JP2007010796A - Pigment-dispersed radiation-sensitive resin composition and colored pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment-dispersed radiation-sensitive resin composition which exhibits high durability, particularly high moisture resistance after photocuring, and a colored pattern forming method. <P>SOLUTION: The pigment-dispersed radiation-sensitive resin composition comprises at least a photopolymerizable compound, a photopolymerization initiator, a pigment and a solvent, and when the pigment-dispersed radiation-sensitive resin composition is formed into a coating film and photocured, a surface of the cured coating film has such hydrophobicity as a contact angle to water droplets of ≥75°. A photopolymerizable colored composition layer formed of the pigment-dispersed radiation-sensitive resin composition is selectively irradiated with light having a predetermined wavelength and is developed, whereby a colored pattern excellent in durability is formed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pigment-dispersed radiation-sensitive resin composition having excellent durability after photocuring and a method for forming a colored pattern. More specifically, the present invention relates to a pigment-dispersed radiation-sensitive resin composition excellent in durability after photocuring and a method for forming a colored pattern, which is suitable for manufacturing a color filter such as a liquid crystal display.

  In a color filter provided in various multicolor displays such as a color liquid crystal display, a black matrix is provided at a boundary portion between colored layers such as R, G, and B in order to enhance display contrast and color development effect. Conventionally, this black matrix has been mainly formed by photoetching a chromium thin film. A black matrix made of a chromium thin film has high dimensional accuracy and high reliability. However, in order to form a chromium thin film, a vacuum film forming process such as vapor deposition or sputtering is necessary, and the size of the apparatus increases with the increase in size of the substrate, resulting in an increase in manufacturing cost. Further, with the recent increase in backlight strength, particularly in TFT liquid crystal displays, there has been a problem of a decrease in display contrast due to internal reflection of a chromium thin film.

  Therefore, in recent years, as described in Patent Document 1, a photopolymerizable composition containing a compound having an unsaturated double bond capable of addition polymerization, a black pigment, and a photopolymerization initiator is applied onto a substrate. It has been dried to form a photopolymerizable composition layer, and a desired black matrix pattern has been formed by photolithography. When a photopolymerizable composition is used, a black matrix pattern can be formed under atmospheric pressure, so that manufacturing costs can be reduced and internal reflection is less likely to occur.

Japanese Patent Laid-Open No. 11-84125

  By the way, in various multicolor displays such as a color liquid crystal display, the black matrix and the color filter are formed on a substrate, and then a display material such as liquid crystal is enclosed between the substrate and the counter substrate to form a display panel. In the formed display panel, since the color filter is formed on the inner surface of the substrate, if the adhesion of the black matrix and the color filter to the substrate deteriorates, the display material such as liquid crystal leaks, and the display panel is defective. Become.

  Therefore, a manufacturer of a multicolor display body manufactures a multicolor display panel, and then leaves the obtained panel under severe conditions of a temperature of 120 ° C., a humidity of 100%, and an atmospheric pressure of 2 atm to display a liquid crystal display or the like. The durability of the product is confirmed by inspecting for material leakage.

  As a result of the severe durability test as described above, the present multicolor display has a result that the durability is insufficient, and an improvement in durability is strongly demanded.

  Accordingly, an object of the present invention is to provide a pigment-dispersed radiation-sensitive resin composition having high durability after photocuring and high adhesion, a method for forming a colored pattern, and a color filter.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies, experiments, and studies, and have obtained the following knowledge.

  The present inventors have investigated the cause of deterioration in the durability test, and since the color matrix exhibits hydrophilicity in order to ensure developability, the humidity test is performed under severe humidity conditions of 100% in the durability test. It was confirmed that it was in swelling. This swelling deteriorates the adhesion between the two panels and causes liquid leakage.

  Accordingly, the present inventors have made various adjustments to the composition of the pigment-dispersed radiation-sensitive resin composition, which is a material for forming a color matrix (colored pattern), and the hydrophobicity of the cured coating film obtained by photocuring the coating film. The degree of was set to several stages, and each was subjected to an endurance test. The degree of hydrophobicity in this case was defined by the contact angle of water droplets formed by dropping pure water on the surface of the cured coating film to the coating film surface.

  As a result, it was first confirmed that the degree of hydrophobicity of the cured coating was strongly related to the strength of durability. It was also confirmed that when the contact angle of water droplets was less than 75 degrees, the coating film could not avoid swelling under a high humidity environment. If a pigment-dispersed radiation-sensitive resin composition whose composition is adjusted so that the contact angle of the cured coating is 75 degrees or more, the obtained color matrix can exhibit sufficient adhesion to the panel over time. There was found.

  The means for adjusting the hydrophobicity of the above-mentioned cured coating film need not be particularly limited. Any of the components of the pigment-dispersed radiation-sensitive resin composition may be made more hydrophobic, or a hydrophobic material may be newly added. In the confirmation test described above, the hydrophobicity of the cured coating film was increased by newly adding a hydrophobic resin.

