JPH09316346A - Radiation-sensitive resin composition, radiation-sensitive resin composition for color filter, and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a radiation-sensitive resin compsn, capable of forming a cured product excellent in thermal resistance and adhesion by incorporating an allylnadimide compd., a specified melamine or guanamine, a photoacid generator, and a diluent. SOLUTION: This composition comprises (A) a copolymer containing an acidic group and a hydroxyl group, (B) an allylnadimide compound, (C) a melamine of the formula I or a guanamine of the formula II (wherein R1 through R10 may be the same or different from one another and each represents a hydrogen atom, -CH2 OR12 group or -(-CH2 -)4 -OR12 group; R12 represents a hydrogen atom or a 1-6C alkyl group; and R11 represents an alkyl group or a (substituted) phenyl group), (D) a photoacid generator, and (E) a diluent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a radiation-sensitive resin composition and a cured product thereof. In particular, the present invention relates to a radiation-sensitive resin composition suitable for a radiation-sensitive resin composition for a color liquid crystal display device, a color filter such as a binder resin for a color filter R, G, B and a protective film used for other purposes, and a cured product thereof.

[0002]

2. Description of the Related Art A protective film is formed on the surface of a color filter by printing or spin coating for the purpose of smoothing the steps of a conventional color filter and protecting the color filter from chemical treatment and heating in a later process. Is applied. As such a protective film, acrylic resin, urethane resin, or epoxy resin is currently used. Further, a polyimide resin having improved heat resistance (for example, JP-A-1-15
No. 6371) is proposed.

[0003]

The acrylic resin or urethane resin is limited in the processing step after film formation because of its low heat resistance and poor chemical resistance. On the other hand, the epoxy-based resin or the polyimide-based resin is excellent in heat resistance and chemical resistance, but has a problem that it is not suitable for forming a fine pattern of a protective film because of its thermosetting property. An object of the present invention is a radiation-sensitive resin composition for a color filter which gives a protective film which is easy to form a fine pattern, has heat resistance, and has good adhesiveness without extracting a dye in a color filter when applied, and The cured product is provided.

The present inventors have arrived at the present invention as a result of intensive research to solve the above-mentioned problems. That is, the present invention includes 1) a copolymer (A) having an acid group and a hydroxyl group, an allylnadiimide compound (B), a melamine represented by the formula (1) or a guanamine represented by the formula (2) (C). ),

[0004]

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[0005]

[Chemical 6]

(In the formulas (1) and (2), R _{1 to} R ₁₀ are
They may be the same or different, and a hydrogen atom, -CH
₂ OR ₁₂ group or — (— CH ₂ —) ₄ —OR ₁₂ group, R ₁₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₁ is an alkyl group or a (substituted) phenyl group. Is. ), A photoacid generator (D) and a diluent (E), and 2) a radiation-sensitive resin composition, 2) a copolymer (A) having an acid group and a hydroxyl group, an allylnadiimide compound ( B) containing the melamines represented by formula (1) or the guanamines (C) represented by formula (2), the photoacid generator (D) and the diluent (E) described in 1). A radiation-sensitive resin composition for a color filter, which is characterized by: 3) A cured product of the radiation-sensitive resin composition according to items 1) and 2).

Each component of the radiation-sensitive resin composition of the present invention will be specifically described below.

In the present invention, the term "radiation" is used as a concept including visible rays, ultraviolet rays, electron beams, X-rays and the like.

Specific examples of the copolymer (A) having an acid group and a hydroxyl group include, for example, an acid monomer (A-1), a monomer having a hydroxyl group (A-2) and the acid monomer (A).
-1), a copolymer of the monomer (A-2) having a hydroxyl group and the comonomer (A-3) capable of copolymerization is preferably used. Examples of such an acid monomer (A-1) include unsaturated carboxylic acids having at least one or more carboxyl groups in the molecule (for example, unsaturated molar carboxylic acid and unsaturated dicarboxylic acid). Specific examples of the unsaturated carboxylic acid include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid and fumaric acid. These may be used alone or in combination. As the monomer (A-2) having a hydroxyl group, specifically,
The unsaturated compound which has at least 1 or more hydroxyl group in a molecule is mentioned. Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl (meth) acrylate. To be Examples of the comonomer (A-3) include aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, benzyl (meth). Unsaturated carboxylic acid alkyl ester such as acrylate, unsaturated carboxylic acid aminoalkyl ester such as aminoethyl (meth) acrylate, unsaturated carboxylic acid glycidyl ether such as glycidyl (meth) acrylate, vinyl acetate, carboxylic acid such as vinyl propionate Acid vinyl ester, (meth) acrylonitrile, α-
Vinyl cyanide compounds such as chloracrylonitrile,
Examples thereof include aliphatic conjugated dienes such as 1,3-butadiene and isoprene, polystyrene having a (meth) acryloyl group at each terminal, macromonomers such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, and polysilicone. These may be used alone or in combination. When forming the copolymer (A) having an acid group and a hydroxyl group, the acid monomer (A-1) as described above is preferably contained in an amount of 5% by weight to 50% by weight based on 100% by weight of the total monomers. And more preferably in an amount of 10% to 40% by weight. The monomer (A-2) having a hydroxyl group is used in an amount of preferably 1 to 30% by weight, more preferably 3 to 20% by weight, based on 100% by weight of the total monomers.

