JPH1195425A - Photosensitive resin composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin compsn. excellent in sensitivity, developability and resolution by incorporating a resin binder having ethylenically unsatd. double bonds and carboxyl groups, an azido compd. and a photopolymn. initiator. SOLUTION: The photosensitive resin compsn. contains a resin binder having ethylenically unsatd. double bonds and carboxyl groups, an azide compd. and a photopolymn. initiator. The resin binder is typically a resin obtd. by allowing a compd. having an ethylenically unsatd. double bond and an epoxy group to react with part of the carboxyl groups of a polymer, a resin obtd. by half- esterifying a resin having a carboxylic acid anhydride as a functional group with a compd. having an ethylenically unsatd. double bond and a hydroxyl group or an acid anhydride modified epoxy acrylate resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel photosensitive resin composition, which can be suitably used for an image forming material such as a PS plate, a photoresist for IC, an etching or solder resist for printed circuit boards, and the like. In particular, the present invention relates to a photosensitive resin composition that can be suitably used for manufacturing a color filter used in manufacturing an optical color filter used in a color television, a liquid crystal display device, a solid-state imaging device, a camera, and the like. More specifically, the present invention relates to a photosensitive resin composition suitable for black matrix production, which has high light-shielding properties, high sensitivity, and excellent developability.

[0002]

2. Description of the Related Art As a photosensitive resin composition using an azide compound as a photosensitive agent, there are a photosensitive resin obtained by combining a low molecular bisazide compound and a resin capable of performing a crosslinking reaction with the compound, and a photosensitive resin obtained by incorporating an azide group into the resin. Are known. USP2852 as an example of the former
No. 379, US Pat. No. 2,408,583, etc., and a cyclized rubber, a novolak resin or a phenol resin such as polyvinyl phenol is known as a resin capable of undergoing a cross-linking reaction with a bisazide compound and used for a PS plate or a photoresist.

Further, as the latter photosensitive resin having an azide group, polyvinyl-p-azidobenzal resin, polyazidebenzoic acid resin, polyazidestyrene and the like are known.
It is applied to the S version. Azide compounds are rich in photoreactivity and have high stability to moisture and heat. Therefore, photosensitive resin compositions using various azides as described above have been developed. However, since the azide compound does not have an ionic structure and is poor in hydrophilicity, it is difficult to develop the azide-based photosensitive resin composition with an alkaline aqueous solution that is less harmful to the environment or the human body. Must be used for For this reason, there is a problem that various protective measures are required in use from the viewpoint of fire danger, environmental pollution, organic solvent poisoning of workers, and the like. In recent years, the standards for these have become increasingly strict and are becoming practically difficult to use.

On the other hand, in the production of a color filter for a liquid crystal display element, a production method using a photosensitive resin in which a pigment is dispersed has become mainstream because of high productivity and excellent fine workability. Also, a manufacturing method using a light-shielding photosensitive resin is being studied earnestly. The light-shielding photosensitive resin is a composition in which a pigment that is completely insoluble in a developing solution, which is insoluble in a large amount of alkali, is dispersed and compounded. Therefore, a photosensitive resin having high alkali developability and high sensitivity is required.