  The present invention has been made based on such knowledge. That is, the pigment-dispersed radiation-sensitive resin composition according to the present invention contains at least a photopolymerizable compound, a photopolymerization initiator, a pigment, and a solvent, and is cured after being coated and photocured. The coating film surface is characterized by having hydrophobicity with a water droplet contact angle of 75 degrees or more.

  The hydrophobicity can be adjusted by compositionally containing a hydrophobic resin.

  As the hydrophobic resin, a styrene-acrylic acid copolymer is suitable. Further, the content of the hydrophobic resin is desirably 5 parts by weight or more and less than 50 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. If the content is less than 5 parts by weight, the durability improving effect does not appear. On the other hand, if the content is 50 parts by weight or more, a residue is generated during development of the color matrix.

  The photopolymerizable compound is conventionally used and is hydrophilic. In the present invention, a photopolymerizable compound capable of obtaining sufficient photocurability even when the optical density is high is desirably used. As such a photopolymerizable compound, the following chemical formula (1)

（式中、ｎは、１〜２０の整数であり、Ｙは、ジカルボン酸無水物の酸無水物基を除いた残基であり、Ｚは、テトラカルボン酸二無水物の酸無水物基を除いた残基であり、Ｘは、下記化学式（２）

(In the formula, n is an integer of 1 to 20, Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, and Z is the acid anhydride group of tetracarboxylic dianhydride. X is a residue removed, and X is the following chemical formula (2)

で表される基であり、Ｒ₁、Ｒ₂は、Ｈ、ＣＨ₃または

Wherein R ₁ and R ₂ are H, CH ₃ or

であり、Ｒ₃は、ＨまたはＣＨ₃である。）
で表される化合物が、好適である。

And R ₃ is H or CH ₃ . )
Are preferred.

  As the pigment, pigments of various colors are used depending on the purpose, but a black pigment is used for a normal black matrix. As such a black pigment, carbon black or titanium black is suitable.

  The method for forming a colored pattern using the pigment-dispersed radiation-sensitive resin composition according to the present invention comprises forming a photopolymerizable colored composition layer comprising a pigment-dispersed radiation-sensitive resin composition having the above composition on a substrate, The composition layer is selectively irradiated with light having a predetermined wavelength and developed to form a colored pattern.

  The pigment-dispersed radiation-sensitive resin composition according to the present invention is much more promising by setting the surface hydrophobicity of the cured coating film to a water droplet contact angle of 75 degrees or more. Since the moisture resistance and durability exceeding can be obtained, it can be suitably used as a photosensitive colored resin composition for forming a color matrix in which a display substance such as liquid crystal is contained. By using the pigment-dispersed radiation-sensitive resin composition of the present invention as a resin composition for creating a color matrix of a multicolor display panel such as a color liquid crystal display device, leakage of display substances such as liquid crystal is possible even under severe conditions. A multicolor display that does not occur can be obtained.

Hereinafter, embodiments of the present invention will be described in detail.
As described above, the pigment-dispersed radiation-sensitive resin composition according to the present invention contains at least a photopolymerizable compound, a photopolymerization initiator, a pigment, and a solvent. The subsequent cured coating film surface has a hydrophobic property with a water droplet contact angle of 75 ° or more. The hydrophobicity of the cured coating film may be improved by adding a polymer binder.

  The polymer binder can be added to adjust the contact angle, and is preferably a hydrophobic resin. Examples of the hydrophobic resin include a copolymer of a hydrophilic monomer having an ethylenically unsaturated double bond capable of addition polymerization and a hydrophobic monomer having an ethylenically unsaturated double bond capable of addition polymerization. The content of the hydrophobic monomer unit is 65 to 95 mol%, preferably 75 to 90 mol%, in terms of a mole fraction with respect to the total number of moles of the constituent monomers of the copolymer. The hydrophobic resin has alkali solubility. Here, the hydrophilic monomer is a monomer having an OH group and a COOH group, and the hydrophobic monomer is a monomer having no OH group and a COOH group.

  The hydrophobic resin preferably has a polystyrene-equivalent weight average molecular weight of 5,000 to 50,000, more preferably 6,000 to 15,000. By setting it in this range, the hardness of the film can be improved and the remaining film rate can be increased.

  Examples of the hydrophobic monomer include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o- Aromatic vinyl compounds such as vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, indene;

  Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl Methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl Acrylate, 2-methoxyethyl methacrylate, 2-phenol Xylethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol Unsaturated carboxylic acid esters such as methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate;

  2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl Unsaturated alkylaminoalkyl esters such as methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate;

  Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate;

  Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;

  Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether;

  Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;

  Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide;

  Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;

  And aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

  These hydrophobic monomers may be used alone or in admixture of two or more.