The weight average molecular weight of the resin (A) having an acid group and a hydroxyl group used in the present invention is preferably 3,000.
0 to 300,000, more preferably 5,000
~ 100,000.

Specific examples of the allyl nadiimide compound (B) used in the present invention include, for example,

[0012]

[Chemical 7]

[0013]

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[0014]

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[0015]

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[0016]

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And the like.

Specific examples of the melamines represented by the formula (1) or the guanamines (C) represented by the formula (2) include, for example, melamine, monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, Partial methylolated melamine such as pentamethylol melamine, partially butyrolized melamine, hexamethylol melamine, hexabutyrol melamine and alkylated versions of these methylol melamine or butyrol melamine, for example, monomethoxymethyl melamine,
Partial methoxymethylated melamine such as dimethoxymethylmelamine, trimethoxymethylmelamine, tetramethoxymethylmelamine, pentamethoxymethylmelamine, partially butoxymethylated melamine, hexamethoxymethylmelamine, hexabutoxymethylmelamine, acetoguanamine, benzoguanamine, partially methylolated Examples thereof include benzoguanamine, tetramethylol benzoguanamine, and alkylated versions of these methylol benzoguanamines.

Specific examples of the photo-acid generator (D) used in the present invention include 1,1-bis [P-chlorophenyl] -2,2,2-trichloroethane and 2-[(2'-
Furyl) vinylene] -4,6-bis (tribromomethyl) -S-triazine, 2 [(3′-furyl (vinylene) -4,6-bis (tribromomethyl) -S-triazine, 2-[( 3'-methyl-2'-furyl) vinylene] -4,6-bis (tribromomethyl) -S-triazine, 2 [(4'-methyl-2'-furyl) vinylene]
-4,6-bis (tribromomethyl) -S-triazine, 2-[(5'-methyl) -3'-furyl) vinylene] -4,6-bis (tribromomethyl) -S-triazine, 2 -[(4'-Ethyl-2'-furyl) vinylene] -4,6-bis (tribromomethyl) -S-tridian, 2-[(4'-t-butyl-2'-furyl) vinylene]- 4,6-bis (tribromomethyl) -S-triazine, 2-[(2'-furyl) vinylene] -4,6-
Bis (trichloromethyl) -S-triazine, 2-
[(3'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine, 2-[(5'-methyl-2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine, 2-[(5'-ethyl-
2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-tridian, 2-[(5'-propyl-
2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine, 2-[(4'-t-butyl-2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine, 2-[(3 ', 4'-dimethyl-2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine, 2 [(4', 5 '
-Dimethyl-2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine, 2-
[(3 ', 4', 5'-Trimethyl-2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine, 2-[(5'-chloro-2'-furyl) vinylene ] -4,6-bis (trichloromethyl) -S-triazine and the like can be mentioned.

Specific examples of the diluent (E) include, for example,
Ethylene glycol monomethyl ether, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, etc. Propylene glycol alkyl ether acetates such as alkyl ethers, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, aromatic hydrocarbons such as toluene and xylene,
Ketones such as methyl ethyl ketone, cyclohexinosan, 2-heptanone and methyl isobutyl ketone, and esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate and 3-methyl-3-methoxybutylacetate can be used. . These solvents can be used alone or as a mixture.

