JP2001272780A - Photosensitive resin composition and color filter for display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high sensitivity to exposure, a photosensitive resin composition capable of forming a pattern uniform in thickness and a color filter for a display with desired patterns such as colored layers, a black matrix, a protective layer and a gap holding material with a high degree of accuracy. SOLUTION: Each of the photosensitive resin compositions contains at least a photopolymerization initiator, a monomer having an unsaturated double bond, an epoxy resin and an alicyclic compound-containing resin obtained by polymerizing a monomer containing at least a vinyl group and/or an isopropenyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a liquid crystal display,
The present invention relates to a color filter used for a flat display such as a plasma display, a field emission display and an electroluminescence panel, and a photosensitive resin composition used for producing the same.

[0002]

2. Description of the Related Art A color filter used for a flat display such as a liquid crystal display (LCD), a plasma display (PDP), a field emission display (FED), an electroluminescence panel (EL), etc. The pattern includes a colored layer, a black matrix (light shielding layer), a protective layer, a gap holding material, and the like.

Heretofore, as a photosensitive resin composition for forming such a pattern, a polymer compound obtained by copolymerizing a monomer such as an alkyl compound, an aromatic esterified acrylic acid or styrene (Japanese Patent Laid-Open No. No. 318816).

[0004]

However, when the above-mentioned polymer compound is used, the photosensitive resin composition may be colored to absorb ultraviolet light or visible light. When such light absorption occurs, energy loss of ultraviolet rays used for exposure at the time of pattern formation occurs, causing a decrease in sensitivity of the photosensitive resin composition, and a residual film ratio (a ratio of a pattern thickness to a coating film thickness). However, there is a problem that the crosslink density decreases.
There is also a problem that coloring due to yellowing or the like occurs in post-baking after exposure and development.

Further, in post-baking after exposure and development, a phenomenon called film thinning (decrease in bulk before and after post-baking) usually occurs. However, in the photosensitive resin composition using the above-described polymer compound, However, there is a problem that the degree of the film reduction is large, and a problem that the pattern is not uniformly reduced, and a bulge occurs at the peripheral portion of the pattern, thereby deteriorating the pattern accuracy.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has been made in consideration of a photosensitive resin composition having high exposure sensitivity, a photosensitive resin composition capable of forming a pattern having a uniform thickness, and a coloring resin composition. It is an object of the present invention to provide a display color filter provided with a desired pattern of a layer, a black matrix (light shielding film), a protective layer, a gap holding material, and the like with high accuracy.

[0007]

In order to achieve the above object, a photosensitive resin composition of the present invention comprises a photopolymerization initiator, a monomer having an unsaturated double bond, an epoxy resin,
The resin containing at least an alicyclic compound-containing resin was formed so that the alicyclic compound-containing resin was obtained by polymerizing a monomer containing at least a vinyl group and / or an isopropenyl group.

[0008] The monomer is a polyfunctional acrylate monomer, and the vinyl group and the isopropenyl group have a carboxyl group at one of the double bond carbons.

A color filter for display of the present invention comprises a support and a pattern provided on the support, wherein the pattern is formed using the above-described photosensitive resin composition. The configuration was adopted.

In the present invention, the alicyclic compound-containing resin serves to prevent the coloring of the photosensitive resin composition and to reduce the energy loss of exposure ultraviolet rays, and the polyfunctional compound contained in the photosensitive resin composition. An acrylate monomer and a vinyl group or an isopropenyl group having a carboxyl group on one of the double bond carbons have a function of reducing the heat shrinkage and uniforming the film thickness by heating.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The preferred embodiments of the present invention will be described below. The photosensitive resin composition of the present invention comprises a photopolymerization initiator, a monomer having an unsaturated double bond,
It contains at least an epoxy resin and an alicyclic compound-containing resin obtained by polymerizing a monomer containing at least a vinyl group and / or an isopropenyl group.

The alicyclic compound constituting the alicyclic compound-containing resin is preferably a polycyclic compound having a plurality of rings formed by carbon atoms. Examples of the alicyclic compound include adamantyl, norbornyl and tricyclodecanyl groups. Can be mentioned.

The alicyclic compound-containing resin used in the present invention is a monomer obtained by adding a vinyl group and / or an isopropenyl group to such an alicyclic compound, for example, methyl adamantyl (meth) acrylate, isonorbornyl (meth) acrylate And a polymer obtained by radical polymerization of tricyclodecanyl (meth) acrylate and the like.