In the case of a photosensitive resin in which a bisazide compound and a phenol resin are combined, since the phenol resin has low alkali solubility, if a large amount of a light-shielding pigment is blended and dispersed, the development property is significantly reduced, and the resolution is extremely reduced and extreme In this case, there is a problem that the image cannot be developed. In addition, the photopolymerizable photosensitive resin in which a photopolymerization initiator and a monomer having an ethylenically unsaturated bond are combined with an acrylic resin having a carboxyl group has a poor curing ability because of being strongly inhibited by polymerization in the air due to oxygen in the air. There are problems such as low sensitivity and in extreme cases, no curing.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems and provides a novel photosensitive resin composition having high alkali developability. In particular, the present invention provides a photosensitive resin composition having high alkali developability and high sensitivity even when a large amount of a light-shielding pigment is dispersed and blended. Further, this photosensitive resin composition is a thin film, a pattern having a high light-shielding property can be easily formed by photolithography method,
In particular, it is suitable for producing a resin black matrix of a color filter and has excellent resolution, adhesion, and the like. Therefore, the use of the composition of the present invention enables production of a high-quality and highly reliable color filter.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that (a) a binder resin having an ethylenically unsaturated double bond and a carboxyl group, (b) an azide compound, and (c) light The inventors have found that a photosensitive resin composition containing a polymerization initiator can solve such an object, and have completed the invention. More specifically, the present invention can perform an extremely high curing reaction by combining an azide compound and a photopolymerization initiator in a specific resin, and is particularly effective when a light-shielding photosensitive resin is used. It was found to be high and completed the present invention.
Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive resin composition of the present invention uses, first, a resin combined with an azide compound, second, a combination of an azide compound and a photopolymerization initiator, and third, an effect when a light shielding material is blended. Is characterized by a high Although the reason for this is not clear, it is considered that the cross-linking reaction is efficiently caused by a complex reaction of a cross-linking reaction with an azide compound and a radical polymerization with a photopolymerization initiator. Hereinafter, each component will be described.

The binder resin having an ethylenically unsaturated double bond and a carboxyl group includes, for example, 1) a carboxyl group of a polymer having a carboxyl group as described below; A resin obtained by reacting a compound having a bond and an epoxy group; 2) a resin obtained by half-esterifying a resin having a carboxylic anhydride as a functional group with a compound having an ethylenically unsaturated double bond and a hydroxyl group; 3) an epoxy acrylate Typical examples thereof include acid anhydride-modified resins, but are not necessarily limited to the above examples.

1) Resin obtained by reacting a compound having an ethylenically unsaturated double bond and an epoxy group with a part of the carboxyl group of the polymer having a carboxyl group. As the polymer having a carboxyl group, for example, (meth) It has a carboxyl group such as acrylic acid, 2-succinoloyloxyethyl methacrylate, 2-maleynoloyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, and the like ( A homo- or copolymer of a (meth) acrylic monomer, or a (meth) acrylic monomer having a carboxyl group as described above, and styrene;
α-methylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonate, (meth) acrylic chloride Benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl Examples include a polymer obtained by copolymerizing a monomer such as acrylamide.

The compound having an ethylenically unsaturated double bond and an epoxy group may be a compound having an ethylenically unsaturated double bond and an epoxy group in one molecule, and specifically, glycidyl (meth) acrylate Aliphatic epoxy compounds such as glycidyl ether, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl ether (iso) crotonate, and (3,4-
Examples include epoxycyclohexyl) methyl (meth) acrylate and the following alicyclic epoxy compounds.

[0012]

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As a method for reacting a compound having an ethylenically unsaturated double bond and an epoxy group with a binder resin having a carboxyl group, a known method can be used. For example, the above-mentioned resin having a carboxyl group and a compound having an ethylenically unsaturated double bond and an epoxy group are converted to a tertiary amine such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride,
Carboxyl groups of the resin can be formed by reacting with a quaternary ammonium salt such as tetramethylammonium chloride, tetraethylammonium chloride, etc., pyridine, triphenylphosphine or the like as a catalyst at a reaction temperature of 50 to 150 ° C. for several to several tens of hours. The epoxy compound can be reacted to introduce an ethylenically unsaturated double bond into the binder resin. As an example of the resin described above, for example, (3, 4)
-Epoxycyclohexyl) methyl acrylate.

[0014]

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2) A resin obtained by half-esterifying a resin having a carboxylic acid anhydride as a functional group with a compound having an ethylenically unsaturated double bond and a hydroxyl group. Examples of the resin having a carboxylic acid anhydride as a functional group include maleic anhydride and the like. Carboxylic acid anhydride and styrene, methyl styrene, ethyl styrene, propyl styrene, isopropyl styrene, butyl styrene, sec-butyl styrene, tert-butyl styrene, dimethyl styrene,
Resins obtained by copolymerizing styrenes such as diethyl styrene, methoxy styrene, ethoxy styrene, propoxy styrene, butoxy styrene, vinyl biphenyl, benzyl styrene, chloro styrene, chloromethis styrene, fluoro styrene and bromo styrene are exemplified.