  Examples of the hydrophilic monomer include an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated polycarboxylic acid such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated polycarboxylic acid. Is mentioned.

  Here, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid.

  Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.

  The unsaturated polyvalent carboxylic acid may be its acid anhydride, and specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester such as succinic acid mono (2-acryloyloxyethyl) or succinic acid mono (2-methacryloyloxy). Ethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of the dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. These hydrophilic monomers may be used alone or in admixture of two or more.

  The content of the hydrophobic resin is desirably 5 parts by weight or more and less than 50 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. If the content is less than 5 parts by weight, the durability improving effect does not appear. On the other hand, if the content is 50 parts by weight or more, a residue is generated during development of the color matrix.

  As the photopolymerizable compound, a conventional photopolymerizable compound that can be developed with water or an alkaline aqueous solution is used.

  Examples of the photopolymerizable compound include compounds having an ethylenically unsaturated double bond capable of addition polymerization.

  Here, the “compound having an ethylenically unsaturated double bond capable of addition polymerization” (hereinafter referred to as “ethylenic compound”) means that the photopolymerizable black composition is irradiated with light of a predetermined wavelength. , A compound having at least one ethylenically unsaturated double bond that undergoes addition polymerization and curing by the action of a photopolymerization initiator, the monomer having the ethylenically unsaturated double bond, the side chain, or the main chain It is a polymer having an ethylenically unsaturated double bond in the chain. The monomer is a differentiated concept relative to a so-called polymer substance, and is not limited to a “monomer” in a narrow sense, but includes a dimer, a trimer, and an oligomer.

  Examples of the monomer include unsaturated carboxylic acids, esters of aliphatic (poly) hydroxy compounds and unsaturated carboxylic acids, esters of aromatic (poly) hydroxy compounds and unsaturated carboxylic acids, and unsaturated carboxylic acids. , Unsaturated carboxylic acid amide, unsaturated carboxylic acid nitrile obtained by esterification reaction of polycarboxylic acid with polyhydric carboxylic acid and polyhydric hydroxy compound such as aliphatic (poly) hydroxy compound and aromatic (poly) hydroxy compound described above Etc.

  Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate, isobutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether acrylate, ethylene glycol monomethyl ether methacrylate, ethylene glycol mono Ethyl ether acrylate, ethylene glycol monoethyl ether methacrylate, glycerol acrylate, glycerol methacrylate, acrylic acid amide, methacrylic acid amide, acrylonitrile, methacrylonitrile, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, ethyl Glycol diacrylate, diethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol Dimethacrylate, Trimethylolethane triacrylate, Trimethylolethane trimethacrylate, Trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, Tetramethylolpropane tetraacrylate, Tetramethylolpropane tetramethacrylate, Pentaerythritol triacrylate, Penta Rithritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 1,6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, cardoepoxy diacrylate, cardoepoxy dimethacrylate, acrylates and methacrylates of these exemplary compounds are replaced with fumarate, maleate, crotonate, itaconate, acrylic acid, methacrylic acid, fumaric acid, maleic acid , Crotonic acid, itaconic acid, hydroquinone monoacrylate, hydroquinone monomer Tacrylate, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol diacrylate, pyrogallol triacrylate, condensate of acrylic acid with phthalic acid and diethylene glycol, condensate of acrylic acid with maleic acid and diethylene glycol, Useful condensates of methacrylic acid with terephthalic acid and pentaerythritol, condensates of acrylic acid with adipic acid and butanediol with glycerin, ethylene bisacrylamide, ethylene bismethacrylamide, allyl ester of diallyl phthalate, divinyl phthalate, etc. is there.

  Examples of the polymer having an ethylenically unsaturated double bond in the side chain or main chain include, for example, a polyester obtained by polycondensation reaction of an unsaturated divalent carboxylic acid and a dihydroxy compound, an unsaturated divalent carboxylic acid, Polyamide, itaconic acid, propylidene succinic acid obtained by polycondensation reaction with diamine, polyester obtained by polycondensation reaction of ethylidene malonic acid and dihydroxy compound, itaconic acid, propylidene succinic acid, ethylidene malonic acid and diamine Polyamide obtained by polycondensation reaction, phenol novolac type epoxy acrylate, phenol novolac type epoxy methacrylate, cresol novolac type epoxy acrylate, cresol novolac type epoxy methacrylate, bisphenol A type epoxy acrylate Bisphenol S-type epoxy acrylate, urethane acrylate oligomer, and urethane methacrylate oligomer. The epoxy (meth) acrylate resin may be further reacted with a polybasic acid anhydride. Polymers having a functional group having a reactive activity such as a hydroxy group or a halogenated alkyl group in the side chain, such as polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, and acrylic acid, methacrylic acid, fumaric acid Polymers obtained by polymer reaction with unsaturated carboxylic acids such as maleic acid, crotonic acid and itaconic acid can also be used. Among them, an acrylic ester or a methacrylic ester monomer can be particularly preferably used.

