrix). It does not specifically limit as a protective film, What is necessary is just to form using a well-known thing.

The color filter manufactured in this way is excellent in sensitivity and developability, and since it is manufactured using the photosensitive resin composition which can harden at low temperature and gives a coloring pattern excellent in solvent resistance, it is excellent with little color change. It has a colored pattern.

<Image display element>

The image display element of this invention is an image display element provided with said color filter, Solid-state imaging elements, such as a liquid crystal display element, an organic electroluminescent display element, a CCD element, and a CMOS element, etc. are mentioned as the specific example. Manufacture of the image display element of this invention may be performed according to a normal method except 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 sequentially formed. And what is necessary is just to form an electrode etc. on another board|substrate, to bond both, and to inject|pour and seal a predetermined amount of liquid crystals.

Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by these Examples. Incidentally, in this example, parts and percentages are all based on mass unless otherwise specified. In addition, the measuring method of an acid value and a weight average molecular weight is as follows.

(1) Acid value: The acid value of the copolymer (A) measured according to JIS K6901 5.3, meaning the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the copolymer (A).

(2) A weight average molecular weight (Mw) means the standard polystyrene conversion weight average molecular weight measured on the following conditions 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 the copolymer

Developing solvent: tetrahydrofuran

Detector: Differential refractometer (Shodex 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 device, the dropping funnel, the condenser, the thermometer, and the gas introduction tube, it stirred, nitrogen substitution, and heated up to 78 degreeC. Next, 22.4 g of dicyclopentanylmethacrylate, 17.2 g of methacrylic acid and 50.2 g of methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl (Kalenz MOI- BP, manufactured by Showa Denko Co., Ltd., dissociation rate of block isocyanato group: 70 mass%), and a monomer mixture comprising 11.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) ) was added to and dissolved in 62.8 g of propylene glycol monomethyl ether acetate, and was added dropwise to the flask from the dropping funnel, respectively. After completion|finish of dripping, it copolymerized by stirring at 78 degreeC for 3 hours, the copolymer was produced|generated, and the polymer composition (component density|concentration other than a solvent 35 mass %) of sample No. 1 was obtained. The weight average molecular weight of the copolymer in the obtained polymer composition was 9,100, and the acid value was 121.5 KOHmg/g.

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

A copolymerization reaction was performed under the same conditions as in Synthesis Example 1 except for using the raw materials shown in Tables 1 and 2 to obtain polymer compositions (concentrations of components other than solvents of 35% by mass) of Sample Nos. Tables 1 and 2 show the weight average molecular weight and acid value of the copolymer in the obtained polymer composition. In addition, in Tables 1 and 2, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylate is the Showa Denko Co., Ltd. make, Karenz MOI-BM, block isocyanato group. Dissociation rate: 18% by mass, malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester is produced by Showa Denko. Karenz MOI-DEM, manufactured by K.K., dissociation rate of blocked isocyanato group: 90 mass%, benzoic acid-4-[[[[2-[(2-methyl-1-oxo-2-propene-1- yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester has a dissociation rate of a blocked isocyanato group: 40 mass%, and benzoic acid-2-[[[[2-[(2-methyl-1-oxy] -2-propen-1-yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester has a dissociation rate of a blocked isocyanato group: 75% by mass, and 2-propenoic acid-2-methyl-2- [[(3,5-dimethylphenoxy)carbonyl]amine]ethyl ester has a dissociation rate of a blocked isocyanato group: 28 mass%.

[Examples 1 to 9 and Comparative Examples 1 to 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, 100 parts by mass of C.I Pigment Green 36 (colorant), 44.98 parts by mass of propylene glycol monomethyl ether acetate, and a dispersing agent (Disperbyk- by Bikkemi Japan Co., Ltd.) 161) was added in 25 parts by mass, mixed with a paint shaker for 2 hours and dispersed to prepare a green pigment dispersion.

This green pigment dispersion liquid was mixed with the other compounding component (namely, a polymer composition, a reactive diluent, a photoinitiator, and a solvent) shown in Table 3, and the photosensitive resin composition was prepared. The compounding ratio of each component is as showing in Table 3. In addition, the photosensitive resin composition of Examples 1-9 is prepared using each polymer composition of Sample No. 1-9, The photosensitive resin composition of Comparative Examples 1-2 is the polymer composition of Sample No.10-11, respectively was prepared using In addition, the quantity of a polymer composition includes the solvent contained at the time of copolymer reaction completion|finish, and the quantity of the solvent contained in each sample is also added up in the solvent as a compounding component.

<Evaluation of the photosensitive resin composition>

(1) alkali developability

After spin-coating each of the photosensitive resin compositions of Examples 1-9 and Comparative Examples 1-2 on a 5 cm horizontal glass substrate (alkali-free glass substrate) so that the thickness after exposure might be set to 2.5 micrometers, at 90 degreeC The solvent was volatilized by heating for 3 minutes. Next, a photomask of a predetermined pattern was placed 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, and the exposed portion was photocured. Next, an unexposed part was dissolved and developed by spraying an aqueous solution containing 0.1 mass % sodium carbonate at a temperature of 23°C and a pressure of 0.3 MPa, followed by baking at 100°C for 20 minutes to form a predetermined pattern. The residue after alkali development was confirmed by observing the pattern after alkali development using the Hitachi High-Technologies Co., Ltd. electron microscope S-3400. The criteria for this evaluation are as follows.

○: no residue

×: Residue

The evaluation result of alkali developability is shown in Table 4.

