KR20230014841A - Copolymer and photosensitive resin composition for color filter - Google Patents

Abstract

A copolymer (A) containing a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group, a solvent (B), a reactive diluent (C), The photosensitive resin composition for color filters containing a photoinitiator (D) and a coloring agent (E).

Description

Photosensitive resin composition for copolymer and color filter {COPOLYMER AND PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER}

The present invention relates to a novel copolymer, a photosensitive resin composition for color filters containing the same, a color filter, an image display element including the same, and a method for producing the color filter.

In recent years, from the viewpoint of resource saving and energy saving, photosensitive resin compositions curable by active energy rays such as ultraviolet rays and electron beams have been widely used in fields such as various coatings, printing, paints, and adhesives. Moreover, also in the field of electronic materials, such as a printed wiring board, the photosensitive resin composition hardenable by an active energy ray is used for a solder resist, a resist for color filters, etc. In addition, the required properties of the curable photosensitive resin composition are becoming increasingly diverse and highly advanced, and among them, short-time curability considering productivity and low-temperature curability that suppresses thermal damage to members 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 on the boundary between the pixels, and pixels and It is composed of a protective film formed on the black matrix. A color filter having such a structure is usually manufactured by sequentially forming a black matrix, pixels, and a protective film on a transparent substrate. As a method of forming the pixels and the black matrix (hereinafter, the pixels and the black matrix are referred to as "coloring patterns"), various methods have been proposed. Among them, a pigment/dye dispersion method produced by a photolithography method using a photosensitive resin composition as a resist and repeating application, exposure, development, and baking provides a coloring pattern with excellent durability and fewer defects such as pinholes. Because of that, it has become the current mainstream.

In general, the photosensitive resin composition used in the photolithography method contains an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant and a solvent. In the pigment/dye dispersion method, while having the above advantages, high heat resistance is required in terms of repeating black matrix, R, G, and B patterns, and it 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 is an alkali-soluble resin, a polymerizable compound having an ethylenically unsaturated bond, a radiation-sensitive polymerization initiator, a colorant, and a compound such as ethyl 3-aminobenzenesulfonate, which enables low-temperature curing and improves storage stability. A coloring composition is disclosed.

Patent Document 2 is a photosensitive resin containing 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 with electromagnetic waves and heating. Low-temperature hardening is made possible by using a composition.

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

In recent years, flexible displays such as electronic paper have spread. As a substrate of this flexible display, plastic substrates such as polyethylene terephthalate are being studied. Since this substrate has a property of elongating or contracting during baking, it is necessary to lower the temperature of the baking process. However, the level achieved in Patent Literature 1 is insufficient to satisfy the above requirements. Further, in Patent Literature 2, low-temperature curability is improved, but storage stability is low, and practical use is difficult.

The present invention has been made to solve the above problems, and while having good developability and storage stability, a photosensitive resin composition for color filters that imparts a colored pattern having excellent solvent resistance even when cured at low temperatures, and the photosensitive resin composition thereof Its object is to provide a copolymer useful for the preparation of

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 the color filter.

That is, this invention is represented by the following [1] - [25].

[1] A copolymer (A) characterized by containing a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group.

[2] The structural unit (a) having a block isocyanato group is a structural unit derived from a (meth)acrylate containing a block isocyanato group, and the block isocyanato group-containing (meth)acrylate The copolymer according to [1], wherein the cyanato group dissociation rate is 5 to 99% by mass when heated at 100°C for 30 minutes.

[3] The blocking agent for the structural unit (a) having a block isocyanato group is diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate and 3,5-xylenol, and the copolymer according to [1] or [2], which is at least one selected from the group consisting of.

[4] The copolymer according to any one of [1] to [3], wherein the structural unit (b) having an acid group is a structural unit derived from an unsaturated carboxylic acid.

[5] The copolymer according to any one of [1] to [4], wherein the structural unit (c) having an epoxy group is a structural unit derived from an epoxy group-containing (meth)acrylate.

[6] The copolymer (A) contains 1 to 60 mol% of the structural unit (a) having the block isocyanato group, 5 to 65 mol% of the structural unit (b) having the acid group, and the epoxy group The copolymer according to any one of [1] to [5], containing 5 to 65 mol% of the structural unit (c).

[7] The molar ratio of the structural unit (a) having the block isocyanato group in the copolymer (A) and the structural unit (c) having the epoxy is 10: 90 to 75: 25 [1 ] to the copolymer described 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-dimethylphenone xi) carbonyl] amine] ethyl ester derived from at least one structural unit (a), (meth)acrylic acid-derived structural unit (b), and glycidyl (meth)acrylate-derived Any one of [1] to [7] containing a structural unit (c) and a structural unit (e) derived from at least one selected from the group consisting of dicyclopentanyl (meth)acrylate and methyl (meth)acrylate; The copolymer described in one.

[9] The copolymer according to any one of [1] to [8], wherein the copolymer (A) further contains a structural unit (d) having a hydroxyl group.

[10] 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-dimethylphenone xi) carbonyl] amine] ethyl ester derived from at least one structural unit (a), (meth)acrylic acid-derived structural unit (b), and glycidyl (meth)acrylate-derived Structural unit (c), structural unit (d) derived from 2-hydroxyethyl methacrylate, and derived from at least one member selected from the group consisting of dicyclopentanyl (meth)acrylate and methyl (meth)acrylate The copolymer as described in [9] containing the structural unit (e).

[11] The copolymer (A) is composed of a structural unit (a) derived from 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl methacrylic acid and a structural unit derived from (meth)acrylic acid ( The copolymer according to [8], comprising b), a structural unit (c) derived from glycidyl (meth)acrylate, and a structural unit (e) derived from dicyclopentanyl (meth)acrylate.

[12] The copolymer (A) is composed of a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit derived from (meth)acrylic acid The copolymer according to [8], comprising (b), a structural unit (c) derived from glycidyl (meth)acrylate, and a structural unit (e) derived from dicyclopentanyl (meth)acrylate.

[13] The copolymer (A) contains a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit derived from (meth)acrylic acid (b), a structural unit derived from glycidyl (meth)acrylate (c), a structural unit derived from 2-hydroxyethyl methacrylate (d), and a structural unit derived from dicyclopentanyl (meth)acrylate The copolymer according to [10], containing the unit (e).

[14] The copolymer (A) is derived from malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester Structural unit (a), structural unit (b) derived from (meth)acrylic acid, structural unit (c) derived from glycidyl (meth)acrylate, and structural unit derived from dicyclopentanyl (meth)acrylate ( The copolymer described in [8] containing e).