  Moreover, in this invention, the photopolymerizable compound shown by following General formula (1) which can improve an optical density and photocurability simultaneously is desirably used.

  However, in the said General formula (1), n is an integer of 1-20, Y is the residue remove | excluding the acid anhydride group of dicarboxylic anhydride, Z is acid anhydride of tetracarboxylic dianhydride. It is a residue excluding physical groups, and X is the following general formula (2)

で表される基であり、Ｒ₁、Ｒ₂は、Ｈ、ＣＨ₃または

Wherein R ₁ and R ₂ are H, CH ₃ or

であり、Ｒ₃は、ＨまたはＣＨ₃である。

And R ₃ is H or CH ₃ .

  Here, the “acid anhydride group” refers to a “—CO—O—CO— group”. Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyl Examples include tetrahydrophthalic anhydride and glutaric anhydride.

  Examples of tetracarboxylic dianhydrides include aromatic polycarboxylic anhydrides such as pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, and biphenyl ether tetracarboxylic dianhydride. Things.

  These photopolymerizable compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  The photopolymerizable compound represented by the general formula (1) can be obtained by the method described in JP-A No. 2001-354735. Since the photopolymerizable compound represented by the general formula (1) has substantially no dicarboxylic anhydride residue in the polymerization chain, it differs from a compound having a dicarboxylic anhydride residue in the polymerization chain, Even at the same solid content concentration, it is easy to control the viscosity of the solution, and it is possible to improve workability during coating, improve coating characteristics, and make the film thickness uniform.

  The photopolymerizable compound represented by the general formula (1) has at least two ethylenically unsaturated double bonds capable of addition polymerization in the compound, and the photopolymerizable black composition has a photopolymerization initiator. When irradiated with light of a predetermined wavelength to be activated, even if the optical density is high, it can be cured by addition polymerization by the action of a photopolymerization initiator. Conversely, when forming the black matrix pattern of a color filter such as a liquid crystal display, if the pigment-dispersed radiation sensitive resin composition of the present invention is used, the content of the black pigment is increased to increase the light shielding property. Can do. For this reason, a color filter having a high display contrast and a beautiful color of R, G, B can be manufactured.

  Examples of the photopolymerization initiator that can be used in the present invention include 2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole (hereinafter, B-CIM (manufactured by Hodogaya Chemical Co., Ltd.)), 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-pro -1-one, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 3,3-dimethyl-4-methoxybenzophenone, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (hereinafter, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (hereinafter referred to as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.)), 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- ( 4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Ethyl acetate, butyl 4-dimethylaminobenzoate, 4-dimethylamine Benzoic acid-2-ethylhexyl ester, 4-dimethylaminobenzoic acid-2-isoamyl ester, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, trichloroacetophenone, p-tert -Butylacetophenone, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, methyl o-benzoylbenzoate, bis (4-dimethylamino) Phenyl) ketone, 4,4′-bisdiethylaminobenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, Nzoin isobutyl ether, benzoin butyl ether, p-dimethylaminoacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, α, α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2,4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methoxy) styryl-s-triazine, etc. And triazine compounds.

  In addition to the above, sulfur compounds such as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2-ethylanthraquinone, octamethylanthraquinone, 1,2 -Anthraquinones such as benzanthraquinone and 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole Thiol compounds such as 2-mercaptobenzothiazole can also be used.

  These photoinitiators may be used individually by 1 type, and may be used in combination of 2 or more type. In particular, B-CIM and EAB-F are preferably used either alone or in combination.

  Specific examples of the combination include B-CIM and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butan-1-one, B-CIM and 2,4-bis (trichloromethyl) -6- (3-bromo-4-methoxy) phenyl-s-triazine or 2,4 -Bis (trichloromethyl) -6- (p-methoxy) styryl-s-triazine, B-CIM and 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one or 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2,4-bis (trichloromethyl) -6- (3-bromo 4-methoxy) phenyl-s-triazine or 2,4-bis (trichloromethyl) -6- (p-methoxy) styryl-s-triazine in combination, EAB-F and 2-benzyl-2-dimethylamino-1 Combination of-(4-morpholinophenyl) -butan-1-one, combination of triazine, EAB-F, 2-mercaptobenzimidazole and p-methoxystyryltriazine, 2-mercaptobenzimidazole and p-methoxystyryltriazine And the like.

  The photopolymerization initiator is preferably 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the total solid content of the black pigment in the pigment-dispersed radiation-sensitive resin composition. More preferably. When the photopolymerization initiator is within the above range, the sensitivity can be increased, the exposure time can be shortened, and the productivity can be improved.

