JPH052107A - Formation of color filter - Google Patents

Abstract

PURPOSE:To provide the method which produces color filters consisting of multicolored patterns on a base with high throughput and produces the multicolored patterns having the higher fineness than the fineness obtd. by having distinctly colored patterns without having blurring at the boundaries of the patterns. CONSTITUTION:This method forms the color filters by repeating the stage for bringing the photosensitive resin layer of an image forming material provided on the colored photosensitive resin layer on a tentative base having UV transmittability into tight contact with an adhesive layer provided on the base and exposing patterns to the photosensitive resin layer, then developing the photosensitive resin layer by using the image forming materials colored to different colors. The adhesive layer in this method consists of a negative type photosensitive resin compsn. which is provided on the base by a layer transfer method and can be developed by an aq. alkaline soln.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a color filter used for a liquid crystal color display or the like.

[0002]

2. Description of the Related Art A liquid crystal color display is a first multilayer structure having a color filter, a protective film, a transparent electrode having a matrix pattern, an insulating film, and an alignment film in this order on a transparent substrate such as glass and glass. A second multi-layer structure having a transparent electrode, an insulating film, and an alignment film in the order of the entire surface or a transparent substrate on the transparent substrate was made to face each other with the alignment film surface facing inside, and was pasted with a spacer therebetween. It has a structure in which a liquid crystal is sealed in a cell and sandwiched between two polarizing plates. In the first multilayer structure, the transparent electrode having a matrix-like pattern may be below the color filter and above the transparent substrate.

The color filter is a red color on a transparent substrate.
This is a structure in which blue and green stripe-shaped images or dot-shaped images are respectively arranged, and in some cases, respective boundaries are divided by a black matrix. One of the excellent methods for forming such a colored pattern on a substrate is Japanese Patent Application No. 2-
82262. in this way,
The photosensitive resin layer of the image-forming material provided with the colored photosensitive resin layer on the ultraviolet-transparent temporary support is brought into close contact with the adhesive layer provided on the support, and the photosensitive resin layer is passed through the temporary support. An image having a color different from the first color is formed by pattern-exposing the photosensitive resin layer, peeling off the temporary support and then developing to form a pattern, and if necessary embedding the pattern in the adhesive layer. A multicolor coloring pattern is obtained by bringing the materials into close contact with each other and repeating exposure and development. In this specification, the material of the adhesive layer is not particularly limited, but it may be necessary to remove the unnecessary adhesive layer after the image formation with the colored layer, and such a function is provided. The adhesive layer must be selected. It is also very important to efficiently provide the adhesive layer on the support, but this has not been described in detail.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a color filter comprising a multicolored coloring pattern on a support at a high throughput, which has no bleeding at the boundary of the pattern and has a clear coloring. Providing a method for producing a multi-color coloring pattern having a higher definition having a pattern, improving the alignment accuracy of each color,
Providing a method for manufacturing a multicolored coloring pattern in which each color is easily aligned, and a manufacturing method that can obtain a multicolored coloring pattern at a low cost with a simpler manufacturing process,
Another object of the present invention is to provide a method capable of easily and accurately removing an unnecessary portion of an adhesive layer provided on a support such as glass. Another object of the present invention is to provide a method for removing an unnecessary portion of the adhesive layer without using a solvent.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming material having a colored photosensitive resin layer provided on a UV-transparent temporary support, the photosensitive resin layer being provided on the support. The step of closely contacting the provided adhesive layer, pattern-exposing the photosensitive resin layer, and then developing the photosensitive resin layer is repeated using image forming materials colored in different colors to form a color filter. In the method, the adhesive layer is composed of a negative photosensitive resin composition which is provided on the support by a layer transfer method and can be developed with an alkaline aqueous solution, thereby achieving a color filter.