[15] The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),

The copolymer (A) contains 1 to 40 mol% of the structural unit (a) having the block isocyanato group, 1 to 60 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group [1] containing 1 to 70 mol% of (c), more than 0 mol% to 50 mol% of the structural unit (d) having the hydroxyl group, and more than 0 mol% to 80 mol% of the structural unit (e) The copolymer described in any one of [5].

[16] The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),

The copolymer (A) contains 3 to 20 mol% of the structural unit (a) having the block isocyanato group, 20 to 50 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group [1] to [5] containing 20 to 40 mol% of (c), more than 0 mol% to 20 mol% of the structural unit (d) having the hydroxyl group, and 20 to 40 mol% of the structural unit (e) The copolymer according to any one of the above.

[17] A polymer composition characterized by containing the copolymer (A) according to any one of [1] to [16], and at least one of a solvent (B) and a reactive diluent (C).

[18] A photosensitive resin composition characterized by containing the copolymer (A) according to any one of [1] to [16], a solvent (B), a reactive diluent (C), and a photopolymerization initiator (D).

[19] Characterized by containing the copolymer (A) according to any one of [1] to [16], a solvent (B), a reactive diluent (C), a photopolymerization initiator (D) and a colorant (E) A photosensitive resin composition for color filters.

[20] Based on 100 parts by mass of the total amount of the copolymer (A) and the reactive diluent (C), the copolymer (A) is 10 to 100 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, the above The color filter according to [19], wherein the reactive diluent (C) is greater than 0 to 90 parts by mass, the photopolymerization initiator (D) is 0.1 to 30 parts by mass, and the colorant (E) is 3 to 80 parts by mass. A photosensitive resin composition.

[21] The photosensitive resin composition for color filters according to [19] or [20], wherein the solvent (B) contains a hydroxyl group-containing organic solvent.

[22] The photosensitive resin composition for color filters according to any one of [19] to [21], wherein the colorant (E) contains a pigment.

[23] A color filter characterized by having a color pattern comprising a cured product of the photosensitive resin composition for color filters according to any one of [19] to [22].

[24] An image display element characterized by comprising the color filter according to [23].

[25] A step of applying the photosensitive resin composition for a color filter according to any one of [19] to [22] to a substrate, exposing, alkali developing, and then baking at a temperature of 160 ° C. or less to form a colored pattern. A method for manufacturing a color filter comprising:

According to the present invention, it is possible to provide a photosensitive resin composition for a color filter which has good developability and storage stability and imparts a colored pattern having excellent solvent resistance even when cured at a low temperature, and a copolymer useful for preparing the photosensitive resin composition. can

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 the color filter can be provided.

<Copolymer (A)>

The copolymer (A) of the present invention is characterized by containing a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group.

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

The structural unit (a) containing a block isocyanato group contained in the copolymer (A) is a structural unit derived from a monomer containing a block isocyanato group. Examples of the monomer include 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 the molecule; The compound block|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 a solvent that is inactive with respect to the isocyanato group. In the case of blocking reaction, you may use organometallic salts, such as tin, zinc, and lead, tertiary amine, etc. as a catalyst. The reaction can generally be carried out at -20 to 150°C, but is preferably carried out at 0 to 100°C. As an example of said isocyanate compound, the compound represented by following formula (1) is mentioned.

[Formula 1]

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

As an isocyanate compound represented by said formula (1), specifically, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate Rate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, meta Chryloyl isocyanate etc. are mentioned. In addition, an equimolar (1 mol: 1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. As the alkyl group of the 2-hydroxyalkyl (meth)acrylate described above, an ethyl group or an n-propyl group is preferable, and an ethyl group is more preferable. Examples of the above diisocyanate compounds 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-) xylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclo Hexane, lysine diisocyanate, etc. are mentioned.

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 methacryloylisocyanate are preferred, and 2-iso Cyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.

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

As a blocking agent which blocks the isocyanato group in an isocyanate compound, For example, Lactam system, such as epsilon caprolactam, delta-valerolactam, gamma-butyrolactam, and 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; butylphenols such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, phenols such as dinonyl phenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; Active methylene type, such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; mercaptan systems such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; amines such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; Acid amide systems, such as acetanilide, acetanisidide, acetic acid amide, and benzamide; acid imide systems such as succinic acid imide and maleic acid imide; Imidazole types, such as imidazole, 2-methylimidazole, and 2-ethylimidazole; pyrazoles such as pyrazole and 3,5-dimethylpyrazole; Urea type|system|group, such as urea, thiourea, and ethylene urea; Carbamidate systems such as phenyl N-phenylcarbamate and 2-oxazolidone: Imine systems such as ethyleneimine and polyethyleneimine; oxime systems such as formaldoxime, acetaldooxime, acetooxime, 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 individually or may be used in combination of 2 or more type.

Although the blocking agent protects the highly reactive isocyanato group, the blocked isocyanato group is dissociated by heating and the isocyanato group is regenerated. In the present invention, the isocyanato group reacts with the reactive functional group contained in the copolymer (A) or the reactive diluent (C), that is, an acid group or optionally a hydroxyl group, an amino group, etc., and the crosslinking density is high. form a cured product.

From the viewpoint of the low-temperature curability and storage stability of the photosensitive resin composition for color filters described later, a block isocyanato group-containing (meth)acrylate is used as a monomer giving the structural unit (a) having a block isocyanato group. It is desirable to do The dissociation rate of the block isocyanato group in the case of heat treatment at 100 ° C. for 30 minutes is preferably 5 to 99% by mass, more preferably 8 to 97% by mass, and most preferably 10 to 95% by mass. It is more preferable to use a (meth)acrylate containing a block isocyanato group. In addition, the dissociation rate of the block isocyanato group of the block isocyanato group-containing (meth)acrylate is determined by preparing an n-octanol solution in which the concentration of the block isocyanato group-containing (meth)acrylate is 20% by mass After adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to the solution, the block isocyanato group-containing after heating at 100 ° C. for 30 minutes (meth) ) Let the mass reduction rate of acrylate be the value measured by HPLC analysis. When a block isocyanato group-containing (meth)acrylate having a dissociation rate in the above range is used, the stability of the copolymer at the time of synthesis can be sufficiently secured, the baking temperature at the time of producing a cured coating film can be sufficiently lowered, and the cured coating film The solvent resistance can also be sufficiently secured. Blocking agents for (meth)acrylates containing a blocked isocyanato group having such a dissociation rate include diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, and 4-hydroxyl. methyl benzoate, 3,5-xylenol, γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol and diisopropylamine. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate and 3,5-xylenol are preferred from the viewpoint of low-temperature curing properties. desirable.