Compounds having an ethylenically unsaturated double bond and a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate,
Examples include hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-phenoxypropyl acrylate. The reaction of a resin having a carboxylic acid anhydride as a functional group and a compound having an ethylenically unsaturated double bond and a hydroxyl group can be performed by a known method. One equivalent of a compound having a double bond and a hydroxyl group is added to a tertiary amine such as triethylamine and benzylmethylamine, a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride and tetraethylammonium chloride, pyridine, triphenylphosphine and the like. Is reacted in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours to carry out half esterification, whereby a resin having an ethylenically unsaturated double bond and a carboxyl group can be obtained. As an example of the resin described above, for example,
A resin obtained by half-esterifying a styrene / maleic anhydride resin with hydroxyethyl acrylate is used.

[0017]

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3) Acid anhydride modified resin of epoxy acrylate resin Epoxy acrylate resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, (o, m, p-) novolak type epoxy resin, Unsaturated monocarboxylic acids such as phenol novolak epoxy resin, halogen-substituted novolak epoxy resin, and naphthol-modified novolak epoxy resin as unsaturated monocarboxylic acids, acrylic acid, methacrylic acid, 2-succinoloyloxyethyl methacrylate, 2-maleinoyl methacrylate Oxyethyl, methacrylic acid 2-
Those to which phthaloyloxyethyl, 2-hexahydrophthaloyloxyethyl methacrylate and the like are added are exemplified.

Examples of the acid anhydride that modifies the epoxy acrylate resin include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, and trimellitic anhydride. And benzophenonetetracarboxylic dianhydride. Known techniques can be used for modifying the epoxy acrylate resin with an acid anhydride. As an example of the resin described above, for example,
A modified resin of tetrahydrophthalic anhydride of novolak epoxy acrylate as shown below is exemplified.

[0020]

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In addition to the above examples, for example, a resin having a hydroxyl group and a carboxyl group, such as a terpolymer of methacrylic acid / methyl methacrylate / 2-hydroxyethyl methacrylate, may be substituted with (meth) acrylic acid chloride or cinnamon Resins to which compounds such as acid chloride and (meth) allyl chloride are added can also be used.

The weight average molecular weight of these binder resins measured by GPC (gel permeation chromatography) is usually 1,000 to 500,000.
If the weight average molecular weight is less than 1,000, it is difficult to obtain a uniform coating film, and if it exceeds 500,000, developability tends to decrease. The preferred content range of the carboxyl group is 5 to 250 in terms of acid value. If the acid value is less than 5, it becomes insoluble in an alkali developer and
If it exceeds, the sensitivity may decrease.

As the above-mentioned resins having a carboxyl group and an ethylenically unsaturated double bond, from the viewpoint of developability, some of the carboxyl groups of the polymer having a carboxyl group have an ethylenically unsaturated double bond and an epoxy resin. A resin obtained by reacting a compound having a group in the same molecule is preferable. As a particularly preferred resin, a polymer having a carboxyl group is a (meth) acrylic copolymer containing at least (meth) acrylic acid as a constituent monomer, and more preferably, an ethylenically unsaturated double bond is a (meth) acryloyl group. It is a resin that is a double bond inside. Further, a resin in which a (meth) acryloyl group is preferably introduced by reacting the (meth) acrylic copolymer with an alicyclic epoxy compound having a (meth) acryloyl group is preferred.

In this specification, “(meth) acryl-”, “(meth) acrylate” and the like mean “acryl- or methacryl-”, “acrylate or methacrylate” and the like. “Meth) acrylic acid” means “acrylic acid or methacrylic acid”.