Each component (A) constituting the composition of the present invention
The proportion of (E) used is preferably 10 to 100 parts by weight, and more preferably 20 to 80 parts by weight, relative to 100 parts by weight of component (A). Component (C) is (A)
The amount is preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the component. The component (D) is
The amount is preferably 0.001 to 50 parts by weight, and particularly preferably 0.01 to 30 parts by weight, relative to 100 parts by weight of the component (A).
The component (E) is 10 parts by weight based on 100 parts by weight of the component (A).
0 to 10000 parts by weight is preferable, and 500 to 500 is particularly preferable.
An amount of 0 parts by weight is preferred.

The composition of the present invention can be prepared by heating, dissolving, mixing and dispersing the components (A) to (E).

The composition of the present invention may contain additives and color pigments, if necessary. Specific examples of such additives include fillers, other polymer compounds, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and aggregation inhibitors. More specifically, glass, alumina, silica, talc, titanium oxide, fillers such as barium sulfate, polyvinyl alcohol, polyethylene glycol, monoalkyl ether, polymer compounds such as polyfluoroalkyl acrylate, nonionic, cationic,
Anionic surfactants, vinyltrimethoxysilane, vinyltriethoxysilane, N, (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N
-(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-methacryloxypropyltrimethoxysilane, 3-
Adhesion promoters such as mercaptopropyltrimethoxysilane, antioxidants such as 2,6-di-t-butylphenol, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole And the like, and anti-aggregation agents such as sodium polyacrylate. Specific examples of the coloring pigment include carbon black and color index CI (The Societyo
Published by f Dyers and Colorists (Pigmen
The compounds classified into t) are mentioned.

Next, an example of how to use the resin composition obtained in the present invention will be described. In advance, a glass or a solid polymer image pickup substrate or the like, a natural composition such as gelatin or glue, or a photosensitive composition comprising a synthetic polymer such as an acrylic resin is applied by a method such as spin coating, and patterned. The radiation-sensitive resin composition of the present invention is applied onto the color filter formed by dyeing by a method such as spin coating, the solvent is usually dried at room temperature to 100 ° C., then a negative mask is applied, and ultraviolet rays are applied. Irradiate 80 ~
It is heat-cured at 150 ° C. for 0.5 to 5 minutes, and the unexposed portion is dissolved and removed with a dilute alkaline aqueous solution such as a tetramethylammonium hydroxide aqueous solution sodium carbonate aqueous solution.
A color filter having a patterned protective film (cured film) can be obtained by heating and curing at ˜250 ° C. The cured film obtained from the radiation-sensitive resin composition of the present invention is used for color video cameras, liquid crystal color TVs.
It is particularly suitable as a protective film for a color filter used for the above. INDUSTRIAL APPLICABILITY The resin composition of the present invention is useful for R, G, B binders for color filters, liquid resists, insulating coatings, etc., as well as for protective films of color filters.

[0025]

EXAMPLES The present invention will be described more specifically with reference to synthesis examples and examples. In addition, in a synthetic example, a part shows a weight part. Synthesis Example of Resin (A) Having Acid Group Synthesis Example 1 Propylene glycol monomethyl ether acetate 1
00 parts were charged, the temperature was raised to 70 ° C, and 80 parts of o-phenylphenyloxyethyl acrylate and 15 parts of methacrylic acid were added.
Part, 5 parts of 2-hydroxy-3-phenyloxypropyl acrylate and 2 parts of azobisisobutyronitrile were added dropwise over 4 hours, and after completion of the addition, 70 ° C.
For 14 hours, then charged with 2 parts of azobisisobutyronitrile, heated up to 80 ° C., reacted at 80 ° C. for 10 hours, and then cooled to obtain a copolymer (A-1). Acid value of solid content of copolymer (A-1) (mgKOH / g) 10
0, hydroxyl value (mgKOH / g) 13.0, average molecular weight 2,2
It was × 10 ⁴ . The viscosity (25 ° C., CPS) of the obtained copolymer (A-1) solution was 4920. Examples 1 to 3 and Comparative Example 1 An ultraviolet curable resin composition for a color filter protective film was blended according to the blending composition shown in Table 1 (numerical values indicate parts by weight), and spin coated on a glass plate to 1 to 3 μm. After coating with a film thickness of 5 minutes, the coating film is dried at 70 ° C. for 5 minutes, a negative film is placed on the coating surface, and ultraviolet rays are irradiated using a 5 kw ultra-high pressure mercury lamp, and then with a 1% sodium carbonate aqueous solution. The unirradiated part of the coating film was removed by dissolution. Various performance tests were performed on each of the obtained test pieces. Table 1 shows the results.