Moreover, it is also preferable to use block isocyanato group-containing (meth)acrylate whose dissociation temperature of the block isocyanato group of a block isocyanato group-containing (meth)acrylate is 80 degreeC or more. When a block isocyanato group-containing (meth)acrylate having a dissociation temperature of 80 ° C. or higher is used, stability of the copolymer during synthesis can be sufficiently secured, and unintended crosslinking reaction can be reduced during the denaturation reaction described later. there is. On the other hand, if the dissociation temperature of a block isocyanato group is 160 degreeC or less, baking temperature can fully be lowered and the solvent resistance of a cured coating film can also fully be ensured. In addition, the dissociation temperature of the block isocyanato group of the block isocyanato group-containing (meth)acrylate prepares an n-octanol solution in which the concentration of the block isocyanato group-containing (meth)acrylate is 20% by mass 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (a polymerization inhibitor) were added to the solution, followed by heating at a predetermined temperature, and containing the block isocyanato group after 30 minutes. The mass reduction rate of (meth)acrylate is measured by HPLC analysis, and the temperature at which the mass reduction rate becomes 80% by mass or more is the dissociation temperature of the block isocyanato group.

An example of the block isocyanato group-containing (meth)acrylate described above is Karenz (registered trademark) MOI-DEM (reaction product of methacryloyloxyethyl isocyanate and diethyl malonate, shown by the following formula (2)) Manufactured by Wa Denko Co., Ltd., dissociation temperature of block isocyanato group: 90 ° C., dissociation rate: 90 mass%), Karenz MOI-BP represented by the following formula (3) (methacryloyloxyethyl isocyanate and 3,5- Reaction product of dimethylpyrazole, manufactured by Showa Denko Co., Ltd., dissociation temperature of block isocyanato group: 110 ° C., dissociation rate: 70% by mass), Karenz MOI-BM represented by the following formula (4) (methacryloyl Methacrylates such as reaction products of oxyethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Electric Co., Ltd., dissociation temperature of block isocyanato group: 130°C, dissociation rate: 18% by mass) and acrylates corresponding thereto, and the like can be heard These block isocyanato group-containing (meth)acrylates may be used alone or in combination of two or more.

[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%, most preferably It is preferably 3 to 25 mol%. When the ratio of the structural unit (a) having a block isocyanato group is 1 to 40 mol%, the solvent resistance of the cured coating film is improved, and the storage stability of the copolymer (A) is also maintained.

<Structural unit (b) having an acid group>

The structural unit (b) containing an acidic radical contained in the copolymer (A) is a structural unit derived from a monomer containing an acidic radical (except for structural units (a) having a block isocyanato group). As an acidic group, a carboxyl group, a sulfo group, a phospho group, etc. are mentioned, Among these, a carboxyl group is preferable from the point of availability. As a monomer giving the structural unit (b) which has an acid group, the monomer which has a polymerizable unsaturated bond and an acid group, 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 or anhydrides thereof such as acids, 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; etc. can be mentioned. These monomers may be used individually or may be used in combination of 2 or more type. Among these, from the viewpoint of excellent alkali developability and ease of availability, unsaturated carboxylic acids are preferred, and (meth)acrylic acid is more preferred.

In the present invention, the alkali developability at the time of using the copolymer (A) as a photosensitive material is greatly improved by including the structural unit (b) having an acid group in the 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 60 mol%. 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 formation of a precise pattern becomes possible.

<Structural unit (c) having an epoxy group>

The structural unit (c) having an epoxy group contained in the copolymer (A) is a structural unit derived from an epoxy group-containing monomer (provided that the structural unit (a) having the block isocyanato group and the structural unit having the acid group ( b) is excluded). As the monomer giving the constituent unit (c) having an epoxy group, a monomer having a polymerizable unsaturated bond and an epoxy group, for example, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglyc Cidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxy (meth)acrylic acid ester derivatives containing an epoxy group such as propyl (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 rings such as 4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate (meth)acrylic acid ester derivatives 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 individually or may be used in combination of 2 or more type. Among these, from the viewpoint of polymerizability and availability, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth) Acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3-glycidyloxypropyl (meth)acrylate, glycidyloxyphenyl (meth)acrylate Epoxy group-containing (meth)acrylates such as the like are preferable, and glycidyl (meth)acrylate is more preferable.

In the present invention, the solvent resistance at the time of using the copolymer (A) as a photosensitive material is greatly improved by including the structural unit (c) having an epoxy group in the copolymer (A).

The proportion of the structural unit (c) having an epoxy group contained in the copolymer (A) is not particularly limited, but is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, and most preferably 10 to 60 mol%. 40 mol%. When the ratio of the constituent unit (c) having an epoxy group is 1 to 60 mol%, the solvent resistance of the cured coating film and the storage stability of the copolymer (A) are compatible.

In the copolymer (A), the molar ratio of the structural unit (a) having a block isocyanato group and the structural unit (c) having an epoxy may be, for example, 1:99 to 99:1, and curing From the viewpoint of the solvent resistance of the coating film and the storage stability of the copolymer (A), the ratio is preferably 5:95 to 85:15, and more preferably 10:90 to 75:25.

<Structural unit (d) having a hydroxyl group>

The copolymer (A) may further contain a structural unit (d) having a hydroxyl group. The structural unit (d) having a hydroxyl group contained in the copolymer (A) is a structural unit derived from a monomer containing a hydroxyl group (however, the structural unit (a) having a block isocyanato group and the structural unit having an acid group ( b), those corresponding to the structural unit (c) having an epoxy group are excluded). As the monomer giving the structural unit (d) 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-hydroxybutyl acrylate and the like. there is. These monomers may be used individually or may be used in combination of 2 or more type. Among these, from a polymerizable viewpoint, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl ( (meth)acrylic acid ester derivatives containing a hydroxyl group such as meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate are preferable, and 2-hydroxyethyl (meth)acrylic acid rate is more preferred.

In the present invention, the structural unit (d) having a hydroxyl group is not essential, but when the copolymer (A) contains the structural unit (d) having a hydroxyl group, the solvent resistance at the time of using the copolymer (A) as a photosensitive material is improved. greatly improved

The ratio of the structural unit (d) having a hydroxyl group contained in the copolymer (A) is not particularly limited, but is preferably greater than 0 mol% to 50 mol%, more preferably greater than 0 mol% to 40 mol%, Most preferably, it is more than 0 mol% - 30 mol%. When the ratio of the structural unit (d) having a hydroxyl group is more than 0 mol% to 50 mol%, the solvent resistance of the cured coating film and the storage stability of the copolymer (A) are compatible.