Next, the azide compound in the present invention is a compound having at least one azide group (—N 3) in a molecule. For example, polyazide vinyl benzoate,
Examples of polymers having an azide group as a photosensitive group, such as polyazide styrene, polyvinyl azido benzal acetal, polyvinyl azido naphthyl acetal, and azidobenzaldehyde phenol resin, and low molecular monomer type azide compounds having an azide group as shown below. be able to.

[0026]

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[0027]

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Among these azide compounds, an azide group-containing compound having two or more azide groups in the same molecule and having a molecular weight of 1,000 or less is preferable because of its excellent developability and curability, and is particularly preferable. Azide compounds of 1000 or less and represented by the following formula are particularly preferred.

[0029]

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The photopolymerization initiator in the present invention is not particularly limited as long as it is a compound capable of polymerizing an ethylenically unsaturated double bond by actinic rays.
Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4, Halomethylated triazine derivatives such as 6-bis (trichloromethyl) -s-triazine, 2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [ β- (2'-benzofuryl) vinyl]-
1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 Halomethylated oxadiazole derivatives such as furyl-1,3,4-oxadiazole, 2- (2 ′
-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2-
(2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl)-
Imidazole derivatives such as 4,5-diphenylimidazole dimer and (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and benzoins such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether Alkyl ethers, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as 1-chloroanthraquinone, benzuanthrone derivatives, benzophenone,
Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-
Benzophenone derivatives such as carboxybenzophenone,
2,2-dimethoxy-2-phenylacetophenone,
2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- ( p-dodecylphenyl) ketone, 2-
Acetophenone derivatives such as methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, thioxanthone, 2-ethylthioxanthone,
Thioxanthone derivatives such as 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-diisopropylthioxanthone, ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like Benzoic acid ester derivatives, acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine, phenazine derivatives such as 9,10-dimethylbenzphenazine, di-cyclopentadienyl-Ti
-Di-chloride, di-cyclopentadienyl-Ti-
Bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-
Yl, di-cyclopentadienyl-Ti-bis-2,
3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-cyclopentadienyl-
Ti-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophenyl-1-yl, di-methylcyclopentadienyl-Ti
-Bis-2,3,4,5,6-pentafluorophenyl-
1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro-3-
And titanocene derivatives such as (pyr-1-yl) -phenyl-1-yl. Among these photopolymerization initiators, a composite initiation system containing at least a biimidazole derivative is preferable because of high polymerization efficiency.

Sensitizing dyes suitable for use as a complex initiation system include, for example, coumarin compounds having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and JP-A-63-221110. 3-ketocoumarin compounds described in Japanese Patent Application Laid-Open Publication No. Hei 4-2219
No. 58, Japanese Patent Application Laid-Open No. 4-219756, xanthene dyes, Japanese Patent Application Laid-Open No. 6-19240, pyromethene dyes, Japanese Patent Application Laid-Open Nos.
(P-dialkylaminobenzylidene) ketones and styryl dyes described in JP-A-4-155292, JP-A-56-166154 and JP-A-59-56403; julolidyl described in Japanese Patent Application No. 5-83588. Sensitizing dyes having a group; and diaminobenzene compounds described in Japanese Patent Application No. 7-10109.

Among these sensitizing dyes, particularly preferred are amino group-containing sensitizing dyes, and more specifically, compounds having an amino group and a phenyl group in the same molecule. Specific examples include, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'- Benzophenone-based compounds such as diaminobenzophenone and 3,4-diaminobenzophenone;
-(P-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole,
2,5-bis (p-diethylaminophenyl) 1,3
4-oxazole, 2- (p-dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-
(Diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-
P- such as diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) pyrimidine and 2- (p-diethylaminophenyl) pyrimidine Examples thereof include compounds containing a dialkylaminophenyl group.

Further, the photosensitive resin composition of the present invention can be particularly suitably used as a photosensitive resin composition having a light-shielding property by adding a black material. The preferred black color material will be described below. As the black color material, a single color material or a plurality of black color materials, or a black color material obtained by mixing red, green, blue and the like can be used. Further, these coloring materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic or organic pigments, the average particle size is 1μ
Hereafter, it is preferable to disperse the particles to 0.5 μm or less.