According to the manufacturing method of the present invention, since an image forming material having a uniform coating film thickness is used in advance, exposure / exposure
Development characteristics are stable, and color density and film thickness can be easily controlled. It is easy to align the patterns of each color.
Since the pattern created above is substantially embedded in the adhesive layer, it has good flatness, and as a whole, a multicolored colored pattern having excellent adhesion of the pattern to the support and excellent pattern definition can be obtained. .. High durability of coloring pattern.
Since the photosensitive material is supplied in the form of a colored layer and an adhesive layer,
There are no problems related to coating such as stability of coating liquid. Since the adhesive layer is provided on the substrate such as glass, the adhesion of the pattern is good, and the post-heating and post-exposure treatment after the pattern formation are unnecessary. Since the adhesive layer is photosensitive, it is possible to accurately form the pattern of the adhesive layer by exposure and development.
Since the adhesive layer is alkali developable, there is no problem in working environment and environmental pollution. There are numerous advantages such as

Next, the materials used in the present invention will be described in detail. As a temporary support for the colored photosensitive resin layer used in the present invention, it is flexible and preferably ultraviolet-transparent, and undergoes significant deformation, shrinkage or elongation even under pressure or under pressure and heating. Need not occur. Examples of such a support include polyethylene terephthalate film, cellulose triacetate film,
A polystyrene film and a polycarbonate film can be mentioned. Biaxially oriented polyethylene terephthalate film is particularly preferred.

On the temporary support, a colored photosensitive resin layer is provided directly or via a peeling layer having an ultraviolet ray transmitting property. When it is directly provided, the temporary support needs to have sufficient ultraviolet light transmittance to cure the photosensitive resin layer, but when it is provided via a release layer,
Since it is also possible to perform exposure after peeling off the temporary support, the UV transparency is not essential. The release layer is a colored photosensitive resin layer as an adhesive layer (may have a colored pattern).
It is provided so that the temporary support can be easily peeled off after being adhered to. Peeling can be done before or after pattern exposure,
In order to increase the resolution of the pattern, it is preferable to peel it off before exposure.

In the case of stripping before exposure, the stripping layer is provided with a temporary support in order to prevent diffusion of oxygen from the air which hinders the photo-curing reaction in the colored photosensitive resin layer during pattern exposure. It is preferable that it can be peeled from the body with appropriate adhesiveness, it should not be mechanically peeled from the colored photosensitive resin layer, and it should have an oxygen blocking ability. Such a release layer is formed by applying a polymer solution onto a temporary support. Suitable polymers include JP-B-46-32714 and JP-B-5.
Polyvinyl alcohol, water-soluble polyvinyl alcohol partial ester, same partial ether, same partial acetal, 88 to 99% described in each publication of 6-40824.
Hydrolyzed polyvinyl acetate, gelatin, gum arabic, methyl vinyl ether / maleic anhydride copolymer,
Polyvinylpyrrolidone, 100,000-3,000,000
Mention may be made of high molecular weight water-soluble ethylene oxide polymers having an average molecular weight of 1 and mixtures of these polymers.

The release layer is coated on the temporary support using an aqueous solution of the above polymer or a solution in a mixture of water and an organic solvent. Furthermore, by adding a surfactant to this solution, a more uniform undercoat layer can be obtained. The thickness of the undercoat layer is preferably 0.2 to 10.0 μm, more preferably 0.5 to 5.0 μm. If it is less than 0.2 μm, the oxygen barrier effect cannot be obtained, and if it exceeds 10 μm, dissolution in a developing solution takes time, which is not preferable.

As the above-mentioned surfactant, anionic,
Cationic and nonionic surfactants, eg 12-1
Sodium alkylsulfate having 8 carbon atoms, or sodium alkylsulfonate (sodium dodecylsulfate, sodium octadecylsulfonate, etc.), N-cetylbetaine, C-cetylbetaine, alkylaminocarboxylate and alkylaminodicarboxylate, Polyethylene glycol having an average molecular weight of 400 or less is used.