<Other structural units (e)>

In this invention, as a structural unit which a copolymer (A) contains, the structural unit (a) which has a block isocyanato group, the structural unit (b) which has an acid group, the structural unit (c) which has an epoxy group, and a hydroxyl group Along with the structural unit (d), other structural units (e) copolymerizable with these may be contained (provided that the structural unit (a) having the block isocyanato group and the structural unit (b) having the acid group) , except those corresponding to the structural unit (c) having an epoxy group and the structural unit (d) having a hydroxyl group). Specific examples of the monomer giving the other structural unit (e) include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, and p -Aromatic vinyl compounds, such as chlorostyrene, o-methoxy styrene, m-methoxy styrene, p-methoxy styrene, 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-ethylnorbornyl(meth)acrylate, dicyclopentenyl(meth)acrylate, dicyclopentanyl(meth)acrylate, dicyclopentenyloxyethyl acrylate isobornyl (meth)acrylate, adamantyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate , perfluoro-n-propyl (meth)acrylate, perfluoro-isopropyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate 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; vinyl compounds such as (meth)acrylic acid anilide, (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 citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide; etc. can be mentioned. Among these, (meth)acrylic acid esters are preferable, and methyl (meth)acrylate and dicyclopentanyl (meth)acrylate are particularly preferable. These monomers may be used individually or may be used in combination of 2 or more type.

The proportion of the other constituent units (e) contained in the copolymer (A) is not particularly limited, but is preferably greater than 0 mol% to 80 mol%, more preferably 5 to 70 mol%, and most preferably It is 10-60 mol%. In the present invention, the other structural unit (e) is not essential, but solvent resistance and the characteristics of the coating film can be appropriately improved by including the other structural unit (e) in the copolymer (A).

<Method for producing copolymer (A)>

The ratio of the block isocyanato group-containing monomer (a0), the acid group-containing monomer (b0) and the epoxy group-containing monomer (c0) used in the production of the copolymer (A) is not particularly limited, but preferably (a0 ) 1 to 60 mol%, (b0) 5 to 65 mol% and (c0) 5 to 65 mol%, more preferably (a0) 5 to 50 mol%, (b0) 15 to 55 mol% and (c0) ) 15 to 55 mol%, most preferably (a0) 10 to 40 mol%, (b0) 25 to 45 mol%, and (c0) 25 to 45 mol%. When the copolymer (A) further contains a structural unit (d) having a hydroxyl group and other structural units (e), a block isocyanato group-containing monomer (a0) used in the production of the copolymer (A) The ratio of the acid group-containing monomer (b0), the epoxy group-containing monomer (c0), the hydroxyl group-containing monomer (d0), and other monomers (e0) is preferably (a0) 1 to 40 mol%, (b0) 1 to 60 mol%, (c0) 1 to 70 mol%, (d0) more than 0 mol% to 50 mol%, and (e0) more than 0 mol% to 80 mol%, more preferably (a0) 2 to 30 mol% , (b0) 10 to 55 mol%, (c0) 10 to 60 mol%, (d0) greater than 0 mol% to 30 mol% and (e0) 5 to 60 mol%, most preferably (a0) 3 to 20 mol%, (b0) 20 to 50 mol%, (c0) 20 to 40 mol%, (d0) more than 0 mol% to 20 mol%, and (e0) 20 to 40 mol%.

The copolymerization reaction of the block isocyanato group-containing monomer (a0), acid group-containing monomer (b0), epoxy group-containing monomer (c0), hydroxyl group-containing monomer (d0), and other monomers (e0) is known in the art. Depending on the radical polymerization method, it can be carried out in the presence or absence of a polymerization solvent. For example, after dissolving these monomers in a solvent as desired, a polymerization initiator may be added to the solution, and a polymerization reaction may be performed at 50 to 100°C for 1 to 20 hours. At this time, when the polymerization reaction is carried out at a temperature at which the block isocyanato group of the block isocyanato group-containing monomer (a0) dissociates, the isocyanato group generated by dissociation of the block isocyanato group reacts with the acid group to form a gel. Since this occurs, it is preferable to carry out the polymerization at a temperature lower than the dissociation temperature of the block isocyanato group, preferably at a temperature lower than the dissociation temperature of the block isocyanato group by about 20 to 50°C.

The solvent that can be used in this copolymerization reaction is not particularly limited as long as it is inactive to the reaction, and examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether. , diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol (Poly)alkyl such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether len glycol monoalkyl ethers; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; Ketones, such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; 2-hydroxymethylpropionate, 2-hydroxyethylpropionate, 2-hydroxy-2-methylmethylpropionate, 2-hydroxy-2-methylethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-Ethoxymethylpropionate, 3-ethoxyethylpropionate, ethoxyacetate ethyl, hydroxyacetate ethyl, 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl- 3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propionic acid esters such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; Aromatic hydrocarbons, such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; Diethylene glycol etc. are mentioned. These solvents may be used individually or may be used in combination of 2 or more type.

Among these solvents, ether solvents are preferred, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether and ethylene glycol monomethyl ether are more preferred.

The amount of the solvent used in the copolymerization reaction is not particularly limited, but is generally 30 to 1,000 parts by mass, preferably 50 to 800 parts by mass, based on 100 parts by mass of the total amount of monomers charged. In particular, by setting the amount of the solvent to 1,000 parts by mass or less, the decrease in molecular weight of the copolymer (A) due to chain transfer action can be suppressed, and the viscosity of the copolymer (A) can be controlled within an appropriate range. Moreover, by making the quantity of a solvent into 30 mass parts or more, while being able to prevent an abnormal polymerization reaction and carrying out a polymerization reaction stably, coloring and gelation of a copolymer (A) can also be prevented.

In addition, the polymerization initiator that can be used for this copolymerization reaction is not particularly limited, but examples thereof include azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethyl Hexanoate etc. are mentioned. These polymerization initiators may be used individually or may be used in combination of 2 or more type. The usage amount of the polymerization initiator is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, based on 100 parts by mass of the total amount of the monomers.

The weight average molecular weight of the copolymer (A) in terms of polystyrene is not particularly limited, but by the above production method, a copolymer having a weight average molecular weight of preferably 1,000 to 50,000, more preferably 3,000 to 40,000 (A ) can be obtained. When the weight average molecular weight of the copolymer (A) is 1,000 or more, the loss of the colored pattern hardly occurs after alkali development when used as a photosensitive resin composition. On the other hand, when the weight average molecular weight of the copolymer (A) is 50,000 or less, the development time becomes appropriate and practicality is ensured.