Specific examples of color materials that can be mixed and used include Victoria Pure Blue (42595) and Auramine O (4
1000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6 GCP (45160), Rhodamine B (45170), Safranin OK 70: 100
(50240), Erioglaucine X (42080),
No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7
B4401 (15850), Fast Gen Blue TG
RL (74160), Lionol Blue SM (261
50), Lionol Blue ES (Pigment Blue 1)
5: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), and the like (the numbers in parentheses indicate the color index (CI)). Do).

Further, regarding other pigments which can be used in combination, C.I. I. The number is, for example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 11
7, 125, 137, 138, 147, 148, 15
3,154,166, C.I. I. Oren Pigment 36,4
3, 51, 55, 59, 61, C.I. I. Red pigment 9,9
7, 122, 123, 149, 168, 177, 18
0,192,215,216,217,220,22
3,224,226,227,228,240, C.I.
I. Violet pigments 19, 23, 29, 30, 37,
40, 50, C.I. I. Blue pigment 15, 15: 1, 15:
4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I.
Brown pigments 23, 25, 26 and the like can be mentioned.

The black coloring material that can be used alone includes
Carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black,
Cyanine black, titanium black and the like. Among these, carbon black is preferred from the viewpoint of light blocking ratio and image characteristics. Examples of the carbon black include the following carbon blacks.

Manufactured by Mitsubishi Chemical Corporation: MA7, MA8, MA1
1, MA100, MA220, MA230, # 52, #
50, # 47, # 45, # 2700, # 2650, # 2
200, # 1000, # 990, # 900 manufactured by Degussa: Printex 95, Printex 9
0, Printex85, Printex75, Pri
ntex55, Printex45, Printex4
0, Printex30, Printex3, Prin
texA, PrintexG, SpecialBlac
k550, SpecialBlack350, Spec
ialBlack250, SpecialBlack1
00

Monarch 460, manufactured by Cabot Corporation
Monarch 430, Monarch 280, Mon
arch120, Monarch800, Monarc
h4630, REGAL99, REGAL99R, RE
GAL415, REGAL415R, REGAL25
0, REGAL250R, REGAL330, BRAC
K PEARLS480, PEARLS130 manufactured by Colombian Carbon: RAVE11, RAV
EN15, RAVE30, RAVE35, RAVE
N40, RAVEN410, RAVEN420, RAV
EN450, RAVEN500, RAVE780, R
AVEN850, RAVE890H, RAVE10
00, RAVEN1020, RAVEN1040
The above carbon black may be used in combination with other black or colored inorganic or organic pigments.

The composition of the present invention is usually used in a state where the above-mentioned essential components such as a binder resin, an azide compound and a photopolymerization initiator are dissolved in an organic solvent. Although there is no particular limitation on the organic solvent, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, Valsol # 2, Apco #
18 solvent, diisobutylene, amyl acetate,
Butyl butyrate, apco thinner, butyl ether,
Diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal
solvent No. 1 and No. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec,
t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl ketone,
Methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethyl pentanol ,
Methyl amyl ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve,
Ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene Propylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 3-
Ethyl methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether , 3
Specific examples thereof include organic solvents such as -methyl-3-methoxybutanol, tripropylene glycol methyl ether, and 3-methyl-3-methoxybutyl acetate.

The solvent is capable of dissolving or dispersing each component, and preferably has a boiling point in the range of 100 to 200 ° C. More preferably, 120 to 17
It has a boiling point of 0 ° C. These solvents can be used alone or as a mixture.

The photosensitive composition of the present invention comprises (a) 100 parts by weight of a binder resin and (b) an azide compound in an amount of 0.0
The content is preferably in the range of 5 to 200 parts by weight from the viewpoint of developability and sensitivity, and the photopolymerization initiator is used in the range of 0.05 to 50 parts by weight. When a black coloring material is compounded, it is preferably added in the range of 30 to 70 wt%, more preferably in the range of 35 to 65 wt%, based on the total solid content.

