JPH04270714A - Ultraviolet curing resin composition for protective film of color filter and its cured product - Google Patents

Abstract

PURPOSE:To provide an ultraviolet curing resin composition for protective films of color filters, capable of forming fine patterns and excellent in water resistance and adhesion with hardly any coloring of its cured film even when allowed to stand at high temperatures and its cured product. CONSTITUTION:An ultraviolet curing resin composition for protective films of color filters containing (A) an epoxy (meth)acrylate and/or (B) a product of reaction between the epoxy (meth)acrylate with a polybasic carboxylic acid or an anhydride, (C) a melamine resin, (D) a photopolymerization initiator and (E) a diluent.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet curable resin composition for a protective film of a color filter used in a color liquid crystal display device or an image pickup device.

0002

[Prior Art] A protective film is coated on the surface of a color filter by printing or spin coating in order to smooth out the steps on a conventional color filter and to protect the color filter from chemical treatment and heating in post-processing. be done. As such a protective film, acrylic resin, urethane resin, or epoxy resin is currently used. Furthermore, polyimide resins with improved heat resistance have been proposed (see, for example, Japanese Patent Application Laid-open No. 1-156371).

0003

[Problems to be Solved by the Invention] The acrylic resin or urethane resin has low heat resistance and poor chemical resistance, and is therefore subject to limitations in processing steps after film formation. On the other hand, epoxy resin or polyimide resin is
Although it has excellent heat resistance, chemical resistance, etc., it has a problem that it is not suitable for forming a fine pattern of a protective film because of heat and curing properties. The purpose of the present invention is to provide an ultraviolet curable resin for a color filter protective film that, when applied, can easily form a fine pattern without extracting the dye in the color filter, and provides a protective film with good heat resistance and adhesion. An object of the present invention is to provide a composition and a cured product thereof.

0004

[Means for Solving the Problems] The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result, they have arrived at the present invention. That is, the present invention provides epoxy (meth)acrylate (
A) and/or a reaction product of epoxy (meth)acrylate and polybasic carboxylic acid or its anhydride (B), melamine resin (C), photopolymerization initiator (D), and diluent (E). The present invention relates to an ultraviolet curable resin composition for a color filter protective film and a cured product thereof.

Each component of the ultraviolet curable resin composition for a color filter protective film of the present invention will be explained below. Epoxy (meth)acrylate (A) used in the present invention
is an epoxy resin [e.g., novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., YDCN-701, YDCN-
704, YDPN-638, YDPN-602; Dow
Made by Chemical Co., Ltd., DEN-431, DEN-439; Made by Ciba Geigy Co., Ltd., EPN-1138, EPN-1235
, EPN-1299; manufactured by Dainippon Ink and Chemicals Co., Ltd.
N-730, N-770, N-865, N-665, N
-673, N-695, VH-4150, VH-424
0, VH-4440; manufactured by Nippon Kayaku Co., Ltd., EOCN-1
20, EOCN-104, BRPN-1020; manufactured by Asahi Kasei Industries, Ltd., ECN-265, ECN-293, EC
N-285, ECN-299, etc.), bisphenol A type, bisphenol F type, hydrogenated bisphenol A type, brominated bisphenol A type, amino group-containing, alicyclic type, or
Glycidyl ether type epoxy resins such as polybutadiene-modified epoxy resins (e.g., Epicort 828, Epicort 1007, Epicort 807 manufactured by Yuka Shell; Epiclon 840, Epiclon 860 manufactured by Dainippon Ink & Chemicals Co., Ltd.)
, Epiclon 3050, Epiclon 830; manufactured by Dow Chemical Company, DER-330, DER-337, DER-
361; Celoxide 20 manufactured by Daicel Chemical Industries, Ltd.
21, Celoxide 3000; manufactured by Mitsubishi Gas Chemical Co., Ltd.
TETRAD-X, TETRAD-C; Nippon Soda Co., Ltd.
manufactured by Toto Kasei Co., Ltd., EPB-13, EPB-27;
YD-116, YD-128, YD-013, YD-0
20, YDG-414, ST-3000, ST-110
, YDF-190, YDF-2004, YDF-200
7; Ciba Geigy, Gy-260, GY-255
, XB-2615; manufactured by Dow Chemical, DER-332
, DER-662, DER-542, etc.) and tris(hydroxyphenyl)methane-based epoxy resins (e.g., Dow Chemical Company, Tactex-742, XD
-9053; manufactured by Nippon Kayaku Co., Ltd., EPPN-502, etc.)
etc. ] and (meth)acrylic acid.