The colored photosensitive resin layer and the adhesive layer provided on the temporary support or the peeling layer are formed of a so-called negative type photosensitive resin composition. Negative-type photosensitive resin compositions that can be used here can be roughly classified into the following four types.

[1] Photosensitive resin composition comprising negative photosensitive diazo resin and binder A negative photosensitive diazo resin is described in US Pat. No. 2063.
The reaction product of the diazonium salt described in each of 631 and 2667415 and an organic condensing agent containing a reactive carbonyl group such as formaldehyde is preferable. Particularly preferred is a condensation product of diazodiphenylamine-p-diazonium salt and formaldehyde. Other useful negative-working photosensitive resins include Japanese Examined Patent Publication Nos. 49-48001, 49-45322 and 49-49.
The thing described in each gazette of No. 45323 is mentioned.

These negative-working photosensitive diazo resins are water-soluble and therefore can be applied as an aqueous solution to form the photosensitive resin layer. Further, these water-soluble diazo resins are prepared by the method described in JP-B-47-1167, and aromatic or aliphatic compounds having one or more phenolic hydroxyl groups or sulfonic acid groups or both in the molecule. It is also possible to use a substantially water-insoluble organic solvent-soluble photosensitive diazo resin obtained by reacting with.

Preferred compounds having a phenolic hydroxyl group are hydroxybenzophenones such as 4-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone and 2,2'-dihydroxy-4,4'-. Examples thereof include dimethoxybenzophenone and 2,2 ′, 4,4′-tetrahydroxybenzophenone, and further 4,4-bis (4 ′
-Hydroxyphenyl) pentanoic acid, resorcinol,
And those having a substituent such as an alkyl group or an alkoxy group on the benzene ring thereof.

Examples of preferable sulfonic acid include aromatic sulfonic acids such as benzene, toluene, xylene, naphthalene, phenol, naphthol, benzophenone and like sulfonic acids, or soluble salts thereof.
Examples include ammonium and alkali metal salts.
Sulfonic acid group-containing compounds include lower alkyl, nitro group,
It may be substituted with a halogen group. Specific examples of preferable sulfonic acid group-containing compounds include benzenesulfonic acid, toluenesulfonic acid, naphthalenesulfonic acid, and 2.
5-dimethylbenzenesulfonic acid, sodium benzenesulfonate, naphthalene-2-sulfonic acid, 1-naphthol-2-sulfonic acid, 1-naphthol-4-sulfonic acid, 2,4-dinitro-1-naphthol-7-sulfone Acids, hydroxy-4-methoxybenzophenone-5-sulfonic acid, o-toluidine-m-sulfonic acid and ethanesulfonic acid.

As a method for producing these substantially water-insoluble photosensitive diazo resins, a water-soluble photosensitive diazo resin and an aqueous solution of the above-mentioned phenol compound or sulfonic acid compound are preferably used, preferably a diazonium group and a phenol group or sulfonic acid. It can be isolated as a precipitate by mixing such that the groups are almost equimolar. Also the British patent No. 1
The photosensitive diazo resin described in No. 312925 is also preferable. The most preferred photosensitive diazo resin is 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonate, which is a condensate of p-diazodiphenylamine and formaldehyde. The content of the photosensitive diazo resin in the photosensitive resin layer is preferably 5 to 50% by weight. When the content of the photosensitive diazo resin is small, the photosensitivity is improved, but the stability with time decreases. The particularly preferred content of the photosensitive diazo resin is 8 to 20% by weight.

Although various polymer compounds can be used as the binder in the present invention, a carboxylic acid group, a hydroxy group, an amino group, a carboxylic acid amide group, a sulfonic acid amide group, an active methylene group, and a thioalcohol group can be used in the molecule. Those containing an epoxy group are preferred.