Such an alicyclic compound-containing resin has a molecular weight of 2,000 to 50,000, preferably 20,000 to 40,000.
000, and preferably in the range of about 40 to 65% by weight in the solid content of the photosensitive resin composition excluding the photopolymerization initiator. In addition, the solid content of the photosensitive resin composition in the present invention means a photopolymerization initiator, a monomer having an unsaturated double bond, an epoxy resin, and a resin containing an alicyclic compound.

Since the photosensitive resin composition of the present invention contains the alicyclic compound-containing resin as described above, there is almost no coloring as in the conventional photosensitive resin composition, and energy loss of exposure ultraviolet rays is reduced. Reduced.

The photopolymerization initiator constituting the photosensitive resin composition of the present invention includes benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone and 4,4-bis (diethylamine). Benzophenone, α-amino acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2
-Diethoxyacetophonone, 2,2-dimethoxy-2
-Phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethylketal, benzylmethoxyethyl Acetal, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-
Amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberone, methyleneanthrone, 4-azidobenzylacetophenone,
2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1-
Phenyl-propanedione-2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-
Benzoyl) oxime, Michler's ketone, 2-methyl-
1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, naphthalenesulfonyl chloride, quinoline sulfonyl chloride, n -Phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, N1717 manufactured by ADEKA CORPORATION, carbon tetrabromide, tribromophenyl sulfone, peroxide Examples include a combination of a photoreducing dye such as benzoin, eosin, and methylene blue with a reducing agent such as ascorbic acid and triethanolamine. In the present invention, one or more of these photopolymerization initiators can be used.

Such a photopolymerization initiator is preferably contained in an amount of about 5 to 15 parts by weight based on 100 parts by weight of the solid content of the photosensitive resin composition excluding the photopolymerization initiator.

The monomers having an unsaturated double bond contained in the photosensitive resin composition of the present invention include allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, and the like. 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobonyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, Phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate Diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5
Pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate,
Glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyl triacrylate Methylolpropane triacrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacrylate,
2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, and the above acrylate is changed to methacrylate. And γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone and the like. In the present invention, the above-mentioned monomers can be used as one kind or a mixture of two or more kinds, or as a mixture with other compounds.

Such a monomer is preferably contained in an amount of about 25 to 40% by weight in the solid content of the photosensitive resin composition excluding the photopolymerization initiator.

The epoxy resin contained in the photosensitive resin composition of the present invention includes Epicoat series manufactured by Mitsubishi Yuka Shell Co., Ltd., Celoxide side series manufactured by Daicel Co., Ltd.
Epold series, or bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol glycidyl ester, aliphatic or alicyclic epoxy resin Amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, copolymerized epoxy compound of glycidyl (meth) acrylate and a radically polymerizable monomer, and the like. In the present invention, the above epoxy resins can be used alone or as a mixture of two or more.

Such an epoxy resin accounts for 10 to 30% by weight in the solid content of the photosensitive resin composition excluding the photopolymerization initiator.
It is preferable that it is contained to a certain extent.

Further, in the photosensitive resin composition of the present invention, the contained monomer is a polyfunctional acrylate monomer,
The vinyl group and the isopropenyl group of the monomer constituting the alicyclic compound-containing resin may have a carboxyl group at one of the double bond carbons. As a result, heat shrinkage due to heating in post-baking after exposure and development is reduced, and the film thickness (decrease in bulk before and after post-baking) is evenly generated, so that a pattern with a uniform thickness without swelling on the peripheral edge can be formed. It becomes possible. Further, alkali development is possible.

As the polyfunctional acrylate monomer, the polyfunctional acrylate monomer or the polyfunctional methacrylate monomer in the above exemplified monomers can be used. Examples of the alicyclic compound-containing resin in which a vinyl group and an isopropenyl group have a carboxyl group at one of double bond carbons include, for example, (meth) acrylic acid;
It contains one or more monomers of (meth) acrylic acid ester, styrene and α-methylstyrene, and contains monomers such as methyl adamantyl (meth) acrylate, isonorbornyl (meth) acrylate, and tricyclodecanyl (meth) acrylate. Copolymers and the like containing at least one kind can be mentioned.

The photosensitive resin composition of the present invention may contain another resin component. Examples of such a resin component include an alkali development type binder resin. Specifically, acrylic acid, methacrylic acid, a dimer of acrylic acid (for example, M-5600 manufactured by Toa Gosei Chemical Co., Ltd.),
Itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, one or more of these acid anhydrides, methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, n-propyl acrylate, n
-Propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate , N-pentyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, styrene, α- And copolymers of at least one of methylstyrene and 1-vinyl-2-pyrrolidone. Copolymers polymers obtained by adding an ethylenically unsaturated compound having a glycidyl group or hydroxyl group in, but not limited thereto.