[0006] The reaction between epoxy resins and (meth)acrylic acid is preferably carried out using about 0.8 to 1.5 chemical equivalents of (meth)acrylic acid, particularly preferably about 0.8 to 1.5 chemical equivalents of (meth)acrylic acid per chemical equivalent of the epoxy group of the epoxy resin. are reacted at a ratio of about 0.9 to 1.1 chemical equivalents, and during the reaction, organic solvents such as butyl cellosolve acetate, carbitol acetate, ethyl methyl ketone, etc. are used, and a catalyst (e.g. , benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, triphenylstibine, etc.), and the amount of the catalyst used is preferably 0.1 to 10% by weight based on the reaction mixture. , particularly preferably from 0.3 to 5% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, phenothiazine, etc.), and the amount used is 0.01% based on the reaction mixture.
~1% by weight is preferred, particularly preferably 0.05~0
．． It is 5% by weight. The reaction temperature is preferably 60 to 150°C, particularly preferably 80 to 120°C.

Next, the reaction product (B) of epoxy (meth)acrylate and polybasic carboxylic acid or its anhydride is the above-mentioned reaction product (B) of epoxy (meth)acrylate (A) and polybasic carboxylic acid or its anhydride ( For example, maleic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, head acid, etc., and anhydrides of these acids, etc.) (esters of hydroxyl groups in epoxy (meth)acrylates) reaction). In the reaction, the amount of the acid or its anhydride is preferably 0.0% per chemical equivalent of hydroxyl group, relative to the hydroxyl group in the epoxy (meth)acrylate.
05 to 1.00 chemical equivalents are reacted. The reaction temperature is preferably 60 to 150°C, particularly preferably 80 to 100°C.
It is.

[0008] The melamine resin (C) used in the present invention is
It is crosslinkable with the OH groups and COOH groups of component (A) and component (B) when heated, and is usually present in component (A) and/or in the composition.
or about 0.5 to 100 parts by weight of the total amount of component (B)
It is used in an amount of 30 parts by weight, preferably 1 to 20 parts by weight. Specific examples of melamine resin (C) include partially or safely etherified polyhydroxymethyl melamine, ie, hexamethoxymethyl melamine, hexabutoxymethyl melamine, and acrylic modified alkylated melamine resins (Sanwa Chemical Co., Ltd.). manufactured by Nikalak MX-3
02, etc.).

The photopolymerization initiator (D) that can be used in the present invention is, for example,

0010

[0011]

0012

[0013]

etc., a copolymerizable photoinitiator, benzoin, etc.
Benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2 -Methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, N,N-
Dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2,
4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketal, benzophenone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, etc. Can be done. These can be used alone or in combination of two or more. Furthermore,
The photopolymerization initiator (D) may be a known and commonly used photosensitizer such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, or triethylamine, alone or in combination. Two or more types can be used in combination. Photopolymerization initiator (D
) is used in an amount of about 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total amount of component (A) and/or component (B) + component (C) in the composition of the present invention. Parts by weight are used.