In the present invention, in addition to these essential components, pigment dispersants, adhesion improvers, coatability improvers, development improvers and the like can be suitably added. In particular, when a black pigment is blended, it is desirable to add a pigment dispersant. Since the photosensitive resin composition of the present invention contains a black coloring material, it is useful as a light-shielding photosensitive resin composition, particularly for forming a black matrix of a color filter. The production method in this case will be described. In the present invention, usually black color material is previously paint conditioner, sand grinder, ball mill, roll mill, stone mill,
The dispersion treatment is preferably performed using a jet mill, a homogenizer, or the like. Since the black color material is finely divided by the dispersion treatment, the light-shielding ability of the resist and the coating characteristics are improved.

In the dispersion treatment, the treatment is preferably carried out in a system further using a black colorant and a solvent, a binder resin having a dispersing function, or a dispersant. In particular, it is preferable to use a polymer dispersant since the dispersion stability over time is excellent. When dispersing with a sand grinder, 0.1
Glass beads or zirconia beads having a diameter of from 1 to several millimeters are preferably used. Dispersing conditions are usually such that the temperature is 0
C. to 100.degree. C., preferably from room temperature to 80.degree. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (black color material, solvent, dispersant), the size of the sand grinder, and the like.

Next, the black ink obtained by the above dispersion treatment is mixed with a binder resin, an azide compound and a photopolymerization initiator and mixed to form a uniform solution. Since fine dust is often mixed with the photosensitive solution in the manufacturing process, it is desirable to filter the obtained resist photosensitive solution with a filter or the like. Subsequently, a method for producing a color filter using the light-shielding photosensitive resin composition of the present invention will be described.

First, the light-shielding photosensitive resin composition of the present invention is applied on a transparent substrate by a coating device such as a spinner, a wire bar, a flow coater, a die coater, a roll coater, a spray and the like, and dried. A photomask is placed on the top, and image exposure, development,
If necessary, a black matrix image for light shielding is formed by heat curing or light curing, and the same operation is further repeated for each of the three colored photosensitive compositions of red, green and blue to form a color filter image.

When pixels of a color filter are formed by using the photosensitive resin composition of the present invention, exposure is performed without providing an oxygen barrier layer of polyvinyl alcohol or the like because of extremely high sensitivity and high resolution. It is possible to form an image by developing. The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited.For example, polyester such as polyethylene terephthalate or polypropylene, polyolefin such as polyethylene, polycarbonate, polymethyl methacrylate, Examples include a thermoplastic plastic sheet of polysulfone, a thermosetting plastic sheet such as an epoxy resin, a polyester resin, and a poly (meth) acrylic resin, and various glass plates. Particularly, a glass plate and a heat-resistant plastic are preferably used from the viewpoint of heat resistance.

Such a transparent substrate is previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as a silane coupling agent and a urethane polymer in order to improve physical properties such as surface adhesiveness. You can also. The coating method is not particularly limited, but the thickness of the resin black matrix after coating and drying is 0.1 to 2 μm, preferably 0.1 to 1.5 μm, more preferably 0.1 to 1 μm.
Should be within the range.

For drying, a hot plate, an IR oven, a convection oven, or the like can be used.
Preferred drying conditions are 40 to 150 ° C., and the drying time is 10 seconds to 60 minutes. Light sources used for exposure include, for example, xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and the like, and argon ion lasers, YAG lasers, excimer lasers, Examples include a laser light source such as a nitrogen laser. When only the wavelength of the specific irradiation light is used, an optical filter can be used.

The development process is not particularly limited as long as it is a solvent capable of dissolving the unexposed resist film.
For example, organic solvents such as acetone, methylene chloride, trichlene, and cyclohexanone are not preferable because they have environmental pollution, harm to humans, and danger of fire. The use of an alkali developing solution is preferred. Examples of such an alkaline developer include sodium carbonate,
An aqueous solution containing an inorganic alkali agent such as potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide or the like, or an organic alkali agent such as diethanolamine, triethanolamine or tetraalkylammonium hydroxide salt can be used. Alkaline developers include
If necessary, a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxylic acid group, or the like can be contained. In particular, a surfactant is preferably added because many of them have an effect of improving the developing property, the resolution and the background stain.

