JPH04236212A - Resin composition, resin composition for protective film of color filter and cured product thereof - Google Patents

Abstract

PURPOSE:To obtain a resin composition, containing a polymer of epoxycyclohexyl acrylates, a cationic photopolymerization catalyst, a solvent, an alicyclic epoxide and an acrylate, excellent in heat resistance and adhesion and useful for protecting ultraviolet ray curing color filters, etc. CONSTITUTION:The objective resin composition is obtained by blending (A) a polymer of a compound (e.g. 3,4-epoxycyclohexylmethyl methacrylate) expressed by the formula (R is H or CH3) or a copolymer (having 200-3000 epoxy equiv.) of the compound expressed by the formula and an ethylenically unsaturated group-containing compound (e.g. methyl methacrylate) with (B) a cationic photopolymerization catalyst (e.g. a polyarylsulfonium hexafluorophosphate) and (C) an organic solvent (e.g. ethylcellosolve acetate), alicyclic epoxides (e.g. 3,4-epoxycyclohexylmethyl 3,4- epoxycyclohexanecarboxylate) and/or an acrylate (e.g. isobornyl acrylate).

Description

[Detailed description of the invention]

0001

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

0002

[Prior Art] Conventionally, in order to smooth out the unevenness of color filters and to protect color filters from chemical treatment and heating in post-processes, protection has been applied to the surface of color filters by printing or spin coating. A membrane is provided. Currently, acrylic resins, urethane resins, or epoxy resins are used as resins for such protective films. Furthermore, polyimide resin with improved heat resistance (
For example, see Japanese Unexamined Patent Publication No. 1-156371).

0003

Problems to be Solved by the Invention The acrylic resins and urethane resins have low heat resistance and poor chemical resistance, so they are subject to limitations in processing steps after forming a film. On the other hand, epoxy resins or polyimide resins have excellent heat resistance and chemical resistance, but because they are thermosetting,
There is a problem in that it is not suitable for forming a fine pattern on a protective film. The purpose of the present invention is to provide a protective film (cured film) that does not extract the dye in the color filter when applied, makes it easy to form fine patterns, and has good heat resistance and adhesion.
An object of the present invention is to provide an ultraviolet curable resin composition suitable for a color filter protective film that provides a color filter protective film, 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

1) Compound represented by formula [1]

00
06]

[Case 2]

(In the formula, R is H or CH3.)
or a copolymer of the compound represented by formula [1] and an ethylenically unsaturated group-containing compound (the epoxy equivalent is 2
00-3000) A resin composition comprising (A), a photocationic polymerization catalyst (B), an organic solvent, an alicyclic epoxide, and/or an acrylate (C). 2) A polymer of the compound represented by the formula [1] described in 1) or a copolymer of the compound represented by the formula [1] with a compound containing an ethylenically unsaturated group (epoxy equivalent: 200 to 300
0) A resin composition for a color filter protective film, comprising (A), a photocationic polymerization catalyst (B), an organic solvent, an alicyclic epoxide, and/or an acrylate (C). 3) A cured product of the resin composition described in item 1) or item 2).

[0008] Next, the resin composition of the present invention and the resin composition for color filter protective film (hereinafter collectively referred to simply as "composition")
Each component of the following will be explained. In the composition of the present invention, a polymer of a compound represented by formula [1] or a compound represented by formula [
Copolymer of the compound represented by 1] and an ethylenically unsaturated group-containing compound (epoxy equivalent is 200 to 3000) (
Use A). Specific examples of the compound represented by formula [1] include, for example:

[0009]

[Chemical formula 3] (Manufactured by Daicel Chemical Industries, Ltd., AETHB)

[C4] (manufactured by Daicel Chemical Industries, Ltd., METHB), etc.

The polymer of the compound represented by formula [1] can be obtained by polymerizing the compound represented by formula [1] using a polymerization initiator such as azobisisobutylnitrile or benzoyl peroxide. Any non-reactive organic solvent can be used as the reaction solvent. Examples include toluene, methyl ethyl ketone, ethyl acetate, and ethyl cellosolve acetate. The polymer of the compound represented by formula [1] can be easily obtained from the market. For example, manufactured by Negami Factory Co., Ltd., E-1 (average molecular weight 9000), E-2 (average molecular weight 10000), E-
3 (average molecular weight 21,000), etc.

Copolymer of the compound represented by formula [1] and a compound containing an ethylenically unsaturated group (epoxy equivalent is 20
0 to 3000) is a compound represented by formula [1] and a compound containing an ethylenically unsaturated group (for example, ethyl (meth)acrylate, methyl (meth)acrylate, butyl (meth)acrylate, styrene, 2- Hydroxyethyl vinyl ether, (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate,

0012

[C5]

[C6]

[0013]

[C7]

[Chemical formula 8]

[0014] etc. can be mentioned. ) can be obtained by polymerizing in an organic solvent using the same polymerization initiator as above. The reaction temperature is preferably 50 to 100°C.