The acid value (JIS K6901 5.3) of the copolymer (A) can be appropriately selected, but when blended in the photosensitive resin composition, it is preferably 20 to 300 KOHmg/g, more preferably 30 to 200 KOHmg/g is the range of When the acid value of the copolymer (A) is 20 KOHmg/g or more, the alkali developability at the time of use as a photosensitive resin composition becomes good. On the other hand, if the acid value of the copolymer (A) is 300 KOHmg/g or less, the exposed portion (photocured portion) is less likely to be dissolved in an alkali developing solution, so the pattern shape becomes good.

In addition, the epoxy equivalent of the copolymer (A) is not particularly limited, but is preferably in the range of 200 to 2,000 g/mol, more preferably 300 to 1500 g/mol, and most preferably 480 to 900 g/mol. to be. Stability becomes favorable as the epoxy equivalent of copolymer (A) is 200 g/mol or more. On the other hand, when the epoxy equivalent is 2,000 g/mol or less, solvent resistance is sufficiently secured. In addition, an epoxy equivalent is the mass of a polymer per 1 mol of epoxy groups of a polymer, and can be calculated|required by dividing the mass of a polymer by the epoxy group weight of a polymer (g/mol). In the present invention, the epoxy equivalent is a theoretical value calculated from the injected amount of the raw material used for introducing the epoxy group.

The copolymer (A) of the present invention contains a block isocyanato group in its molecule. What is necessary is just to select content of a block isocyanato group suitably, but normally, a block isocyanato group equivalent is 400-6,000, Preferably it is selected in the range used as 1,000-5,000. The block isocyanato group equivalent is the mass of the polymer per mole of the block isocyanato group contained in the polymer, and can be obtained by dividing the mass of the polymer by the number of moles of the block isocyanato group contained in the polymer (g/mol ). In the present invention, the block isocyanato group equivalent is a theoretical value calculated from the preparation amount of the block isocyanato group-containing monomer.

<Polymer composition>

In this invention, in addition to the copolymer (A) described above, a polymer composition containing at least one of a solvent (B) and a reactive diluent (C) is provided. The solvent (B) is not particularly limited as long as it is an inactive solvent that does not react with the copolymer (A), and a solvent of the same category as the solvent used when producing the copolymer (A) can be used. A preferable solvent (B) is a hydroxyl group-containing organic solvent, such as propylene glycol monomethyl ether and diethylene glycol, from the viewpoint of preventing abnormal polymerization and stably carrying out the polymerization reaction.

The polymer composition of the present invention may be prepared by appropriately mixing the desired solvent (B) with the copolymer (A) isolated from the polymerization system, but it is not always necessary to isolate the copolymer (A) from the polymerization system, and the copolymerization reaction The solvent contained at the end can be used as it is, and at that time, a desired solvent can also be further added as needed. Moreover, the solvent contained in the other components used when preparing a polymer composition can also be used as a component of solvent (B).

The reactive diluent (C) is a compound having at least one polymerizable ethylenically unsaturated group as a polymerizable functional group in the molecule, and among these, a compound having a plurality of polymerizable functional groups is preferable. By using such a reactive diluent (C) in combination with the copolymer (A), the viscosity can be adjusted, the strength of the cured product formed, and the adhesion to the substrate can be improved.

As the monofunctional monomer used as the 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 Roxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acrylate ) Acryloyloxy-2-hydroxypropylphthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, glycidyl(meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylates such as (meth)acrylates, 2,2,3,3-tetrafluoropropyl (meth)acrylates, and half (meth)acrylates of phthalic acid derivatives; Aromatic vinyl compounds, such as styrene, (alpha)-methylstyrene, (alpha)-chloromethylstyrene, and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. 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)acrylate. 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 (i.e., 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, diallylphthalate, and diallylbenzenephosphonate; dicarboxylic acid esters such as divinyl adipate; triallyl cyanurate, methylene bis(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 individually or may be used in combination of 2 or more type.

What is necessary is just to adjust the compounding quantity of the copolymer (A) in a polymer composition, a solvent (B), and a reactive diluent (C) suitably according to the purpose of use. When the polymer composition contains the copolymer (A), the solvent (B), and the reactive diluent (C), usually, the copolymer ( 10 to 90 parts by mass of A), 30 to 1,000 parts by mass of solvent (B), 10 to 90 parts by mass of reactive diluent (C), preferably 20 to 80 parts by mass of copolymer (A), solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) is 20 to 80 parts by mass, more preferably, the copolymer (A) is 30 to 75 parts by mass, and the solvent (B) is 100 to 700 parts by mass , 25 to 70 parts by mass of the reactive diluent (C). A blending amount within this range results in a polymer composition having an appropriate viscosity, and can be used for preparing a photosensitive resin composition for color filters described later, as well as various coatings, adhesives, binders for printing inks, etc. It is also possible to use.

<Photosensitive resin composition>

In this invention, the photosensitive resin composition containing a copolymer (A), a solvent (B), a reactive diluent (C), and a photoinitiator (D) is provided. As the solvent (B) and the reactive diluent (C), those described above can be used.

Although it does not specifically limit as a photoinitiator (D), For example, Benzoins, such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)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-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 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; etc. can be mentioned. These photoinitiators (D) may be used independently or may be used in combination of 2 or more type.

<Photosensitive resin composition for color filters>

In this invention, the photosensitive resin composition for color filters containing a copolymer (A), a solvent (B), a reactive diluent (C), a photoinitiator (D), and a coloring agent (E) is provided. As the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D), those described above can be used.

The colorant (E) is not particularly limited as long as it is dissolved or dispersed in the solvent (B), and examples thereof include dyes and pigments. As the dye, from the viewpoints of solubility in the solvent (B) and alkaline developing solution, interaction with other components in the photosensitive resin composition, heat resistance, etc., acid dyes having acidic groups such as carboxylic acid and sulfonic acid, and nitrogen compounds of acid dyes It is preferable to use a salt with, a sulfonamide form of an acidic dye, and the like.

Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and derivatives thereof; and the like. Among these, acid dyes of azo type, xanthene type, anthraquinone type or phthalocyanine type are preferable. These dyes may be used alone or in combination of two or more, 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 , 147, 148, 150, 153, 154, 166, 173, 194, yellow pigments such as 214; 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, and 60; C.I. Violet color pigments, such as Pigment Violet 1, 19, 23, 29, 32, 36, 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. Black pigments, such as Pigment Black 1 and 7, carbon black, titanium black, and iron oxide, etc. are mentioned.

These coloring agents (E) may be used independently, or may be used in combination of 2 or more types, depending on the color of the target pixel. In addition, it is also possible to use a combination of the above dyes and pigments according to the target color of the pixel.

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 polymeric dispersant excellent in dispersion stability over time. Examples of the polymer dispersant include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, aliphatic modified ester-based dispersants, and the like. As such a polymer dispersant, it is marketed under trade names such as EFKA (manufactured by EFKA Chemicals Co., Ltd.), Disperbyk (manufactured by Big Chemie Co., Ltd.), Disparon (manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (manufactured by Zeneca Co., Ltd.). 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. used.