As the water-soluble photosensitive resin composition, a combination of the above-mentioned water-soluble photosensitive diazo resin and a water-soluble binder is used. Typical examples of the water-soluble binder include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, hydroxymethyl cellulose, gelatin and the like. Further, as a binder which is preferable for use in a water-insoluble photosensitive resin composition, which is more preferable in terms of stability with time, is described in British Patent No. 13505021.
Shellac as described in British Patent No. 14
60978 and US Pat. No. 4,123,276, polymers containing hydroxyethyl (meth) acrylate units as the main repeating unit, polyamide resins described in US Pat. No. 3,751,257, Phenolic resins and polyvinyl acetal resins such as polyvinyl formal resins and polyvinyl butyral resins described in British Patent No. 1,074,392, linear polyurethane resins described in US Pat. No. 3,660,973, polyvinyl alcohol phthalates. Resin, epoxy resin which is a polycondensate of bisphenol A and epichlorohydrin, amino group-containing polymer such as polyaminostyrene and polyalkylamino (meth) acrylate, cellulose acetate,
Examples thereof include cellulose derivatives such as cellulose alkyl ether and cellulose acetate phthalate, and water-soluble polyvinyl alcohol.

The content of the binder in the photosensitive resin layer is
50 to 95% by weight is preferable. When the content of the photosensitive diazo resin is small, the photosensitivity is improved, but the stability with time decreases. Particularly preferred content of the photosensitive diazo resin is 80
-92% by weight.

[2] Photopolymerizable Composition The photopolymerizable composition that can be used in the present invention contains an addition polymerizable unsaturated monomer, a photopolymerization initiator and a binder as basic constituent elements. The addition-polymerizable unsaturated monomer is a compound having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. For example, polyethylene glycol mono (meth) acrylate,
Polypropylene glycol mono (meth) acrylate,
Monofunctional acrylates and monofunctional methacrylates such as phenoxyethyl (meth) acrylate. Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxy) Ethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri Meth) acrylate, after the addition reaction of ethylene oxide by propylene oxide to a polyfunctional alcohol such as trimethylolpropane or glycerol (meth) those acrylated. Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 50
Urethane acrylates described in JP-A-6034 and JP-A-51-37193. JP-A-48-6
No. 4183, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-
Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, described in each publication of 30490 can be mentioned. More preferable examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate. The content of the addition-polymerizable unsaturated monomer in the photopolymerizable composition is 5 to 50% by weight, more preferably 10 to 40% by weight. If it is less than 5% by weight, the photosensitivity and pattern strength are low, and if it exceeds 50% by weight, the tackiness of the photosensitive resin layer becomes excessive, which is not preferable.

As the photopolymerization initiator, US Pat. No. 236 is used.
Vicinal polyketaldonyl compounds disclosed in 7660, acyloin ether compounds described in U.S. Pat. No. 2,448,828, U.S. Pat.
.Alpha.-hydrocarbon substituted aromatic acyloin compounds described in US Pat. No. 7,225,512, US Pat. No. 3,046,127.
Nos. 2951758 and 2951758, polynuclear quinone compounds, combinations of triarylimidazole dimers and p-aminoketones described in U.S. Pat. No. 3,549,367, and JP-B-51-48516. Benzothiazole compound and trihalomethyl-s-triazine compound, trihalomethyl-s-triazine compound described in U.S. Pat. No. 4,239,850, and trihalomethyloxadiazole compound described in U.S. Pat. No. 4,212,976. Etc. Particularly preferred are trihalomethyl-s-triazine, trihalomethyloxadiazole, and triarylimidazole dimer. The content of the photopolymerization initiator in the photopolymerizable composition is 0.5 to 20% by weight, more preferably 2 to 15% by weight.
Is. If it is less than 0.5% by weight, the photosensitivity and pattern strength are low, and if it exceeds 20% by weight, no good effect on the performance is observed.