As the photocationic polymerization catalyst (B), any known photocationic polymerization catalyst can be used. For example, polyarylsulfonium hexafluorophosphate (manufactured by 3M Company, FC-508,
FX-512), polyarylsulfonium hexafluoroantimony salt (manufactured by General Electric Company, UVE-1014), SP-150, SP-1
70 (manufactured by Asahi Denka Co., Ltd., polyarylsulfonium hexafluoroantimonate, polyarylsulfonium hexafluorophosphate), and the like. These photocationic polymerization catalysts (B) can be used alone or in combination of two or more in any proportion.

The preferred range of the amount of photocationic polymerization catalyst (B) used is 0.1 to 100 parts by weight of component (A).
5% by weight is preferred, particularly preferably 0.5-2% by weight
It is.

Among the organic solvents, alicyclic epoxides and/or acrylates (C) used in the composition of the present invention,
Examples of the organic solvent include ethyl cellosolve acetate, isopropyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl cellosolve, butyl cellosolve, carbitol acetate, methyl ethyl ketone, and the like.

Examples of alicyclic epoxides include 3
, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1-methylcyclohexanecarboxylate, 6-methyl-3,4-epoxy Cyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methyl Cyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane, bis(3,4- Epoxycyclohexylmethyl)oxalate, bis(3,4
-epoxycyclohexylmethyl)adipate, bis(
3,4-epoxy-6-methylcyclohexylmethyl)
Examples include adipate, 4-vinylcyclohexane monoepoxide, and the like.

Examples of acrylates include isobornyl acrylate, hydrogenated dicyclopentadiene acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513A), tricyclodecane diacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate. Acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, epoxy acrylate (e.g., reaction product of novolak type epoxy resin and acrylic acid, etc.), urethane acrylate (e.g., diol compound such as polytetramethylene glycol, ethylene glycol, etc.) Examples include reaction products of diiricyanate compounds such as isophorone diisocyanate and acrylate compounds having one hydroxyl group in the molecule such as 2-hydroxyethyl acrylate. The amount of the organic solvent, alicyclic epoxide and/or acrylate (C) used is the total amount of component (A) + component (B) 100
When expressed as parts by weight, it is preferably 30 to 900 parts by weight,
Particularly preferably 100 to 700 parts by weight.

[0020] In the composition of the present invention, each component is kept at room temperature to 80°C.
It can be obtained by mixing and dissolving.

[0021] The composition of the present invention further includes, if necessary,
Photopolymerization initiators (e.g. benzoin, benzoin and its alkyl ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2- Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 2-methylanthraquinone, 2
- Anthraquinones such as ethyl anthraquinone and 1-chloroanthraquinone, thioxanthone such as 2,4-diethylthioxanthone, 2-chlorothioxanthone, and diisopropylthioxanthone, benzyl dimethyl ketal, 2-hydroxycyclohexyl phenyl ketone, benzophenone, etc.), antioxidants , silane coupling agent (e.g.

[0022]

[Chemical formula 9]

[Chemical formula 10]

[0023]

embedded image etc.) A light stabilizer, a leveling agent, an antifoaming agent, etc. can be added.

Curing of the composition of the present invention by irradiation with ultraviolet rays can be carried out by a conventional method. For example, ultraviolet rays may be irradiated using a low-pressure or high-pressure mercury lamp or xenon lamp. The resin composition of the present invention is particularly useful as a protective film for color filters, but can also be used for metals, plastics, rubber, paper, wood and glass, ceramic coatings, inks, paints, etc. can.

Next, an example of a method of using the resin composition for a color filter protective film of 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 on a substrate such as glass or a solid-state image sensor by a known method by a method such as spin coating, and patterned. The resin composition for a color filter protective film of the present invention is applied by printing or spin coating onto a color filter formed by dyeing, dried at room temperature to 80°C to remove the solvent, and then a negative mask is applied. The patterned protection is then cured by irradiation with ultraviolet rays, followed by dissolving and removing the unirradiated parts of the coating with an organic solvent such as methylene chloride, and then heating at 150 to 200°C. Film (cured film)
A color filter having the following properties can be obtained. The cured film obtained from the resin composition for color filter protective film 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. When the resin composition for a color filter protective film of the present invention is used, it is easy to form a fine pattern, and the cured product (cured film) thereof has excellent heat resistance and adhesion.

[0026]

[Examples] The present invention will now be explained in more detail with reference to Examples.