  As the pigment, a pigment for black matrix and color filter use may be used, and an organic pigment is particularly preferably used.

  Examples of the organic pigment include compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), specifically, the following color index (C .. I.) Numbers can be mentioned.

  C. I. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185;

  C. I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73;

  C. I. Pigment violet 1, 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50;

  C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 94,202,206,207,208,209,215,216,217,220,223,224,226,227,228,240,242,243,245,254,255,264,265;

  C. I. Pigment Blue 1, 2, 15, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66;

  C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37;

  C. I. Pigment brown 23, C.I. I. Pigment brown 25, C.I. I. Pigment brown 26, C.I. I. Pigment brown 28;

  C. I. Pigment Black 1 and Pigment Black 7.

  In the pigment-dispersed radiation-sensitive resin composition of the present application, it is particularly used for a black matrix, and a black pigment is particularly preferably used.

  As the black pigment, carbon black or titanium black can be preferably used. In addition, Cu, Fe, Mn, Cr, Co, Ni, V, Zn, Se, Mg, Ca, Sr, Ba, Pd, Ag, Cd, In, Sn, Sb, Hg, Pb, Bi, Si, and Al Inorganic pigments such as various metal oxides, composite oxides, metal sulfides, metal lead sulfates, metal carbonates and the like can also be used.

  As the carbon black, known carbon blacks such as channel black, furnace black, thermal black, and lamp black can be used. In particular, channel black is preferably used because of its excellent light shielding properties. Resin-coated carbon black can also be used. Specifically, carbon black and a resin-coated carbon black obtained by mixing a resin having reactivity with a carboxyl group, a hydroxyl group, and a carbonyl group present on the surface of carbon black and heating at 50 to 380 degrees, water Examples thereof include resin-coated carbon black obtained by dispersing an ethylenic monomer in an organic solvent mixed system or water-surfactant mixed system and performing radical polymerization or radical copolymerization in the presence of a polymerization initiator. This resin-coated carbon black has lower electrical conductivity than carbon black without resin coating, so there is less current leakage when used as a color filter for liquid crystal displays, etc., forming a highly reliable display with low power consumption it can.

  As the black pigment, an organic pigment may be added as an auxiliary pigment. The following effects can be obtained by appropriately selecting and adding a black pigment that exhibits a complementary color of an inorganic pigment. For example, carbon black exhibits a reddish black color. Therefore, by adding an organic pigment having a blue color which is a complementary color of red as an auxiliary pigment to the carbon black, the redness of the carbon black disappears, and a more preferable black color as a whole is exhibited.

  The amount of the organic pigment in the black pigment is preferably 10 to 80 parts by weight, more preferably 20 to 60 parts by weight, and most preferably 20 to 100 parts by weight of the total of the black pigment and the organic pigment. ~ 40 parts by weight.

  As the black pigment and the organic pigment, a solution in which the pigment is dispersed at an appropriate concentration using a dispersant can be used. For example, as black pigments, Marco 5333 Black (containing 20% carbon concentration) manufactured by Special Colorant Industries, carbon dispersion CF Black EX-1455 (containing 24% high resistance carbon) manufactured by Gokoku Dye, titanium manufactured by Gokoku Dye Examples thereof include black dispersion CF black EX-1610 (containing 20% of black titanium pigment). Examples of the organic pigment include a blue pigment dispersion CF Blue UM (containing 20% blue pigment) made by Gokoku Dye, a violet dispersion OM made by Gokoku Dye (containing 10% violet pigment), and the like.

  As the dispersant, a polyethyleneimine-based, urethane resin-based, or acrylic resin-based polymer dispersant is preferably used.

  The pigment is preferably 10 to 60 parts by weight, more preferably 20 to 55 parts by weight, and more preferably 30 to 50 parts by weight in 100 parts by weight of the total solid content in the pigment-dispersed radiation-sensitive resin composition. Is more preferable. By making it within this range, a sufficient color density can be obtained.

  Further, when forming a black pattern using the pigment-dispersed radiation-sensitive resin composition of the present invention, as described later, the pigment-dispersed radiation-sensitive resin composition of the present invention is applied on a substrate and dried. A photopolymerizable black composition layer is formed.

  Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2- Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl Acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2 Methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl- 4-methoxypentyl acetate, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl carbonate, ethyl carbonate, propyl carbonate, butyl carbonate, benzene, toluene, xylene, cyclohexanone, methanol, ethanol, propanol, butanol, Examples include hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and glycerin. Of these, 3-methoxybutyl acetate can be preferably used.

  The said solvent can be contained so that the density | concentration of solid content (components other than a solvent) of a pigment dispersion type radiation sensitive resin composition may be 5-100 mass%, Preferably it is the range of 20-50 mass%. By making it in this range, the coating property can be improved and the flatness can be improved.