The compounding amounts of the copolymer (A), the solvent (B), the reactive diluent (C), the photopolymerization initiator (D) and the colorant (E) are the total amount of the copolymer (A) and the reactive diluent (C) in the photosensitive resin composition 100 With respect to parts by mass, the copolymer (A) is 10 to 100 parts by mass, the solvent (B) is 30 to 1,000 parts by mass, the reactive diluent (C) is more than 0 to 90 parts by mass, and the photopolymerization initiator (D) is 0.1 to 30 parts by mass, the colorant (E) is 3 to 80 parts by mass, preferably, the copolymer (A) is 20 to 80 parts by mass, the solvent (B) is 50 to 800 parts by mass, the reactive diluent (C) 20 to 80 parts by mass, 0.5 to 20 parts by mass of photopolymerization initiator (D), 5 to 70 parts by mass of colorant (E), more preferably 30 to 75 parts by mass of copolymer (A), solvent (B) is 100-700 mass parts, a reactive diluent (C) is 25-70 mass parts, a photoinitiator (D) is 1-15 mass parts, and a coloring agent (E) is 10-60 mass parts. If it is a compounding quantity within this range, it will become the photosensitive resin composition which has an appropriate viscosity. In addition, even in the case of a photosensitive resin composition containing no colorant (E), the above numerical range applies to the compounding amounts of the copolymer (A), the solvent (B), the reactive diluent (C), and the photopolymerization initiator (D). It is possible.

In addition to the components described above, the polymer composition and photosensitive resin composition of the present invention may contain known additives such as a known coupling agent, a leveling agent, and a thermal polymerization inhibitor in order to impart predetermined properties. The blending amount of these additives is not particularly limited as long as it does not impair the effect of the present invention.

The photosensitive resin composition of this invention can be manufactured by mixing said component using a well-known mixing apparatus. Moreover, if desired, after preparing the polymer composition containing a copolymer (A) and a solvent (B) first, it can also manufacture by mixing a reactive diluent (C), a photoinitiator (D), and a coloring agent (E). .

Since the photosensitive resin composition obtained by performing it above has alkali developability, it is suitable as a resist. Curing of the photosensitive resin composition may be performed by appropriately selecting the baking temperature within the range of 250° C. or lower. However, since the copolymer (A) of the present invention has excellent curing properties at low temperatures, the baking temperature can be lowered compared to conventional materials. can When a pigment is used as the coloring agent (E) in the photosensitive resin composition, sufficient curability is obtained even at a baking temperature of 160°C or lower. The photosensitive resin composition of the present invention is advantageous in terms of energy consumption because the crosslinking reaction sufficiently proceeds even at a low baking temperature. In addition, it is possible to use even a colorant (E) or a substrate having poor heat resistance, and the original characteristics of the colorant can be obtained, and application to various substrates is also possible. From that standpoint, the baking temperature is preferably 210°C or lower, more preferably 180°C or lower, and most preferably 160°C or lower. The lower limit of the baking temperature is not necessarily constant depending on the type of block isocyanato group contained in the copolymer (A), but is required 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 is too low, it becomes difficult to sufficiently improve the solvent resistance of the coating film. Moreover, although baking time can be selected suitably, it is 10 minutes - 4 hours normally, Preferably they are 20 minutes - 2 hours.

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

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 having excellent solvent resistance even when the baking temperature at the time of pattern formation is low. Do. Moreover, the photosensitive resin composition of this invention can contribute also to the development of a flexible display accompanying low-temperature hardening, the reduction of energy consumption in a manufacturing process, and relaxation of restrictions of the colorant to be used.

＜Color filter＞

Next, a color filter having a color pattern made of a cured product of the photosensitive resin composition of the present invention will be described. The color filter of the present invention has a color pattern formed using the photosensitive resin composition described above. The color filter is usually composed of a substrate, RGB pixels formed thereon, a black matrix formed at the boundary between the respective pixels, and a protective film formed on the pixels and the black matrix. In this structure, except that the pixels and the black matrix (coloring pattern) are formed using the above photosensitive resin composition, other structures can employ known ones.

Next, an embodiment of a method for manufacturing a color filter will be described. 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 a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate, etc. are appropriately selected. can be used

A coloring pattern can be formed by a photolithography method. Specifically, after applying the above photosensitive resin composition on a substrate to form a coating film, the coating film is exposed to light through a photomask having 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 method of applying the photosensitive resin composition, A screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, etc. can be used. Moreover, you may volatilize the solvent (B) by heating using heating means, such as a circulation type oven, an infrared heater, and a hot plate, after application|coating of the photosensitive resin composition 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.

Subsequently, active energy rays such as ultraviolet rays and excimer laser light are irradiated to the formed coating film through a negative mask to partially expose it. The amount of energy radiation to be irradiated may be appropriately selected according to the composition of the photosensitive resin composition, and is preferably 30 to 2000 mJ/cm 2 , for example. The light source used for exposure is not particularly limited, but a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like 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, and 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-phenyl such as sulfates, hydrochlorides or p-toluenesulfonates thereof An aqueous solution of a rendiamine-based compound or the like 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 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, the solvent resistance of the colored pattern is insufficient when the baking temperature is 200 ° C. or less, but in the photosensitive resin composition of the present invention, the colored pattern showing sufficient solvent resistance even when baking at a temperature of 120 ° C. or less can form Therefore, the baking temperature can be lowered and, in the case of baking at a high temperature, the processing time can be shortened, which is a great advantage in terms of manufacturing. From such a standpoint, the baking temperature is usually 210 ° C. or less, preferably 160 ° C. or less, more preferably 120 ° C. or less, and the baking time is usually 10 minutes to 4 hours, preferably 20 minutes to It is carried out for 2 hours.

A desired coloring pattern can be formed by sequentially repeating the above coating, exposure, development, and baking using the photosensitive resin composition for black matrix and the photosensitive resin composition for red, green, and blue pixels. In addition, although the formation method of the coloring pattern by photocuring was explained above, if the photosensitive resin composition which mix|blended the hardening accelerator and a well-known epoxy resin was used instead of the photoinitiator (D), it applied by the inkjet method Then, by heating, a desired coloring pattern can also be formed. Next, a protective film is formed on the color pattern (each pixel of RGB and the 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 produced in this way is produced using a photosensitive resin composition that is excellent in sensitivity and developability, can be cured at low temperatures and provides a coloring pattern with excellent solvent resistance, it has excellent color change with little color change. It has a color pattern.