[Synthesis example of component (A), Synthesis examples 1 and 2] Synthesis example 1. 193 parts by weight of the compound represented by the above formula [2], 193 parts by weight of ethyl acrylate, and 600 parts by weight of methyl ethyl ketone were added to a reaction vessel purged with N2 gas, and the reaction solution was heated at 70°C.
and azobisisobutyronitrile 4 as a polymerization initiator.
Parts by weight were added little by little to carry out solution polymerization, and then the solvent was removed to obtain a copolymer having an average molecular weight of 40,000 and an epoxy equivalent of 400.

Synthesis Example 2. 208 parts by weight of the compound represented by the above formula [3], 104 parts by weight of ethyl methacrylate, and 600 parts by weight of methyl ethyl ketone were added to a reaction vessel purged with N2 gas, the reaction solution was heated to 70°C, and azobisisomer was added as a polymerization initiator. 5 parts by weight of butyronitrile was added little by little to perform solution polymerization, and then the solvent was removed to obtain a copolymer with an average molecular weight of 25,000 and an epoxy equivalent of 312.

Examples 1 to 6 A resin composition for a color filter protective film of the present invention was prepared by mixing each component according to the composition shown in Table 1 (the composition is expressed in parts by weight). After coating the plate with a film thickness of 1 to 3 μm by spin coating, the coating film was dried at 70°C for 30 minutes, a negative film was placed on the coating film, and then ultraviolet rays were irradiated using a 5KW ultra-high pressure mercury lamp. Then, the unirradiated portion of the coating film was dissolved and removed with methylene chloride, and the developability was evaluated. (Those with a fast dissolution rate were indicated as ○, and those that did not dissolve or had an extremely slow dissolution rate were indicated as ×.) Next, the unirradiated portion was dissolved and removed, and the product was left in a dryer at 180°C for 1 hour. The heat resistance and adhesion (initial stage) of the cured product (cured film) formed on the glass plate were evaluated, and the adhesion after being left in hot water at 100°C for 1 hour (after hot water treatment) was evaluated. ) were also evaluated.

[0029]

[Heat resistance] The coloring of the cured product after being left at 200° C. for 1 hour was evaluated. ○...No coloring of the cured film, no abnormal appearance. △...Slight discoloration of the cured film is observed. ×...The coloring of the cured film is strong.

[0030]

[Adhesion] Cuts were made in the cured product to cut into 100 square pieces of 1 mm on each side, and cellophane tape was pasted on the surface and immediately peeled off. It was expressed by the number of small pieces of the cured product remaining at that time. The larger the number, the better the adhesion.

[0031]

[Table 1]

Note) *■ E-1: Manufactured by Negami Kogyo Co., Ltd.
Polymer of the compound represented by the above formula [2], average molecular weight 9
000, epoxy equivalent weight 193 *■ E-2: Manufactured by Neagami Kogyo Co., Ltd., polymer of the compound represented by the above formula [2], average molecular weight 10000, epoxy equivalent weight 193 *■ SP-170: Manufactured by Asahi Denka Co., Ltd. , photocationic polymerization catalyst. *■ KAYARAD DPHA: Dipentaerythritol penta and hexaacrylate mixture manufactured by Nippon Kayaku Co., Ltd. *■ Celloxide 2021: 3,4-epoxycyclohexylmethyl-3,4- manufactured by Daicel Chemical Industries, Ltd.
Epoxycyclohexane carboxylate *■ FA-513A: Hydrogenated dicyclopentadiene acrylate *■ manufactured by Hitachi Chemical Co., Ltd. Irgacure 184: manufactured by Ciba Geigy, photopolymerization initiator *■ Silane coupling agent: Formula [10] ]Compounds shown by

[0033]

[Effects of the Invention] Using the resin composition of the present invention, it is possible to form fine patterns, and the cured film shows little discoloration even when left at high temperatures, and has excellent adhesion, making it suitable for use as a color filter protective film. .

Claims (3)

[Claims] Claim 1: A polymer of a compound represented by formula [1] [Formula 1] (wherein R is H or CH3) or a compound represented by formula [1] and an ethylenically unsaturated group-containing compound Copolymer with compound (epoxy equivalent is 200-3000
) A resin composition comprising (A), a photocationic polymerization catalyst (B), an organic solvent, an alicyclic epoxide, and/or an acrylate (C). Claim 2: A polymer of the compound represented by formula [1] according to claim 1, or a copolymer of the compound represented by formula [1] and an ethylenically unsaturated group-containing compound (epoxy equivalent: 200
~3000) (A), photocationic polymerization catalyst (B), organic solvent, alicyclic epoxides and/or acrylates (
C) A resin composition for a color filter protective film, comprising: 3. A cured product of the resin composition according to claim 1 or 2.