  If necessary, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a surfactant, an antifoaming agent, and other additives can be further added to the pigment-dispersed radiation-sensitive resin composition of the present invention.

  Specific examples of the sensitizer include eosin B (C.I.No. 45400), eosin J (C.I.No. 45380), alcohol-soluble eosin (C.I.No. 45386), cyanocin (C I. No. 45410), Bengalrose, erythrosine (C.I. No. 45430), 2,3,7-trihydroxy-9-phenylxanthen-6-one, and xanthene dyes such as rhodamine 6G, thionine ( CI No. 52000), thiazine dyes such as Azure A (CI No. 52005) and Azure C (CI No. 52002), pyronin B (C.I. No. 45005), and Pyronin dyes such as pyronin GY (CI No. 45005), 3-acetylcoumarin, 3-acetyl7-diethylaminocoumarin, etc. They include coumarin compounds.

  As the thermal polymerization inhibitor, hydroquinone, hydroquinone monoethyl ether, p-methoxyphenol, pyrogallol, catechol, 2,6-di-tert-butyl-p-cresol, β-naphthol and the like can be used.

  As the plasticizer, dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerol and the like can be used.

  As the surfactant, various anionic, cationic and nonionic surfactants can be used. As the antifoaming agent, various silicone-based and fluorine-based antifoaming agents can be used.

The method for forming a colored pattern of the present invention is as follows: 1) preparation of a pigment-dispersed radiation-sensitive resin composition, 2) formation of a pigment-dispersed radiation-sensitive resin composition layer on a substrate, 3) exposure, 4) development, 5 ) It can be basically formed by a post-bake process.
Hereinafter, each process will be described.

1) Preparation of pigment-dispersed radiation-sensitive resin composition The pigment-dispersed radiation-sensitive resin composition, if necessary, a binder, a solvent, a sensitizer, a thermal polymerization inhibitor, a plasticizer, a surfactant, an antifoaming agent, etc. In addition, it is well dispersed and kneaded with a three-roll mill, ball mill, sand mill, jet mill or the like.

2) Formation of pigment-dispersed radiation-sensitive resin composition layer The above-prepared pigment-dispersed radiation-sensitive resin composition is applied onto a substrate whose surface has been previously cleaned. Examples of the substrate include materials such as glass, polyethylene terephthalate, and acrylic resin. Further, in order to improve the adhesion between the substrate and the pigment-dispersed radiation sensitive resin composition, a silane coupling agent may be added to the pigment-dispersed radiation sensitive resin composition, or may be previously applied to the substrate. . For the application of the pigment dispersion type radiation sensitive resin composition, a contact transfer type coating device such as a roll coater, a reverse coater or a bar coater or a non-contact type coating device such as a spinner or a curtain flow coater is used. In particular, in the case of a thick film, it is preferable to apply a plurality of times or to use several kinds of the application devices together. After application of the pigment-dispersed radiation-sensitive resin composition, it is allowed to stand at room temperature for several hours to several days, or is placed in a warm air heater or infrared heater for several tens of minutes to several hours to remove the solvent, and the coating film thickness 1 A pigment-dispersed radiation-sensitive resin composition layer of about 10 μm is used.

3) Exposure After formation of a pigment dispersion type radiation sensitive resin composition layer, it exposes through a negative mask. The light beam having a predetermined wavelength used for exposure is an activation light beam that emits light having a wavelength that activates the photopolymerization initiator to generate radicals, and specifically includes ultraviolet rays, excimer laser light, X-rays, gamma rays, and electron beams. Is preferred. The amount of irradiation light varies slightly depending on the composition of the pigment-dispersed radiation-sensitive resin composition used, but is preferably in the range of 30 to 2000 mJ / cm ² .

4) Development After the exposure process, development is performed by using a developer by a dipping method, a spray method, or the like. Examples of the developer include alkali metal hydroxides such as lithium, sodium, and potassium, carbonates, bicarbonates, phosphates, pyrophosphates, primary amines such as benzylamine and butylamine, dimethylamine, and dibenzyl. Secondary amines such as amine and diethanolamine, tertiary amines such as trimethylamine, triethylamine and triethanolamine, cyclic amines such as morpholine, piperazine and pyridine, polyamines such as ethylenediamine and hexamethylenediamine, tetraethylammonium hydroxide, trimethylbenzyl Ammonium hydroxide such as ammonium hydroxide, trimethylphenylbenzylammonium hydroxide, trimethylsulfonium hydroxide, diethylmethylsulfonium hydroxide, di Sulfonium hydroxides, such as chill benzyl sulfonium hydroxide, an aqueous solution of other choline is used.

5) Post-bake In the post-bake process, the temperature may be adjusted to be in the range of 150 to 250 ° C. in order to impart strength, chemical resistance and heat resistance of the colored pattern formed by development.