For example, as a surfactant for a developer,
Examples thereof include an anionic surfactant having a sodium naphthalene sulfonate group and a sodium benzene sulfonate group, a nonionic surfactant having a polyalkyleneoxy group, and a cationic surfactant having a tetraalkylammonium group. The developing method is not particularly limited, but is usually 10 to 50 ° C., preferably 15 to 50 ° C.
It is carried out at a development temperature of up to 45 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development.

[0051]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

Synthesis Example 1 20 g of a styrene-acrylic acid resin having an acid value of 200 and a weight average molecular weight of 5,000, 0.2 of p-methoxyphenol
g, dodecyltrimethylammonium chloride 0.2
g, propylene glycol monomethyl ether acetate (40 g) was charged into the flask, and (3,4-epoxycyclohexyl) methyl acrylate (7.6 g) was added dropwise.
The reaction was carried out at a temperature of 0 ° C. for 30 hours. The reaction solution was reprecipitated in water and dried to obtain a resin. As a result of neutralization titration with KOH, the acid value of the resin was 80 mgKOH / g.

Preparation of Carbon Black Dispersion Ink Carbon black MA-220 (manufactured by Mitsubishi Chemical Corporation) 5
0 parts by weight, BYK-182 (a polymer dispersant manufactured by BYK-Chemie) was added in an amount of 5 parts by weight in terms of solid content, and propylene glycol monomethyl ether acetate was further added to adjust the dispersion so that the solid content concentration became 50 wt%. 50 g of the dispersion was collected by weight, and the mixture was sufficiently stirred by a stirrer to perform premixing. Next, 25 ~ 4 by paint shaker
Dispersion treatment was performed at 5 ° C. for 6 hours. 0.5 beads
Using zirconia beads of mmφ, the same weight as the dispersion was added. After the dispersion, the beads and the dispersion were separated by a filter to obtain a dispersion ink.

Example 1 Using the above-described carbon black-dispersed ink, each component was added so as to have the following compounding ratio as a solid content, and stirred and dissolved by a stirrer to prepare a light-shielding photosensitive resin liquid. Binder resin (Synthesis example-1) 25 g Azide compound 4,4'-diazidostilbene-2,2'-bis- [N, N-di (2-ethoxyethyl) sulfonamide] 15 g Photopolymerization initiator 2,2 ' -Bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole 3g 4,4'-bis (diethylamino) benzophenone 2g Pigment carbon black (MA-220) 50g Solvent Propylene glycol monomethyl ether acetate 300 g Polymer dispersant BYK-182 (manufactured by BYK-Chemie) 5 g Surfactant FC-430 (manufactured by Sumitomo 3M) 100 ppm

Using the obtained light-shielding photosensitive resin liquid, a resist pattern was formed as follows and evaluated. A light-shielding photosensitive resin liquid is applied to a glass substrate (7059,
Corning Co., Ltd.), 80 ℃ on hot plate,
Dry for 1 minute. The thickness of the dried resist was measured by a stylus-type film thickness meter (α-step, manufactured by Tencor Corporation) and found to be 1 μm. Next, this sample was passed through a mask with a high-pressure mercury lamp at 300 mj, 500 mj, and 3000 mj.
Image exposure was performed at various exposure doses. Temperature 25 ° C, concentration 0.05
Then, the resist pattern was obtained by immersion and development in an aqueous solution of potassium hydroxide. Next, the sample was image-exposed through a mask with a high-pressure mercury lamp while changing the exposure amount.
The resist pattern was obtained by immersion development in a 05% aqueous potassium hydroxide solution.

Developability Those which can form an image within a development time of 1 minute have good developability.
Those requiring more than one minute development time were regarded as poor developability.