The binder is preferably a linear organic polymer compatible with the addition-polymerizable unsaturated monomer, soluble in an organic solvent, soluble in a weak alkaline aqueous solution, or at least swellable. As such a linear organic polymer, a polymer having a carboxylic acid group in the side chain,
For example, JP-A-59-44615 and JP-B-54-34.
327, Japanese Patent Publication 58-12577, Japanese Patent Publication 54-2
5957, JP-A-59-53836, JP-A-59-
Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer as described in each specification of No. 71048. Examples thereof include cellulosics, which have a carboxylic acid group in the side chain. In addition, a polymer having a hydroxyl group and a cyclic acid anhydride is also useful. Particularly preferably, U.S. Pat. No. 413
Copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in 9391 and benzyl (meth)
Mention may be made of multi-component copolymers of acrylate, (meth) acrylic acid and other monomers. The above are water-insoluble binders, but as a water-soluble polymer,
Examples thereof include polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol and the like. Besides the above,
In order to improve various properties, for example, the strength of the cured film, an alkali-insoluble polymer can be added within a range that does not adversely affect the developability and the like. Examples of these polymers include alcohol-soluble nylon and epoxy resin. The content of the binder in the photopolymerizable composition is 50.
˜95% by weight, more preferably 60 to 90% by weight. If it is less than 50% by weight, the tackiness of the photosensitive resin layer is too high, and if it exceeds 95% by weight, the strength and photosensitivity of the formed pattern are poor.

In addition to the above components, it is preferable to add a thermal polymerization inhibitor. Examples thereof include hydroquinone, p-methoxyphenol, di-t-butyl-p.
-Cresol, pyrogallol, t-butylcatechol,
Benzoquinone, 4,4'-thiobis (3-methyl-6-
t-butylphenol), 2,2'-methylenebis (4
-Methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

[3] Photosensitive resin composition comprising azide compound and binder As a preferable example, for example, British Patent No. 123528.
No. 1 and No. 1495861 each specification and JP-A-51
-32331, JP-A-51-36128, etc., and a photosensitive resin composition comprising an azide compound and a water-soluble or alkaline aqueous solution-soluble polymer binder, as well as JP-A-50-5102. JP-A-50-84
No. 302, JP-A No. 53-12984, etc., and a photosensitive resin composition comprising a polymer containing an azide group and a polymer compound as a binder is included.

[4] Cinnamic acid type photosensitive resin As a preferable example, for example, JP-A-52-96696.
Photosensitive polyesters disclosed in U.S. Pat. Nos. 1,112,277, 13,133,390 and 134.
The polyvinyl cinnamates described in each specification of No. 1004 and No. 1377747 are included.

In order to form a colored photosensitive resin layer from a pigment or dye and a negative photosensitive resin composition, the negative photosensitive resin composition is dissolved in an appropriate solvent to prepare a single or two or more kinds. A pigmented photosensitive resin coating liquid of one hue is prepared by dispersing a mixed pigment or dissolving a dye, and the coating liquid is applied to a spinner, a whiler, a roller coater, a curtain coater, a knife coater, a wire bar coater. , Extruder or the like is used to coat the temporary support.

For the color filter, red, green, blue and black pigments are used. Carmin 6B (C.I. 12490), phthalocyanine green (C.I. 74260), phthalocyanine blue (C.I. 74160) and Mitsubishi carbon black MA-100 can be mentioned as preferable specific examples thereof. However, the present invention is not limited to these. The content of the pigment or dye in the colored photosensitive resin layer is preferably 1 to 30% by weight. It is more preferably 5 to 20% by weight.

Preferred solvents are benzene, toluene, xylene, cyclohexane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate. , Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl lactate, ethyl lactate, methanol, ethanol, 1-propanol, 2-propanol, butanol, sec-butanol , T-butanol, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, .gamma.-butyrolactone, .epsilon.-caprolactam, dimethyl sulfoxide, hexamethylphosphoramide, and water. These can be used alone or as a mixture of two or more kinds. The solid content concentration of the coating liquid is preferably in the range of 1 to 50% by weight, more preferably 5 to 40% by weight. The dry film thickness of the colored photosensitive resin layer is preferably 0.3 to 10 μm, more preferably 0.5 to 5 μm.