  As described above, the pigment-dispersed radiation-sensitive resin composition of the present invention and the colored pattern formed using this pigment-dispersed radiation-sensitive resin composition are rich in moisture resistance and adhesiveness, and can be used in color displays such as liquid crystal displays. Suitable for filters. In particular, since the black matrix has a large area in contact with the substrate, the adhesion with the substrate greatly affects. Therefore, the pigment-dispersed radiation-sensitive resin composition (using a black pigment as a pigment) of the present application is particularly suitable for forming a black matrix.

  Furthermore, as a colored layer of another color, the pigment-dispersed radiation-sensitive resin composition of the present application is applied to the substrate on which the black matrix formed as described above is formed, dried, exposed and developed in the same manner as described above to obtain a predetermined layer. The colored layer is formed so that a pattern (a stripe or a dot) is formed at a predetermined position (opening) of the black matrix. For example, in the case of producing an RGB colored layer, the pigment dispersion type radiation sensitive resin composition of the present application for each color of R, G, B (using a red pigment, a green pigment, a blue pigment as a pigment), The steps of the colored pattern forming method are repeated to form three colored layers. Thereby, a color filter can be manufactured. These colored layers are also suitable because they are rich in moisture resistance and adhesion.

  Further, as described above, a black pattern serving as a black matrix pattern is formed on the substrate using the pigment-dispersed radiation-sensitive resin composition of the present invention, and R, G, and the like are obtained by a dyeing method, a printing method, a pigment dispersion method, or the like. By coloring B or the like, it is possible to produce a color filter such as a liquid crystal display in which the durability does not deteriorate due to swelling even when placed under high humidity over time.

  Hereinafter, the present invention will be specifically described by way of examples. Examples described below are merely examples for suitably explaining the present invention, and do not limit the present invention.

(Examples 1-4)
1. Production of Photopolymerizable Compound A According to JP 2001-354735 A, in a 500 ml four-necked flask, 235 g of bisphenolfluorene type epoxy resin (epoxy equivalent 235), 110 mg of tetramethylammonium chloride, 2,6-di- 100 mg of tert-butyl-4-methylphenol and 72.0 g of acrylic acid were heated and dissolved at 90 to 100 ° C. while air was blown into the flask at a rate of 25 ml / min.

  Next, the temperature was gradually raised while the solution was clouded, and the solution was heated to 120 ° C. to be completely dissolved. At this time, although the solution gradually became transparent and viscous, stirring was continued until the acid value was less than 1.0 kgKOH / g. It took 12 hours for the acid value to be less than 1.0 kg KOH / g.

  Then, it cooled to room temperature and obtained the colorless and transparent solid bisphenolfluorene type epoxy acrylate (following formula (2)).

After adding and dissolving 600 g of propylene glycol monomethyl ether acetate to 307.0 g of the bisphenolfluorene type epoxy acrylate thus obtained, 80.5 g of benzophenonetetracarboxylic dianhydride and 1 g of tetraethylammonium bromide were mixed and gradually added. The temperature was raised and reacted at 110 to 115 degrees for 4 hours. After confirming the disappearance of the acid anhydride group, 38.0 g of 1,2,3,6-tetrahydrophthalic anhydride was mixed and reacted at 90 ° C. for 6 hours to obtain photopolymerizability represented by the general formula (1). Compound A was obtained. In the general formula (1), R ₁ and R ₂ are each H. Further, the Y / Z molar ratio in the formula was 50.0 / 50.0. The disappearance of the acid anhydride was confirmed by infrared absorption spectrum.

2. Preparation of pigment-dispersed radiation-sensitive resin composition 150 g of the above photopolymerizable compound A (55% solid content), 30 g of pentaerythritol tetraacrylate, 2 g of B-CIM as a photopolymerization initiator, and 2-methyl- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one (Irgacure 907: Ciba Specialty Chemicals) 5 g, 2-mercaptobenzimidazole 5 g, and styrene-acrylic acid copolymer to adjust the water droplet contact angle of the cured coating film With a stirrer, 7.5 g, 15 g, 30 g, and 75 g of a combination, 500 g of a pigment dispersion Marco 5333 black (carbon concentration 20%, manufactured by Special Colorant Industries) as a black pigment, and 300 g of 3-methoxybutyl acetate as a solvent Mix for 2 hours and filter with 5 μm membrane filter to separate the black pigment. Four pigment-dispersed radiation-sensitive resin composition obtained by (Examples 1-4) were prepared.

3. Formation of Black Matrix Pattern Using the spin coater (TR25000: manufactured by Tokyo Ohka Kogyo Co., Ltd.) on the glass substrate having a clean surface with a thickness of 1 mm, the four types of pigment-dispersed radiation-sensitive resin compositions prepared above. The coating was applied so that the dry film thickness was 1.4 μm, and dried at 90 ° C. for 2 minutes to form four types of pigment-dispersed radiation-sensitive resin composition layers (photopolymerizable black composition layers).