The diluent (E) that can be used in the present invention is preferably a photopolymerizable vinyl monomer and/or an organic solvent. Typical photopolymerizable vinyl monomers include hydroxyethyl acrylate, 2-hydroxybutyl acrylate, tripropylene diacrylate, and N
, N-dimethylacrylamide, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol penta and hexaacrylate, tris-hydroxyethyl isocyanurate di and triacrylate, phenonexyacrylate,
Examples include acrylate of ethylene oxide adduct of bisphenol A, trimethylolpropane triethoxy triacrylate, and acrylate of trimethylolpropane triglycidyl ether. On the other hand, examples of organic solvents include ethyl methyl ketone, cyclohexanone, toluene, xylene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, and acetic acid. Examples include ethyl, butyl acetate, propanol, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The above diluents may be used alone or in a mixture of two or more.

The amount of diluent (E) used is 30 to 900 parts by weight, particularly preferably 100 to 5 parts by weight, based on 100 parts by weight of the total amount of component (A) and/or component (B) + component (C).
00 parts by weight. The composition of the present invention is prepared by keeping each component at room temperature to 8.
It can be obtained by mixing and dissolving at 0°C. Furthermore, if necessary, novolac type epoxy resin, bisphenol type epoxy resin, glycidyl (meth)acrylate and (meth)acrylic ester (for example, methyl methacrylate ester)

[0017]

etc.), epoxy resins containing two or more epoxy groups in one molecule such as alicyclic epoxy resins, amine compounds, imidazole compounds, and phenols such as phenol novolak and cresol novolac. It can be used in combination with epoxy curing agents such as derivatives.

Furthermore, various additives such as antioxidants, light stabilizers, antifoaming agents, leveling agents, and silane coupling agents can also be used. The composition of the present invention can be made into a cured product by irradiating it with ultraviolet rays and, if necessary, further heating. Next, an example of a method of using the ultraviolet curable resin composition obtained by the present invention will be explained. A photosensitive composition made of natural polymers such as gelatin, glue, or synthetic polymers such as acrylic resin is coated and patterned on a substrate such as glass or a solid-state image sensor in advance by a method such as spin coating, Applying the ultraviolet curable resin composition of the present invention on the color filter formed by dyeing by a method such as spin coating,
Dry the solvent at room temperature to 80°C, then apply a negative mask and irradiate it with ultraviolet rays to cure it. Then, coat it with an organic solvent such as methylene chloride or a dilute alkaline aqueous solution such as aqueous sodium carbonate solution or trisodium phosphate solution. A color filter having a patterned protective film (cured film) can be obtained by dissolving and removing the unirradiated portion of the film, and then heating and curing at 150 to 200° C. if necessary. The film obtained from the ultraviolet curable resin composition of the present invention is particularly suitable as a protective film for color filters used in color video cameras, liquid crystal color TVs, and the like.

[0020]

[Examples] The present invention will be specifically explained below using examples. Synthesis example of epoxy (meth)acrylate (A) Synthesis example 1 Phenol novolac type epoxy resin (Nippon Kayaku Co., Ltd.)
manufactured by EPPN-201, epoxy equivalent weight 180) 1800
g, acrylic acid 720g, triphenylstibine 26g
, 1.25 g of hydroquinone and 1091.7 g of butyl cellosolve acetate were charged, and then reacted at 95° C. to obtain epoxy acrylate.

Synthesis Example 2 Cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd.)
EOCN-103, epoxy equivalent weight 218) 2180
g, acrylic acid 720g, triphenylstibine 26g
, 1.25 g of hydroquinone and 1254.5 g of butyl cellosolve acetate were charged, and then reacted at 95° C. to obtain epoxy acrylate.

Synthesis example of reaction product (B) of epoxy (meth)acrylate and polybasic carboxylic acid or its anhydride Synthesis example 3 Epoxy acrylate 3638.9 obtained in the above synthesis example 1
5 g, butyl cellosolve acetate, 315.3 g, and hexahydrophthalic anhydride, 740.6 g, and heated to 90°C.
A compound having an acid value (excluding butyl cellosolve acetate) of 86 mgKOH/g was obtained.