<Image display element>

The image display element of the present invention is an image display element provided with the above color filter, and specific examples thereof include solid-state imaging elements such as liquid crystal display elements, organic EL display elements, CCD elements and CMOS elements. What is necessary is just to manufacture the image display element of this invention in accordance with a conventional method other than using the said color filter. For example, when manufacturing a liquid crystal display element, the said color filter is formed on a board|substrate, and then electrodes, a spacer, etc. are formed one by one. Then, an electrode or the like is formed on another substrate, and the two are bonded together, and a predetermined amount of liquid crystal is injected and sealed.

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 embodiment, parts and percentages are all based on mass unless otherwise specified. Moreover, 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, which means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the copolymer (A).

(2) The weight average molecular weight (Mw) means the standard polystyrene equivalent weight average molecular weight measured under 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

[Example 1]

After putting 257.3 g of diethylene glycol methyl ethyl ether in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube, the mixture was stirred while purging with nitrogen, and the temperature was raised to 78°C. Next, 110.0 g of dicyclopentanyl methacrylate, 17.0 g of glycidyl methacrylate, 28.4 g of methacrylic acid and 12.1 g of methacrylic acid 2-[O-(1'-methylpropylideneamino) Carboxyamino] ethyl (Karenz MOI-BM, manufactured by Showa Electric Co., Ltd., dissociation rate of block isocyanato group: 18% by mass) and a monomer mixture consisting of 13.4 g of 2,2'-azobis (2,4 -Dimethylvaleronitrile) (polymerization initiator) was added and dissolved in 78.7 g of diethylene glycol methyl ethyl ether and each was added dropwise into the flask from the dropping funnel. After completion of the dropwise addition, a copolymerization reaction was carried out by stirring at 78°C for 3 hours to form a copolymer to obtain a polymer composition of Sample No. 1 (concentration of components other than the solvent: 40% by mass). The weight average molecular weight of the copolymer in the obtained polymer composition was 7,500, and the acid value was 102.3 KOHmg/g.

[Examples 2 to 12 and Comparative Examples 1 to 3]

Except for using the raw materials described in Tables 1 and 2, a copolymerization reaction was carried out under the same conditions as in Example 1 to obtain polymer compositions of Sample Nos. 2 to 15 (concentration of components other than the solvent: 40% by mass). The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Tables 1 and 2. In Tables 1 and 2, 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate is Showa Electric Co., Ltd., Karenz MOI-BP, block isocyanato group Dissociation rate: 70% by mass, and malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester is Showa Manufactured by Denko Corporation, Karenz MOI-DEM, block isocyanato group dissociation rate: 90% by mass, benzoic acid-4-[[[[2-[(2-methyl-1-oxo-2-propene-1 -yl)oxy]ethyl]amine]carbonyl]oxy]methyl ester has a block isocyanato group dissociation rate of 40% by mass, and is benzoic acid-2-[[[[2-[(2-methyl-1- Oxy-2-propen-1-yl) oxy] ethyl] amine] carbonyl] oxy] methyl ester has a block isocyanato group dissociation rate: 75% by mass, and 2-propenoic acid-2-methyl-2 -[[(3,5-dimethylphenoxy)carbonyl]amine] ethyl ester has a block isocyanato group dissociation rate: 28% by mass.

[Examples 13 to 24 and Comparative Examples 4 to 6]

<Preparation of photosensitive resin composition (pigment type)>

In a stainless steel container filled with 200 parts by mass 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 Big Chemie Japan Co., Ltd.) 161) was added in 25 parts by mass, and mixed and dispersed in a paint shaker for 2 hours to prepare a green pigment dispersion.

The photosensitive resin composition was prepared by mixing this green pigment dispersion with other compounding components shown in Table 3 (ie, polymer composition, reactive diluent, photopolymerization initiator and solvent). The blending amount of each component is as shown in Table 3. In addition, the photosensitive resin compositions of Examples 13 to 24 were prepared using each of the polymer compositions of Examples 1 to 12 (Sample Nos. 1 to 12), and the photosensitive resin compositions of Comparative Examples 4 to 6 were prepared using Comparative Example 1 It prepared using each of the polymer compositions of -3 (sample No. 13-15). In addition, the amount of the polymer composition includes the solvent contained at the end of the copolymer reaction, and the amount of the solvent contained in each sample is added to the solvent as a compounding component.

<Evaluation of photosensitive resin composition>

(1) alkali developability

After spin-coating each of the photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 on a 5 cm square glass substrate (alkali-free glass substrate) so that the thickness after exposure is 2.5 μm, at 90 ° C. The solvent was volatilized by heating for 3 minutes. Next, a photomask of a predetermined pattern was arranged at a distance of 100 μm from the coating film, the coating film was exposed through the photomask (exposure amount: 150 mJ/cm 2 ), and the exposed portion was photocured. Next, after 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 to dissolve the unexposed portion and developing, a predetermined pattern was formed by baking at 100°C for 20 minutes. The residue after alkali development was confirmed by observing the pattern after alkali development using an electron microscope S-3400 manufactured by Hitachi High-Technologies Co., Ltd. The criteria for this evaluation are as follows.

○: no residue

×: with residue

The evaluation results of alkali developability are shown in Table 4.

(2) Evaluation of solvent resistance

On a 5 cm square glass substrate (alkali-free glass substrate), each of the photosensitive resin compositions of Examples 13 to 24 and Comparative Examples 4 to 6 was spin-coated so that the thickness after baking was 2.5 μm, and then at 90 ° C. The solvent was volatilized by heating for 3 minutes. Next, after exposing the coating film to light with a wavelength of 365 nm and photocuring the exposed portion, it was left to stand for 20 minutes in a dryer with a baking temperature of 100°C to produce a cured coating film. 200 ml of propylene glycol monomethyl ether acetate was placed in a 500 ml capped glass bottle, and the mixture was allowed to stand still at 80°C. After immersing the said test piece with a cured coating film in it, it was left still for 5 minutes in the state maintained at 80 degreeC. The color change (ΔE*ab) before and after immersing the test piece in propylene glycol monomethyl ether acetate was measured with a spectrophotometer UV-1650PC (manufactured by Shimadzu Corporation). The measurement results of ΔE*ab are shown in Table 4. When ΔE*ab is 1.5 or less, it can be said that the solvent resistance is excellent.

(3) Evaluation of storage stability

Equal amounts of the copolymers of Examples 1 to 12 and Comparative Examples 1 to 3 were weighed and put into a glass container, and the inlet was closed with an aluminum foil to prevent dust or the like from entering. Next, each of these samples was left still in an incubator maintained at 23°C, and the weight average molecular weight (Mw) of the sample after one month was measured. Table 5 shows the change rate of Mw after one month. If the change rate of Mw after one month is within 20%, it can be said that the copolymer has excellent storage stability.