Sensitivity Sensitivity was defined as an exposure amount (appropriate exposure amount) capable of forming a 50 μm pattern. Those which can form an image with an exposure amount of 500 mj or less were determined as having good sensitivity, and those requiring an exposure amount of 3000 mj or more were determined as having poor sensitivity.

Resolution The resolution was evaluated using the minimum resist pattern size capable of forming an image. In addition, those which can reproduce a resist pattern of 15 μ or less were defined as having good resolution.

Light Shielding Property The optical density (OD) of the solid portion after development was measured with a Macbeth reflection densitometer TR927 (manufactured by Kolmorgun). The OD value is a numerical value indicating the light-shielding ability, and the larger the numerical value, the higher the light-shielding property. The results are shown in Table 1.

Example 2 Example 2 was repeated except that the azide compound of Example 1 was changed to 4,4'-diazidochalcone-2,2'-bis- [N, N-di (2-ethoxyethyl) sulfonamide]. A light-shielding photosensitive resin solution was prepared and evaluated in the same manner as in Example-1. The results are shown in Table 1.

Comparative Example 1 The binder resin of Example 1 was replaced with a weight average molecular weight of 5,000.
A light-shielding photosensitive resin solution was prepared and evaluated in the same manner as in Example 1, except that m-cresol novolak resin was used. The results are shown in Table 1.

Comparative Example 2 A light-shielding photosensitive resin solution was prepared in the following mixing ratio, and
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. Binder resin (Synthesis example-1) 25 g Acrylic monomer Dipentaerythritol hexaacrylate 15 g Photopolymerization initiator Benzophenone 3 g Michler's ketone 2 g Pigment carbon black (MA-220) 50 g Solvent Propylene glycol monomethyl ether acetate 300 g Polymer dispersant BYK-182 (BIC Chemie) 5g Surfactant FC-430 (Sumitomo 3M) 100ppm

A black matrix was formed on a glass substrate using the light-shielding photosensitive resin liquids of Examples 1 and 2, and then red, green and blue pixels were formed, whereby excellent light-shielding properties were obtained. A color filter having a black matrix was manufactured.

[0064]

[Table 1]

[0065]

The photosensitive resin composition of the present invention is excellent in sensitivity, developability and resolution especially as a high light-shielding photosensitive resin containing a large amount of a black coloring material. Therefore, a resin black matrix of a color filter used for a liquid crystal display element can be formed with high precision. Since the color filter using the resin black matrix of the present invention is excellent in accuracy, flatness and durability, the display quality of the liquid crystal element can be improved more than before. Further, since the manufacturing process and the color filter itself do not contain harmful substances, the danger to the human body is reduced and the environmental safety is improved.

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Claims (9)

[Claims] 1. A photosensitive resin composition comprising (a) a binder resin having an ethylenically unsaturated double bond and a carboxyl group, (b) an azide compound and (c) a photopolymerization initiator. . 2. The photosensitive resin composition according to claim 1, further comprising (d) a black coloring material. 3. The photosensitive resin composition according to claim 1, wherein the binder resin is a (meth) acrylic resin containing at least (meth) acrylic acid as a constituent monomer. 4. The photosensitive resin composition according to claim 1, wherein (a) the ethylenically unsaturated double bond is a double bond in a (meth) acryloyl group. 5. The resin according to claim 1, wherein the binder resin is a resin obtained by reacting a polymer having a carboxyl group with a compound having an ethylenically unsaturated double bond and an epoxy group in the same molecule. The photosensitive resin compositions of 1 to 4. 6. The photosensitive resin composition according to claim 5, wherein the epoxy group is an alicyclic epoxy group. (B) the azide compound has a molecular weight of 1000
The photosensitive resin composition according to any one of claims 1 to 6, wherein the compound is a compound having two or more azide groups in the same molecule. 8. A color filter comprising a transparent substrate and a black matrix formed of the photosensitive resin composition according to claim 1. Description: 9. An optical density (O) of a black matrix.
9. The color filter according to claim 8, wherein D) is 3.0 / μ or more.