Subsequently, each of the four types of photopolymerizable black composition layers was selectively irradiated with ultraviolet rays through a negative mask. The exposure amount was 300 mJ / cm ² . Then, after spray development with 0.04 wt% aqueous potassium hydroxide solution at 25 degrees for 80 seconds, it is post-baked in an oven at 220 ° C. for 30 minutes to form four types of black matrix patterns as black patterns including 20 μm lines. did.

(Comparative example)
In the above examples, a pigment dispersion type radiation sensitive resin composition layer was formed on a glass substrate in the same manner except that no styrene-acrylic acid copolymer was added, and a black matrix was obtained and a liquid crystal panel was prepared.

(Hydrophobic property evaluation of pigment dispersion type radiation sensitive resin composition layer)
Pure water was dropped on the four types of pigment-dispersed radiation-sensitive resin composition layers (Examples 1 to 4) formed on the glass substrate in Examples 1 to 4, and the contact angles of the water droplets formed on the layers were determined. It was measured. The results are shown in Table 1 below. Similarly, pure water was dropped on the pigment-dispersed radiation-sensitive resin composition layer formed on the glass substrate in the comparative example, and the contact angle of the water droplet formed on the layer was measured. The results are also shown in Table 1 below.

(Durability evaluation of black matrix)
The black matrices prepared in Examples 1 to 4 and the comparative example were left in a 120 ° C., 100 RH%, 2 atm environment for 5 hours to confirm the presence and extent of peeling. The results are shown in Table 1 below. In Table 1, the evaluation when the peeling was even a little was indicated by x, the evaluation when the peeling was practical with almost no peeling was indicated by ◯, and the good case without peeling was indicated by ◎.

  As is apparent from Table 1, the water droplet contact angles of the cured coating films obtained in Examples 1, 2, 3, and 4 are 76 degrees, 80 degrees, 80 degrees, and 80 degrees, respectively. The black matrix prepared in the above does not peel off even after the durability test. On the other hand, the water droplet contact angle of the cured coating film obtained in Comparative Example 1 was 70 degrees, and in Comparative Example 1, peeling occurred.

  As described above, the pigment-dispersed radiation-sensitive resin composition according to the present invention contains at least a photopolymerizable compound, a photopolymerization initiator, a pigment, and a solvent. Since the surface of the cured coating film has a hydrophobicity with a water droplet contact angle of 75 degrees or more, moisture resistance and durability much higher than expected can be obtained, so a color matrix that can contain display substances such as liquid crystal inside It can use suitably as a photosensitive coloring resin composition for forming.

  By using the pigment-dispersed radiation-sensitive resin composition of the present invention as a resin composition for preparing a color matrix of a multicolor display panel such as a color liquid crystal display device, leakage of display substances such as liquid crystal is possible even under severe conditions. A multicolor display that does not occur can be obtained.

Claims (9)

  It comprises at least a photopolymerizable compound, a photopolymerization initiator, a pigment, and a solvent, and has a water droplet contact angle of 75 degrees or more on the surface of the cured coating film after being formed into a coating film and photocured. A pigment-dispersed radiation-sensitive resin composition.   The pigment-dispersed radiation-sensitive resin composition according to claim 1, further comprising a polymer binder for adjusting the contact angle.   The pigment-dispersed radiation-sensitive resin composition according to claim 2, wherein the polymer binder is a styrene-acrylic acid copolymer.   The pigment-dispersed radiation-sensitive resin composition according to claim 2 or 3, wherein the content of the polymer binder is 5 parts by weight or more and less than 50 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. .   The pigment-dispersed radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the photopolymerizable compound is hydrophilic. The hydrophilic photopolymerizable compound is represented by the following chemical formula (1)

(In the formula, n is an integer of 1 to 20, Y is a residue excluding the acid anhydride group of dicarboxylic anhydride, and Z is the acid anhydride group of tetracarboxylic dianhydride. X is a residue removed, and X is the following chemical formula (2)

Wherein R ₁ and R ₂ are H, CH ₃ or

And R ₃ is H or CH ₃ . )
The pigment-dispersed radiation-sensitive resin composition according to claim 1, wherein the pigment-dispersed radiation-sensitive resin composition is a compound represented by the formula:   The pigment-dispersed radiation-sensitive resin composition according to claim 1, wherein the pigment is a black pigment.   The pigment-dispersed radiation-sensitive resin composition according to claim 7, wherein the black pigment is carbon black or titanium black.   A photopolymerizable coloring composition layer comprising the pigment-dispersed radiation-sensitive resin composition according to any one of claims 1 to 8 is formed on a substrate, and light having a predetermined wavelength is selectively applied to the composition layer. Irradiating and developing to form a colored pattern.