(2) Evaluation of solvent resistance

After spin-coating each of the photosensitive resin compositions of Examples 1-9 and Comparative Examples 1-2 so that the thickness after baking may be set to 2.5 micrometers on a 5 cm horizontal glass substrate (alkali-free glass substrate), it is 90 degreeC The solvent was volatilized by heating for 3 minutes. Next, after exposing the light of wavelength 365nm to the coating film and photocuring the exposed part, it was left to stand for 20 minutes in the dryer with a baking temperature of 100 degreeC, and the cured coating film was produced. 200 ml of propylene glycol monomethyl ether acetate was put into a 500 ml glass bottle with a lid, and it left still under the conditions of 80 degreeC. After immersing the said test piece with a cured coating film therein, it left still for 5 minutes in the state hold|maintained at 80 degreeC. The color change (ΔE*ab) before and after the test piece was immersed 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 to 2 were weighed in equal amounts in a glass container, and the inlet was closed with aluminum foil so that dust, etc. might not enter. Next, these samples were left still in the thermostat maintained at 23 degreeC, respectively, and the weight average molecular weight (Mw) of the sample after 1 month was measured. Table 5 shows the rate of change of Mw after 1 month. When the change rate of Mw after 1 month is within 20%, it can be said that the storage stability of the copolymer is excellent.

The photosensitive resin composition of Examples 1-9 using the polymer composition of Sample No. 1-9 had favorable alkali developability and solvent resistance so that the result of Table 4 might show. In addition, since the storage stability of a copolymer has 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 using the polymer composition of sample No. 1-9. It can be said that the storage stability of silver is also good. On the other hand, although the photosensitive resin composition of Comparative Examples 1-2 using the polymer composition of Sample No.10-11 has favorable storage stability, the photosensitive resin composition of Comparative Example 1 using the polymer composition of Sample No.10 is , solvent resistance was not enough, and alkali developability and solvent resistance were not enough for the photosensitive resin composition of the comparative example 2 using the polymer composition of sample No. 11.

According to this invention, while developability is favorable, the photosensitive resin composition excellent in solvent resistance and storage stability can be provided so that the above result may show.

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

Claims (13)

A copolymer (A), a hydroxyl group-containing organic solvent (B), a reactive diluent (C), and a photoinitiator (D) are contained;
The copolymer (A) is 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-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)car a structural unit derived from at least one selected from the group consisting of bornyl]amine]ethyl ester, a structural unit (b) having an acid group, and other structural units (c);
The said other structural unit (c) contains the structural unit (c-2) which has a hydroxyl group, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1,
The hydroxyl group-containing organic solvent (B), 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, C5-6 cycloalkanediol, C5-6 cycloalkanedimethanol, ethyl lactate, and diacetone alcohol. 3. The method according to claim 1 or 2,
The photosensitive resin composition in which the structural unit (b) which has the said acidic radical is a structural unit derived from an unsaturated carboxylic acid. 3. The method according to claim 1 or 2,
The copolymer (A) is the methacrylic acid 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl, methacrylic acid 2-[O-(1'-methylpropylideneamino)carboxy Amino]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) The photosensitive resin composition containing 1-40 mol% of the structural unit derived from at least 1 type selected from the group which consists of carbonyl] amine] ethyl ester, and 1-60 mol% of the structural unit (b) which has the said acidic radical. 3. The method according to claim 1 or 2,
2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid 2-[O-(1'-methylpropylideneamino) in the copolymer (A) 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-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy) ) The photosensitive resin composition in which the molar ratio of the structural unit derived from at least 1 type selected from the group which consists of carbonyl] amine] ethyl ester, and the structural unit (b) which has the said acidic radical is 10:90-50:50. 3. The method according to claim 1 or 2,
The copolymer (A) is 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-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)car A structural unit (a) derived from at least one selected from the group consisting of bornyl]amine]ethyl ester, a structural unit (b) derived from (meth)acrylic acid, glycidyl (meth)acrylate, 2-hydroxy The photosensitive resin composition containing the structural unit (c) derived from at least 1 sort(s) selected from the group which consists of ethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and methyl (meth)acrylate. 3. The method according to claim 1 or 2,
The photosensitive resin composition for color filters which further contains a coloring agent (E). 8. The method of claim 7,
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), 30 to 1000 parts by mass of the hydroxyl group-containing organic solvent (B), the above The photosensitive resin composition in which more than 0 mass parts - 90 mass parts of reactive diluents (C), 0.1-30 mass parts of said photoinitiators (D), and 5-80 mass parts of said coloring agents (E) contain. 8. The method of claim 7,
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 Claim 7, The color filter characterized by the above-mentioned. The color filter of Claim 10 is provided, The image display element characterized by the above-mentioned. A method for producing a color filter comprising the step of applying the photosensitive resin composition according to claim 7 to a substrate, exposing it, alkali developing, and then baking at a temperature of 160° C. or less to form a colored pattern. 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid, 2-[O-(1'-methylpropylideneamino) methacrylic acid in the presence of a hydroxyl group-containing organic solvent (B) 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-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy) ) carbonyl] amine] ethyl ester, at least one selected from the group consisting of, an unsaturated carboxylic acid and a monomer having a polymerizable unsaturated bond and a hydroxyl group are copolymerized to react to synthesize a copolymer (A), followed by a reactive diluent (C) And the manufacturing method of the photosensitive resin composition including the process of mix|blending a photoinitiator (D).