JPH04164970A - Photopolymerizable resin composition, photopolymerizable resin composition for protective film for color filter, and cured material thereof - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizable resin composition which can easily form a fine pattern and has good heat resistance and adhesiveness by mixing a specified compound and a copolymer of glycidyl methacrylate and a specified fluorine compound. CONSTITUTION:A photopolymerizable resin composition which contains a copolymer (having an epoxy equivalent of 200 to 3,000) of glycidyl methacrylate with a fluorinated compound containing ethylenically unsaturated groups (e.g. a copolymer obtained by copolymerizing glycidyl methacrylate of, e.g. formula I or II with a fluorinated compound containing ethylenically unsaturated groups in the presence of a polymerization initiator); and a compound of formula III (wherein n is 1 or 2; a is 4 or 6) (e.g. a compound of formula IV or V). When applied to a color filter, this composition does not extract the dye, can easily form a fine pattern, and can give a protective film (cured film) having good heat resistance and adhesiveness.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a photopolymerizable resin composition, particularly a photopolymerizable resin composition for a protective film of a color filter used in a liquid crystal display device or an image sensor, and its use. Regarding cured products.

(Prior art) Conventionally, in order to smooth out the steps on a color filter and to protect the color filter from chemical treatment and heating in the subsequent process, printing or spin-coding methods have been used to coat the surface of the color filter. A protective film is provided. At present, acrylic resins,
Urethane resin or epoxy resin is used.

Furthermore, polyimide resin with improved heat resistance, for example,
This method has been proposed in Japanese Patent Application Publication No. 1-156371.

(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, chemical resistance, etc., but have a problem in that they are not suitable for forming fine patterns in protective films because of their thermosetting properties. The purpose of the present invention is to protect a color filter by easily forming a fine pattern without extracting the dye in the color filter when applied, and by providing a protective film (cured film) with good heat resistance and adhesion. An object of the present invention is to provide a photopolymerizable resin composition for films and a cured product thereof.

(Means for Solving the Problems) The present inventors have conducted extensive research to solve the above problems, and as a result, have arrived at the present invention.

That is, the present invention comprises: 1. A copolymer of glycidyl methacrylate and a fluorine-containing ethylenically unsaturated group-containing compound (epoxy equivalent is 200 to 3000) (A) and a compound represented by general formula (1) (B ) (wherein, n is 1 or 2, and a is 4 or 6.) A photopolymerizable resin composition or a photopolymerizable resin composition for a color filter protective film.

Z It relates to a cured product of the photopolymerizable resin composition or the photopolymerizable resin composition for color filter protective film according to item 1.

Hereinafter, each component of the composition of the present invention (hereinafter, the photopolymerizable resin composition and the photopolymerizable resin composition for a color filter protective film will be simply referred to as a composition) will be explained.

Copolymer of glycidyl methacrylate and fluorine-containing ethylenically unsaturated group-containing compound (epoxy equivalent is 200
~3000) (A) is a compound containing glycidyl methacrylate and a fluorine-containing ethylenically unsaturated group (for example, H(CF2CFSaeCH!-〇-'6-cH=c mountain 0
0 CHI c, p, ca-o-3-cH=cx c, p, ca
-o-e-<=ch, etc. can be mentioned. ) can be obtained by copolymerizing 9 using a polymerization initiator such as azobisisobutylnitrile or benzoyl peroxide. The copolymer (A) of glycidyl methacrylate and a fluorine-containing ethylenically unsaturated group-containing compound can be easily obtained from the market. For example, manufactured by Kijo Kogyo ■,
These are F-1, F-2, F-3, F-4, etc.

Specific examples of the compound (B) represented by the general formula (11) include the following.These can be used alone or in combination of two or more.In the present invention, the compound (B) represented by the general formula (1) The amount of compound (B) to be used is 1 part by weight per 100 parts by weight of the copolymer (A) of glycidyl methacrylate and a fluorine-containing ethylenically unsaturated group-containing compound.
0 to 500 parts by weight is preferred, particularly preferably 50 to 2 parts by weight.
00 parts by weight.