It is necessary that the support having an adhesive layer is, in some cases, UV-permeable and does not undergo significant deformation, shrinkage or elongation under pressure or under pressure and heating. Examples of such a support include polyethylene terephthalate film, cellulose triacetate film, polystyrene film, polycarbonate film, and glass plate. Biaxially stretched polyethylene terephthalate film and glass plate are particularly preferable.

When used as a color filter, the support is required to be substantially transparent to visible light, and the above polymer film or glass plate is used. A transparent support provided with transparent electrodes in a matrix may be used.

An adhesive layer is provided on these supports. The adhesive layer is required to have good adhesiveness when the colored photosensitive resin layer is adhered thereon, and further, the colored pattern obtained by pattern exposure and development of the colored photosensitive resin layer is embedded. It is also necessary to obtain sufficient adhesion. For this purpose, the adhesive layer must be soft at room temperature or capable of being softened by heating. Further, it is necessary that the colored photosensitive resin layer has resistance to an alkaline aqueous developer. Preferred examples include the photopolymerizable image-receiving layer described in JP-A-59-97140 or the mold release described in JP-A-61-189535 and Japanese Patent Application No. 1-65064. An image-receiving layer having a two-layer structure having layers can be mentioned. The adhesive layer can be cured by using these and irradiating with ultraviolet rays after embedding the pattern in the adhesive layer. By this treatment, this adhesive layer exhibits stronger adhesion to the support.

In this case, it is necessary to avoid hardening of the photopolymerizable image-receiving layer when the colored image-forming layer is subjected to pattern exposure. For this purpose, the photosensitivity of the photopolymerizable image receiving layer is set to about 1/3 or less of the photosensitivity of the colored image forming layer, or a photopolymerization initiator having a different photosensitive wavelength is used. For example, the photopolymerization initiator for the colored image forming layer has a photosensitive wavelength range of 400 to 450 n.
A compound having m (long wave) is used, and the photopolymerization initiator of the photopolymerizable image-receiving layer has a photosensitive wavelength range of 300 to 400 n.
The compound at m (short wave) is used.

As the long-wavelength photosensitizer, a combination of Michler's ketone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,4-diethylxanthone and ethyl p-dimethylaminobenzoate is used. In combination with 4,4'-bis (diethylamino) benzophenone and 2,4-bis (trichloromethyl) -6- (4'-
A combination with methoxyphenyl) -s-triazine, 2,4-bis (trichloromethyl) -6- (4′-methoxystyryl) -s-triazine and the like can be mentioned.

As the short wavelength photoinitiator, benzyl dimethyl ketal, benzoin isopropyl ether, benzophenone, 2,4,6-tris (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -phenyl- Examples thereof include s-triazine and 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole.

The film thickness of the adhesive layer may be a thickness sufficient for embedding the colored pattern after pattern formation,
1 to 100 μm is preferable, and 5 to 30 μm is particularly preferable. When the thickness is less than 1 μm, the embedding of the colored pattern is insufficient and the adhesion after the second colored pattern is poor, and when the thickness exceeds 100 μm, there is a problem in storage of the sheet having the adhesive layer.

The medium used for developing the colored photosensitive resin layer after exposure is an aqueous medium, that is, a medium composed mostly of water. Further, it is preferable to add an alkaline substance and, if necessary, an organic solvent miscible with water to this developing solution.

Suitable alkaline substances are alkali metal hydroxides (sodium hydroxide, potassium hydroxide), alkali metal carbonates (sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium hydrogen carbonate, potassium hydrogen carbonate), Alkali metal silicate (sodium silicate, potassium silicate), alkali metal metasilicate (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, trialkylammonium hydroxide, or phosphoric acid It is trisodium.