Synthesis Example 4 Epoxy acrylate 4181.7 obtained in Synthesis Example 2 above
5 g of butyl cellosolve acetate, 396.5 g of tetrahydrophthalic anhydride, and 925 g of tetrahydrophthalic anhydride were charged and reacted at 90° C. to obtain a compound having an acid value of 94.6 mg/KOH/g (excluding butyl cellosolve acetate).

Examples 1 to 4, Comparative Examples 1 and 2 Ultraviolet curable resin compositions for color filter protective films were blended according to the formulations shown in Table 1 (numbers indicate parts by weight), and the compositions were spun onto a glass plate. After coating with a film thickness of 1 to 3 μm, the coating film was dried at 70 ° C. for 5 minutes, a negative film was placed on the coating surface, and a 5 kW ultra-high pressure mercury lamp was used to irradiate ultraviolet rays, and then, The unirradiated portion of the coating film was dissolved and removed with methylene chloride or a 1% aqueous sodium carbonate solution. Various performance tests were conducted on each of the obtained specimens. The results are shown in Table 1.

(Developability) Using a 5 kW ultra-high pressure mercury lamp, ultraviolet rays were irradiated, and then methylene chloride at 25°C (Examples 1 and 2, Comparative Example 1) or 1% aqueous sodium carbonate solution at 25°C (Example 3) , 4, Comparative Example 2), the unirradiated portion was dissolved and removed, and the developability was evaluated. The judgment criteria are as follows. ○───Dissolution rate is fast. ×─── Does not dissolve or dissolves extremely slowly. (Heat resistance) The state of the coating film after being left in a dryer at 200° C. for 1 hour was evaluated. The judgment criteria are as follows. ○─── No coloration of paint film, no abnormal appearance. ×───Coloration of the paint film is observed. (Adhesion) After being left in a dryer at 200°C for 1 hour, the coating film was cut into 100 goblets of 1 x 1 mm in size, and the adhesion was evaluated after peeling off with cellophane tape. did. On the other hand, after being left in a dryer at 200°C for 1 hour, the specimen was left in hot water at 95°C for 30 minutes, and then an adhesion test was conducted.

Table-1
Example
Comparative example

1 2 3 4 1
2 Compound obtained in Synthesis Example 1 (A)
24 4
24 distribution 〃 2 〃
(A) 24 cases
〃 3 〃 (B
) 24
24 groups 〃 4
(B)
20 Hexamethoxymethylmelamine 2.0 3.2
3.0 3.0 Nikalak MX-30
2 *1 (C) 1.0
Irgacure 907 *2 (
D) 0.75 0.75 0.75 0.7
5 0.75 0.75 KAYARAD
DPHA *3 (E) 9
．． 5 9.5 9.5 9.5 9.
5 9.5 Ethyl cellosolve acetate (E) 97 97 97
97 97 97 SH-606
2 (Sila coupling agent) 0.75 0.75
0.75 0.75 0.75 0.75
*
4 Continuation of Table-1
Example
Comparison example
1 2 3
4 1
2 Developability ○
○ ○ ○
○ ○ Heat resistance
○ ○ ○
○ ○ ○
Adhesion Initial 100/100 10
0/100 100/100 100/100
100/100 100/100 After hot water test 100/100 100/100
100/100 100/100 0/1
00 0/100 Note) *1 Nikalac MX-302: Manufactured by Sanwa Chemical Co., Ltd.
Acrylic modified alkylated melamine resin

[0027]

Effects of the Invention The ultraviolet curable resin composition for a color filter protective film of the present invention can be formed into fine patterns, and the cured film shows little discoloration and has excellent adhesion even when left at high temperatures.

Claims (2)

[Claims] [Claim 1] Epoxy (meth)acrylate (A)
and/or containing a reaction product (B) of epoxy (meth)acrylate and a polybasic carboxylic acid or its anhydride, a melamine resin (C), a photopolymerization initiator (D), and a diluent (E). Features: Ultraviolet curable resin composition for color filter protective film. 2. A cured product of the resin composition according to claim 1.