The photocurable resin composition and the photocurable resin composition for color filter protective film of the present invention are blended with a photopolymerization initiator (C) and a photocationic polymerization catalyst (D) before or before use. It is preferable to use

Typical photopolymerization initiators (C) include 2-
Methyl-1-(4-(methylthio)phenyl]-2-morpholino-propan-1-one, ■-hydroxycyclohexylphenyl ketone, benzophenone 2-ethylanthraquinone, 2,4-diethylthioxanthone, 2゜4-diisopropyl Examples include thioxanthone, acetophenone dimethyl ketal, 4-(2-acryloyl)oxyethoxy-phenyl-2-hydroxy-2-propyl ketone, etc. These can be used alone or in combination of two or more.

Further, the photopolymerization initiator (C) may optionally be a photosensitizer such as N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, etc. alone or in combination. Can be used in combination with more than one species. Preferred examples of these photopolymerization initiators (C) include 2-methyl-1-(4-(methylthio)phenyl]-2-morpholino-propan=1-one, 2,4
-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like.

The amount of photopolymerization initiator (C) to be used is preferably 0.1 to IO per 100 parts by weight of the total amount of component (A) + component (B).
Parts by weight, particularly preferably 1 to 5 parts by weight.

Typical photocationic polymerization catalysts (D) include, for example, complexes of one or more metal fluoroborates and boron trifluoride described in U.S. Pat. No. 3,379,653, and U.S. Pat. No. 3,586,616. bis(perfluoroalkylsulfonyl)methane metal salt as described in the specification,
Aryldiazonium compounds described in U.S. Pat. No. 3,708,296, aromatic onium salts of Group VIa elements described in U.S. Pat. No. 4,058,400, aromatic onium of Group Va elements as described in U.S. Pat. No. 4,069,055. salts, dicarbonyl chelates of Group IV a-Va elements described in US Pat. No. 4,086,091, thiopyrylium salts as described in US Pat. No. 4,139,655, MP as described in US Pat. No. 4,161,478, anions (
where M is selected from P, A, and sb), a polyarylsulnium complex salt described in U.S. Pat. No. 4,231,951, and U.S. Pat. No. 425
The aromatic iodonium complex salts and aromatic sulfonium complex salts described in No. 6828 are included.

The most preferred cationic photopolymerization catalyst is a polyalyl sulfonium complex salt. Some of these salts include, for example, FC-508 or FX-512 (polyarylsulfonium hexafluorophosphate and FC-508
(manufactured by 3M Company) or UVE-1014
(Manufactured by General Electric Company, polyarylsulfonium hexafluoroantimony salt) SP-
A commercially available product is available as 170,5P-150 (manufactured by Asahi Denka ■, polyarylsulfonium hexafluorophosphate, polyarylsulfonium hexafluorophosphate). These photocationic polymerization catalysts (D) can be used alone or in combination of two or more in any proportion.

The amount of photocationic polymerization catalyst (D) used is component (A) + (
It is 0.05 to 5 parts by weight, particularly preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the total amount of component B).

It is preferable to use solvents in the composition of the present invention in order to facilitate handling during use. Examples of the solvents include ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve acetate, methyl ethyl ketone, and the like. The amount of organic solvent used is the total amount of component (A) + component (B) + component (C) + component (D).
When 0 parts by weight, the amount is preferably 30 to 900 parts by weight, particularly preferably 100 to 500 parts by weight. The composition of the present invention can be obtained by mixing and dissolving each component at room temperature to 80°C.

The composition of the present invention may further contain an epoxy curing agent (for example, 2-ethyl-4-methylimidazole, 1-
Phenyl-2-methylimidazole, 2-phenyl-4
-methyl-5-hydroxymethylimidazolephenol novolak, etc.), light stabilizers, antioxidants, silane coupling agents (e.g. H3-ClCH2CH25i (OCHs)sCHt=
CH-COCH-CH-CH2Si (QC, etc.)
This can be done by adding a leveling agent, etc.

After removing the solvent, the composition of the present invention can be made into a cured product by irradiating it with light such as ultraviolet rays by a conventional method and further heating if necessary.

Next, an example of a method of using the photopolymerizable resin composition for a color filter protective film of the present invention will be explained.