Examples of the non-alkali developing type binder resin include polyvinyl alcohol, polyvinyl butyral, acrylate polymer, methacrylate polymer, polystyrene, α-methylstyrene polymer,
-Vinyl-2-pyrrolidone polymers and copolymers thereof.

Such a resin component is preferably contained in an amount of about 10 to 20% by weight in the solid content of the photosensitive resin composition excluding the photopolymerization initiator.

[0027] The photosensitive resin composition of the present invention may contain a coloring material such as a pigment or a dye. As the pigment to be used, known red pigments, yellow pigments, green pigments, blue pigments, purple pigments, black pigments and the like can be used. When a specific example of the pigment is represented by a color index number, the red pigment is PR177, PR48: 1, PR254, the yellow pigment is PY83, PY138, PY139, PY150, the green pigment is PG7, PG36, the blue pigment is PB15,
PB1, PB19, PB60, PB61, purple pigment
PV23, black pigment is carbon black, metal oxide black pigment (titanium black, Cu, Fe, Mn, V,
Pigments containing oxides such as Ni).

The coloring material may be contained in an amount of 5 to 100 parts by weight, preferably about 10 to 60 parts by weight, based on 100 parts by weight of the solid content of the photosensitive resin composition excluding the photopolymerization initiator. desirable.

When the photosensitive resin composition of the present invention contains the above-mentioned coloring material, it can contain a known dispersant. As the dispersant to be used, for example, cationic,
Examples of the surfactant include anionic, nonionic, amphoteric, silicone, and fluorine-based surfactants. Such a dispersant is preferably contained in an amount of about 1 to 80 parts by weight based on 100 parts by weight of the coloring material.

The photosensitive resin composition of the present invention further contains, as additives, a sensitizer, a polymerization terminator, a chain transfer agent, a leveling agent, a dispersant, a plasticizer, a surfactant, an antifoaming agent and the like. Used as needed.

The solvent used in the photosensitive resin composition of the present invention includes propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methoxybutyl 3-acetate, EEP, cyclohexanone, diethylene glycol dimethyl ether, methyl carbitol, ethyl carbitol and the like. be able to.

The photosensitive resin composition of the present invention as described above comprises the above-mentioned photopolymerization initiator, monomer, epoxy resin, resin containing an alicyclic compound, a solvent, and if necessary, other resin components and additives. Can be mixed and produced.

The color filter for display of the present invention is used for flat displays such as liquid crystal display (LCD), plasma display (PDP), field emission display (FED), and electroluminescence panel (EL). It is provided with a colored layer, a black matrix (light shielding layer), a protective layer, a gap holding material, and the like in a predetermined pattern according to the application.

The basic structure of the display color filter of the present invention comprises a support and desired patterns such as a coloring layer, a black matrix (light-shielding layer), a protective layer, and a gap holding material provided on the support. Things.

The support is made of a transparent rigid material having no flexibility such as quartz glass, Pyrex (registered trademark) glass or a synthetic quartz plate, or a transparent transparent material having flexibility such as a transparent resin film or an optical resin plate. A flexible material can be used.

The pattern can be formed by applying the photosensitive resin composition of the present invention by a conventional coating method such as a spin coating method, and exposing and developing it in a predetermined pattern. In this pattern formation, the alicyclic compound-containing resin contained in the photosensitive resin composition of the present invention used prevents coloring of the photosensitive resin composition and reduces energy loss of exposure ultraviolet rays. Thus, the color filter of the present invention has a desired pattern with high accuracy.

[0037]

Next, the present invention will be described in more detail with reference to examples.

Example 1 First, as an alicyclic compound-containing resin, a (methyladamantyl methacrylate)-(methacrylic acid)-(cyclohexyl methacrylate) copolymer was prepared by radical polymerization.

Next, using this alicyclic compound-containing resin,
A photosensitive resin composition (Example 1) having the following composition was prepared. Composition of photosensitive resin composition (Example 1) / photopolymerization initiator: 10 parts by weight (Irgacure 369 manufactured by Ciba Geigy) Monomer: 30 parts by weight (dipentaerythritol hexaacrylate) Epoxy resin: 20 parts by weight ( (Eporide GT401 manufactured by Daicel Corporation)-Resin containing alicyclic compound ... 50 parts by weight-Solvent ... 300 parts by weight (propylene glycol monomethyl ether acetate)

For comparison, a (styrene)-(methacrylic acid)-(benzyl methacrylate) copolymer was prepared by radical polymerization instead of the alicyclic compound-containing resin described above, and this copolymer was used. In the same manner as in Example 1, a photosensitive resin composition (Comparative Example 1) was prepared.