Suitable organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone. , Methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide,
Hexamethylphosphoramide.

A wetting agent may be added to the developing solution. As the wetting agent, an alkylnaphthalene sulfonate having a low foaming property is particularly preferable. Particularly preferred developing solutions are aqueous solutions of ethylene glycol mono-n-butyl ether and sodium carbonate, benzyl alcohol, sodium carbonate, sodium hydroxide and sodium butylnaphthalene sulfonate.

The developing solution can be used as a bath solution or a spray solution. Removal of the unexposed portion from the colored photosensitive resin layer can be advantageously performed by rubbing with a brush, rubbing with a wet sponge, rubbing, or any other known method.

As the developer for the adhesive layer, the above-mentioned alkaline aqueous solution (including a small amount of an organic solvent miscible with water) is preferable. However, it is necessary that the adhesive layer is not developed by the developing solution for the colored photosensitive resin layer provided on the adhesive layer. Therefore, the alkaline aqueous solution used for developing the colored photosensitive resin layer needs to have a pH lower than that of the alkaline aqueous solution for developing the adhesive layer. Therefore, the pH of the developer for the colored photosensitive resin layer and the adhesive layer is preferably 8 to 11.5 for the former and 2 or more higher than the pH for the former. As an example of such a combination of developers, the former is a developer containing 1 to 5% by weight of an alkali metal carbonate as a main component, and the latter is mainly 0.05 to 10% by weight of an alkali metal hydroxide. A developer as a component can be used.

To embed the colored pattern in the adhesive layer,
It is preferable to pressurize the adhesive layer on which the colored pattern is formed through a material having a surface energy smaller than that of both the adhesive layer and the colored pattern. Examples of such a material include silicon resin and fluorine resin. As a method of pressing, a roller made of a material having a small surface energy is used, or a film made of such a material having a small surface energy or a material having a small surface energy is applied to the surface of a flexible synthetic polymer film. This can be advantageously carried out by sandwiching the product between the colored pattern on the adhesive layer and a rubber roller. In this case, the film thickness of the material having a small surface energy is preferably 5 to 200 μm, particularly preferably 7 to 100 μm. As preferable conditions for the embedding treatment, the pressure is 1 to 3 kg / cm ² , and the treatment speed is 0.1.
1-3 m / min, and particularly preferably the pressure is 1.5
~ 2.5 Kg / cm ² , processing speed 0.2 ~ ² m / mi
n.

During this treatment, it is preferable to heat at the same time as pressurization. It is convenient to use a roller having a heating element inside for heating, and the temperature of the roller surface is 50 to 1
The temperature is 60 ° C, preferably 80 to 120 ° C. The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto.

[0045]

【Example】

 Example The materials shown below were mixed to prepare a uniform solution. Methyl methacrylate / ethyl acrylate / methacrylic acid copolymer (molar ratio = 70/25/5, 35 wt% solution of weight average molecular weight = 70,000, solvent is methyl ethyl ketone / 1-methoxy-2-propanol = 2/1) 860 parts Pentaerythritol tetraacrylate (A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.) 300 parts Benzyl dimethyl ketal (Irgacure 651 manufactured by Ciba Geigy) 15 parts Megafac F-177P (fluorine-based surfactant) , Manufactured by Dainippon Ink and Chemicals, Inc. 4 parts Hydroquinone monomethyl ether 0.5 part

The solution prepared above was applied onto a polyethylene terephthalate temporary support having a thickness of 100 μm using a bar coater and dried at 100 ° C. for 2 minutes to give a thickness of about 10 μm.
A sheet having a photosensitive adhesive layer of m was obtained. Laminate this on glass (first laminator 8B-5
50-80, manufactured by Taisei Corporation, pressure 2〓 /
〓, roller temperature 105 ℃, laminating speed 0.9m /
Lamination was performed under the condition of min. On the other hand, as the coating liquid for forming the colored photosensitive resin layer, four color photosensitive solutions of black (for light shielding layer), red (for R layer), green (for G layer) and blue (for B layer) are shown. Each was prepared so as to have the composition shown in FIG.