A photosensitive composition consisting of a natural polymer such as gelatin, glue, or a synthetic polymer such as acrylic resin is coated on a substrate such as glass or a solid-state image sensor by a known method using a method such as a spin cord, and patterned. The composition of the present invention is applied by a method such as printing or spin cording onto a color filter formed by dyeing, and the composition is heated at room temperature to 80℃.
The solvent is removed by drying at °C, then a negative mask is brought into contact with the film, the film is cured by irradiation with ultraviolet rays, and the unirradiated parts of the film are dissolved and removed with an organic solvent such as methylene chloride. , a patterned protective film (cured film) by heating at 150-200°C as necessary.
A color filter having the following properties can be obtained.

The cured film obtained from the 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.

When the composition 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.

The photopolymerizable resin composition of the present invention can be applied to color filters R and G in addition to the color filter protective film.

It can be used for B resin, solder resist, etc.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

Examples 1 to 4 A photopolymerizable resin composition for a color filter protective film was blended according to the formulation shown in Table 1 (numbers are parts by weight), and this was coated onto a glass plate with a thickness of 1 to 3 μm using a spin cord.
After coating with a film thickness of
Ultraviolet rays were irradiated using a 5KW ultra-high pressure mercury lamp, and then the unirradiated portions of the coating film were dissolved and removed with methylene chloride, and the developability was evaluated. (Those with a fast dissolution rate were expressed as 0, and those with an extremely slow dissolution rate were expressed as x.) Next, heat curing was performed at 180° C. for 1 hour.

Next, the heat-cured product was left in a dryer at 250"C for 1 hour, and the heat resistance and adhesion (initial and initial stages) of the cured product (cured film) formed on the glass plate were evaluated. Also,
Furthermore, the adhesion after being left in hot water at 100'C for 1 hour (after hot water treatment) was also evaluated.

The evaluation method is shown below.

(Heat-resistant) O: No coloration of cured film, no abnormal appearance.

△・・・・・・Slightly visible.

×...The coloring of the cured film is strong.

(Adhesion) Make a cut in the cured film and cut a small square piece with one side IM.
Cut each piece into pieces, attach cellophane tape to the surface, and immediately peel it off. It is expressed by the number of small pieces of cured film remaining at that time.

The larger the number, the better the adhesion.

Note) *■ F-1: Manufactured by Itagami Kogyo ■, copolymer of glycidyl methacrylate and part tetra-octyl acrylate, powder, epoxy equivalent 300° *■ F-2 = Manufactured by Negami Kogyo ■, glycidyl methacrylate and octafluoropentyl Copolymer of methacrylate, powder, epoxy equivalent weight 300° *■ F-3: Manufactured by Itagami Kogyo ■, copolymer of glycidyl methacrylate and octafluoropentyl methacrylate, powder, epoxy equivalent weight 500° *■ F-4: On board Manufactured by Kogyo ■, copolymer of glycidyl methacrylate and perfluorooctylethyl acrylate, powder, epoxy 650° *■ Irgacure 907: Manufactured by Ciba Geigy, photopolymerization initiator *■ 5P-170: Manufactured by Asahi Denka ■, Hikari Cationic polymerization catalyst, 50% diluted product of brovidine carbonate) *■ 1-Phenyl-2-methylimidazole [Curing of the invention] Using the photopolymerizable resin composition of the present invention, fine patterning is possible, and The cured film shows little discoloration even when left at high temperatures, and has excellent adhesion and is suitable for use as a color filter protective film.

Claims (1)

[Scope of Claims] 1. Copolymer of glycidyl methacrylate and fluorine-containing ethylenically unsaturated group-containing compound (epoxy equivalent is 2
00-3000) (A) and the compound (B) represented by the general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In the formula, n is 1 or 2, a is 4 or 6, A photopolymerizable resin composition comprising: 2. Copolymer of glycidyl methacrylate and fluorine-containing ethylenically unsaturated group-containing compound (epoxy equivalent: 20
0-3000) (A) and the general formula (1) according to claim 1
A photopolymerizable resin composition for a color filter protective film, comprising a compound (B) represented by: 3. A cured product of the photopolymerizable resin composition according to claim 1 or 2.