Next, the above-described photosensitive resin composition (Example 1, Comparative Example 1) was spin-coated on a glass substrate and dried (dry thickness: 5.0 μm). The coating film was irradiated with ultraviolet rays through a photomask having the pattern, developed using a developer (aqueous potassium hydroxide solution), and baked (post-baked) to form a pattern.
By changing the amount of exposure, the residual film ratio of the pattern (the ratio of the pattern thickness to the coating film thickness) was measured. The results are shown in FIG. As shown in FIG. 1, Example 1 was higher in sensitivity and higher in residual film ratio than Comparative Example 1.

Example 2 First, as a resin containing an alicyclic compound, (methyl methacrylate)-(methacrylic acid)-
(Methyl adamantyl methacrylate) copolymer was prepared by radical polymerization.

Next, using this alicyclic compound-containing resin,
A photosensitive resin composition (Example 2) having the following composition was prepared. Composition of photosensitive resin composition (Example 2) Photopolymerization initiator: 10 parts by weight (Irgacure 369 manufactured by Ciba Geigy) Monomer: 30 parts by weight (dipentaerythritol hexaacrylate) Epoxy resin: 20 parts by weight ( Epicoat 180S70 manufactured by Mitsubishi Yuka Shell Co., Ltd.)-Alicyclic compound-containing resin: 50 parts by weight-Solvent: 300 parts by weight (propylene glycol monomethyl ether acetate)

For comparison, in place of the alicyclic compound-containing resin, a (methyl methacrylate)-(methacrylic acid)-(styrene) copolymer was prepared by radical polymerization, and this copolymer was used. In the same manner as in Example 2, a photosensitive resin composition (Comparative Example 2) was prepared.

Next, the above-mentioned photosensitive resin composition (Example 2, Comparative Example 2) was spin-coated on a glass substrate and dried (dry thickness: 5.0 μm). The coating film was irradiated with ultraviolet rays (exposure amount: 50 mJ) through a photomask having the pattern, and developed using a developing solution (aqueous potassium hydroxide solution) to form a pattern. As a result of measuring the residual film ratio of this pattern, it was 95% in Example 2 and 80% in Comparative Example 2.

Thereafter, post-baking (2
(30 ° C., 30 minutes), and the cross-sectional shape was observed. As a result, in Example 2, the pattern thickness was almost uniform (about 4.75).
μm), and no discoloration occurred in the pattern. However, in Comparative Example 2, a height of about 0.15 μ
m was observed, and the pattern was yellowed.

[0047]

As described in detail above, according to the present invention, a photosensitive resin composition is obtained by using an alicyclic compound-containing resin obtained by polymerizing a monomer containing at least a vinyl group and / or an isopropenyl group. Coloring is prevented, whereby the energy loss of the exposure ultraviolet light is extremely small and the sensitivity is improved. Further, the pattern is prevented from being colored due to discoloration even by heating in post-baking after exposure and development. Furthermore, the monomer contained in the photosensitive resin composition is a polyfunctional acrylate monomer, and a vinyl group or an isopropenyl group constituting the alicyclic compound-containing resin has a carboxyl group on one of double bond carbons. In addition, the film thickness is reduced uniformly by heating in post-baking after exposure and development, and a uniform pattern can be formed with a thickness with almost no bulge at the peripheral portion, and alkali development can be performed. Then, by performing pattern formation using the photosensitive resin composition of the present invention, a colored layer,
A display color filter having a desired pattern of a black matrix, a protective layer, a gap holding material, and the like with high accuracy can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram showing a relationship between an exposure amount and a residual film ratio in Example 1 and Comparative Example 1.

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Claims (3)

[Claims] 1. A resin comprising at least a photopolymerization initiator, a monomer having an unsaturated double bond, an epoxy resin, and an alicyclic compound-containing resin, wherein the alicyclic compound-containing resin has at least a vinyl group and / or an isopropenyl group. A photosensitive resin composition obtained by polymerizing a monomer containing: 2. The method according to claim 1, wherein the monomer is a polyfunctional acrylate monomer, and the vinyl group and the isopropenyl group are
The photosensitive resin composition according to claim 1, wherein one of the heavy bond carbons has a carboxyl group. 3. A support comprising: a support; and a pattern provided on the support, wherein the pattern is formed using the photosensitive resin composition according to claim 2. Color filter for display.