As can be seen from the results of Table 4, the photosensitive resin compositions of Examples 13 to 24 using the polymer compositions of Sample Nos. 1 to 12 had good alkali developability and solvent resistance. In addition, since the storage stability of the copolymer correlates with the storage stability of the photosensitive resin composition blended with it, from the results of Table 5, the photosensitive resin compositions of Examples 13 to 24 using the polymer compositions of Sample Nos. 1 to 12 It can be said that the storage stability is also good. In contrast, the photosensitive resin compositions of Comparative Examples 4 to 6 using the polymer compositions of Sample Nos. 13 to 15 have good storage stability, but do not have sufficient solvent resistance, and the photosensitive resin compositions of Comparative Example 6 , alkali developability was also not sufficient.

As can be seen from the above results, according to the present invention, a photosensitive resin composition having excellent developability and excellent solvent resistance and storage stability can be provided. Moreover, according to this invention, the copolymer useful for preparation of the photosensitive resin composition which has the above characteristics can be provided.

In addition, this international application claims priority based on Japanese Patent Application No. 2017-150501 for which it applied on August 3, 2017, and uses all the content of this Japanese patent application for this international application.

Claims (19)

containing a copolymer (A), a solvent (B), a reactive diluent (C) and a photopolymerization initiator (D);
The copolymer (A) contains a structural unit (a) having a block isocyanato group, a structural unit (b) having an acid group, and a structural unit (c) having an epoxy group,
Structural unit (a) having the block isocyanato group 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]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2 -[(2-methyl-1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methyl ester and 2-propenoic acid-2-methyl-2-[[(3, 5-dimethylphenoxy) carbonyl] amino] a structural unit derived from at least one member selected from the group consisting of ethyl esters;
A photosensitive resin composition having an acid value of 20 to 300 KOHmg/g. According to claim 1,
The copolymer (A) contains 1 to 60 mol% of the structural unit (a) having the block isocyanato group, and 5 to 65 mol% of the structural unit (b) having the acid group and the structural unit having the epoxy group The photosensitive resin composition containing 5-65 mol% of (c). According to claim 1,
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 (c) which has the said epoxy group is 10:90 - 75:25. According to claim 1,
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]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl- 1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methylester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carb A structural unit (a) derived from at least one selected from the group consisting of [bornyl] amino] ethyl ester, a structural unit (b) derived from (meth)acrylic acid, and a structural unit (c) derived from glycidyl methacrylate and a structural unit (e) derived from at least one member selected from the group consisting of dicyclopentanyl methacrylate and methyl (meth)acrylate. According to claim 1,
The photosensitive resin composition in which the said copolymer (A) further contains the structural unit (d) which has a hydroxyl group. According to claim 5,
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]amino]carbonyl]oxy]methyl ester, benzoic acid-2-[[[[2-[(2-methyl- 1-oxy-2-propen-1-yl)oxy]ethyl]amino]carbonyl]oxy]methylester and 2-propenoic acid-2-methyl-2-[[(3,5-dimethylphenoxy)carb A structural unit (a) derived from at least one selected from the group consisting of bornyl] amino] ethyl ester, a structural unit (b) derived from (meth)acrylic acid, and a structural unit derived from glycidyl (meth)acrylate ( c), a structural unit derived from 2-hydroxyethyl methacrylate (d), and a structural unit derived from at least one selected from the group consisting of dicyclopentanyl (meth)acrylate and methyl (meth)acrylate ( A photosensitive resin composition containing e). According to claim 4,
The copolymer (A) is a structural unit (a) derived from methacrylic acid 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl, a structural unit (b) derived from (meth)acrylic acid, and , The photosensitive resin composition containing the structural unit (c) derived from glycidyl (meth)acrylate, and the structural unit (e) derived from dicyclopentanyl (meth)acrylate. According to claim 4,
The copolymer (A) contains a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit (b) derived from (meth)acrylic acid and a structural unit (c) derived from glycidyl (meth)acrylate and a structural unit (e) derived from dicyclopentanyl (meth)acrylate. According to claim 5,
The copolymer (A) contains a structural unit (a) derived from 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylic acid and a structural unit (b) derived from (meth)acrylic acid and a structural unit (c) derived from glycidyl (meth)acrylate, a structural unit (d) derived from 2-hydroxyethyl methacrylate, and a structural unit (e) derived from dicyclopentanyl (meth)acrylate ) Photosensitive resin composition containing. According to claim 4,
The copolymer (A) is a structural unit derived from malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester ( a), (meth)acrylic acid-derived structural unit (b), glycidyl (meth)acrylate-derived structural unit (c), and dicyclopentanyl (meth)acrylate-derived structural unit (e) Photosensitive resin composition containing. According to claim 1,
The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),
The copolymer (A) contains 1 to 40 mol% of the structural unit (a) having the block isocyanato group, 1 to 60 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group The photosensitive resin composition containing 1-70 mol% of (c), more than 0 mol% - 50 mol% of the structural unit (d) which has the said hydroxyl group, and more than 0 mol% - 80 mol% of the said structural unit (e). According to claim 1,
The copolymer (A) further contains a structural unit (d) having a hydroxyl group and a structural unit (e) other than the structural units (a) to (d),
The copolymer (A) contains 3 to 20 mol% of the structural unit (a) having the block isocyanato group, 20 to 50 mol% of the structural unit (b) having the acid group, and the structural unit having the epoxy group The photosensitive resin composition containing 20-40 mol% of (c), more than 0 mol% - 20 mol% of the structural unit (d) which has the said hydroxyl group, and 20-40 mol% of the said structural unit (e). The photosensitive resin composition according to claim 1, which further contains a coloring agent (E) and is for color filters. According to claim 13,
10 to 100 parts by mass of the copolymer (A), 30 to 1,000 parts by mass of the solvent (B), and the reactive diluent ( The photosensitive resin composition in which C) contains more than 0 mass part - 90 mass parts, 0.1-30 mass parts of the said photoinitiator (D), and 3-80 mass parts of the said coloring agent (E). According to claim 13,
The photosensitive resin composition in which the said solvent (B) contains the organic solvent containing a hydroxyl group. According to claim 13,
The photosensitive resin composition in which the said coloring agent (E) contains a pigment. A color filter characterized by having a color pattern comprising a cured product of the photosensitive resin composition according to claim 13. An image display element comprising the color filter according to claim 17. A method for producing a color filter comprising the steps of applying the photosensitive resin composition according to claim 13 to a substrate, exposing to light, alkali developing, and then baking at a temperature of 160°C or lower to form a colored pattern.