(Developability) Using a 5 kW ultra high pressure mercury lamp,
Irradiation with ultraviolet rays was performed to dissolve and remove unirradiated portions with a 1% sodium carbonate aqueous solution at 25 ° C., and the developability was evaluated. The judgment criteria are as follows. ○ ・ ・ ・ ・ The dissolution rate is fast. × ・ ・ ・ ・ Not dissolved or extremely slow.

(Heat resistance) The test piece was allowed to stand at 250 ° C. for 1 hour, and the degree of coloring before and after the test was measured with a color difference meter (model: Macbeth CE-3000, manufactured by Kormogen Co.), and the numerical value was obtained. The smaller, the less discoloration. (Adhesion) 1 m on the test piece according to JIS K5400
100 peeled eyes of m were made and a peeling test was performed with a cellophane tape. The peeling state of the first eye was observed and evaluated according to the following criteria. ○ ・ ・ ・ ・ 100/100 without peeling △ ・ ・ ・ ・ 50/100 to 90/100 × ・ ・ ・ ・ 0/100 to 50/100 (Pencil hardness) Evaluation is performed according to JIS K5400. It was

[0028]

Table 1 Table 1 Example Comparative Example 1 2 3 1 Copolymer (A-1) obtained in Synthesis Example 1 200 200 200 Bisallylnadiimide compound (I) * 1 30 40 Allylnadiimide compound (II) * 2 60 Hexamethoxymethylmelamine 10 Hexabutoxymethylmelamine 10 20 2-[(5'-methyl-2'-furyl) vinylene] -4,6-bis (trichloromethyl) -S-triazine 10 10 10 Propylene glycol monomethyl Ether acetate 500 500 500 700 EPPN-201 * 3 100 Phenol novolac (softening point 83 ° C) 65 2-Methylimidazole 3.0 Developability ○ ○ ○ × Heat resistance (color difference value) 0.3 0.2 0.2 3.0 Adhesion ○ ○ ○ ○ Pencil Hardness 6H 6H 6H 6H

From the evaluation results in Table 1, the composition of the present invention is
It has excellent developability, excellent heat resistance of the cured product, and satisfactory adhesion and pencil hardness.

Note) * 1 Bisallylnadiimide compound (I): structural formula

[0031]

[Chemical 12]

* 2 Allyl nadiimide compound (I
I): Structural formula

[0033]

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* 3 EPPN-201: phenol novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd.

INDUSTRIAL APPLICABILITY The resin composition of the present invention is applied to a developer in an exposed area in the formation of a pattern for a color filter protective film by developing an unexposed area selectively exposed to ultraviolet rays through a patterned film. It has resistance, the obtained cured product has little coloring even when left at high temperature, and has excellent adhesiveness, and is suitable as a resin composition for a color filter.

Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/3477 KBN C08K 5/3477 KBN C09D 4/00 PDQ C09D 4/00 PDQ PDS PDS G02B 5/20 101 G02B 5/20 101 G03F 7/004 503 G03F 7/004 503 7/038 7/038

Claims (3)

[Claims] 1. A copolymer having an acid group and a hydroxyl group (A), an allylnadiimide compound (B), a melamine represented by the formula (1) or a guanamine (C) represented by the formula (2). ] Embedded image (In the formulas (1) and (2), R _{1 to} R ₁₀ may be the same or different and are a hydrogen atom, a —CH ₂ OR ₁₂ group or — (— CH ₂ —) ₄ —OR. ₁₂ groups, R ₁₂ is
A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₁₁
Is an alkyl group or a (substituted) phenyl group. ),
A radiation-sensitive resin composition comprising a photoacid generator (D) and a diluent (E). 2. A copolymer (A) having an acid group and a hydroxyl group,
Allylnadiimide compound (B), melamines represented by formula (1) or guanamines represented by formula (2) (C) Embedded image (In the formulas (1) and (2), R _{1 to} R ₁₀ may be the same or different and are a hydrogen atom, a —CH ₂ OR ₁₂ group or — (— CH ₂ —) ₄ —OR. ₁₂ groups, R ₁₂ is
A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ₁₁
Is an alkyl group or a (substituted) phenyl group. ),
A radiation-sensitive resin composition for a color filter, which comprises a photoacid generator (D) and a diluent (E). 3. A cured product of the radiation-sensitive resin composition according to claim 1.