[0047]

[Table 1]

Each of these four color photosensitive solutions was uniformly coated and dried on a polyethylene terephthalate film (thickness = 20 μm) as a temporary support to give a dry film thickness of 0.5.
A colored photosensitive resin layer of μm was provided. A polyethylene film having a thickness of 30 μm was laminated as a protective film on the colored photosensitive resin layer of each color at room temperature. In this way, a colored photosensitive resin sheet (negative-type colored photosensitive sheet) comprising a temporary support, a colored photosensitive resin layer and a protective film in this order
Four types were manufactured.

The protective film was peeled off from the red photosensitive resin sheet, and the photosensitive resin layer was superposed on the glass plate from which the protective film had been removed so that the photosensitive resin layer was in contact with the adhesive layer on the glass plate, and then adhered. Lamination was performed under the same conditions as the agent layer. Then, the temporary support of the red photosensitive resin sheet was peeled off to transfer the red photosensitive resin layer onto the glass plate via the adhesive layer.

Then, a photomask having a matrix pattern of 120 μm on each side from the red photosensitive resin layer side on this adhesive layer was overlaid, and 400 nm or less was irradiated from the photomask side with an ultrahigh pressure mercury lamp of 2 Kw. Filters to be cut were overlapped and exposed from a distance of 50 cm. The exposed red photosensitive resin layer was developed with a developer having the following composition at a temperature of 35 ° C. for 20 seconds. Subsequent washing with water and drying gave a red pattern on the adhesive layer.

Developer: Sodium carbonate 15g Water 985g

A green photosensitive resin layer was transferred onto this adhesive layer having a red pattern in the same manner. Then, a matrix-shaped photomask was superposed on the photosensitive resin layer so as to be adjacent to the red pattern, and 400 n
Exposure was carried out with UV light that cut m or less, and development was performed in the same manner as described above. A green pattern adjacent to the red pattern was obtained on the adhesive layer. This green pattern had excellent adhesion, and no pattern loss or shape defect was observed.

Next, the same operation was repeated for the blue pattern to obtain a glass plate having a three-color pattern on the adhesive layer. Next, a black light-shielding pattern was formed in the same manner as described above. However, this time, pattern exposure was performed through a photomask having a stripe pattern. Thus, a glass plate having a red, green, and blue pattern having a light-shielding pattern (black stripe) was obtained. No defect was found in any pattern shape, and no pinhole was observed.

The adhesive layer portion of the sample thus obtained in which the red, green and blue patterns and the black stripes were formed in a pattern was composed of a developing solution for forming the red, green, blue and black stripe patterns. Even though it was immersed in, the surface did not change at all.

Next, using a photomask which shields only a portion without a pattern, both sides of the glass plate are exposed without passing through a filter which cuts 400 nm or less, and then developed with a 2% NaOH aqueous solution at 30 ° C. for 30 seconds. did.
As a result, it was possible to develop the adhesive layer without affecting the pixels.

[0056]

EFFECTS OF THE INVENTION According to the method of the present invention, it is possible to prepare a color filter having a finer definition and having a clear coloring pattern without bleeding at the boundary of the pattern.

Claims (1)

Claim: What is claimed is: 1. An adhesive comprising a colored photosensitive resin layer provided on an ultraviolet-transparent temporary support, and the photosensitive resin layer of an image forming material provided on the support. In the method for producing a color filter, the step of closely contacting a layer and subjecting the photosensitive resin layer to pattern exposure and then developing the photosensitive resin layer is repeated using image forming materials colored in different colors,
A method for producing a color filter, wherein the adhesive layer is composed of a negative photosensitive resin composition developable with an alkaline aqueous solution provided on the support by a layer transfer method.