JPH06324296A - Method for correcting defect of color filter - Google Patents

Abstract

PURPOSE:To finally produce a color filter excellent in flatness and having a defectless and stable pattern by correcting a color filter having a small number of defective picture elements by a convenient method. CONSTITUTION:The defect is corrected as follows. Namely, red, green, blie and black matrix picture elements are formed on a substrate, a colored photosensitive transfer material having a colored photosensitive resin layer of the same color as the omissive picture element is firmly attached to the region including the omission part of any of the picture elements, the region is exposed through the substrate, and the uncured part of the colored photosensitive resin layer is removed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of correcting a missing pixel or the like generated during manufacturing of a color filter used for a color television, a color display device, a color image pickup device or the like using a liquid crystal.

[0002]

2. Description of the Related Art As a method for producing a color filter for a liquid crystal display device, a printing method, a dyeing method, a pigment dispersion method (JP-A-57-16407), an electrodeposition method, a colored photosensitive layer transfer method ( Japanese Patent Application No. 2-400047) is known. In a device using a liquid crystal display element, a still image is often viewed, and it is desirable that pixels of each color forming a color filter have zero defects. However, many difficulties are involved in manufacturing a large number of color filters in which there are no missing pixels due to minute dust in the periphery or insufficient substrate cleaning process. Therefore, in order to further improve the yield, a method for correcting a color filter having a small number of missing pixels has been required.

However, in the conventional defect repairing method using a colored photosensitive resin coating liquid, it is very difficult to form a repaired pixel having good flatness in the defective portion due to the limitation of the coating technique. Further, when there are defects of a plurality of colors, it is necessary to repeat the steps of applying, exposing and developing the colored photosensitive resin coating liquid a plurality of times, which requires enormous labor and may cause new defects. It was

[0004]

In view of the above, the present invention corrects a color filter having a small number of missing pixels by a simple method, and finally has a stable pattern having excellent flatness and no defect. It is an object to provide a method for manufacturing a color filter.

[0005]

The object of the present invention is (1).
A step of forming red, green, blue and black matrix pixels on a substrate, (2) a colored photosensitive resin having a colored photosensitive resin layer of the same color as the missing pixel in a region including a missing part of any of the above pixels Process of closely attaching a hydrophilic transfer material, (3)
A step of exposing the area to which the colored photosensitive transfer material is adhered through the substrate to cure the colored photosensitive resin layer in the missing portion, and (4) removing an uncured portion of the colored photosensitive resin layer. The present invention is achieved by a method of correcting defects in a color filter, which comprises: According to the defect repairing method of the present invention, the flatness of the pixel of the repaired portion is good, and even when there are multicolored defects, the photosensitive coloring transfer material selected for each defective portion is brought into close contact with a necessary portion, It is possible to make a batch correction with one exposure and one development process. Hereinafter, the present invention will be described in detail.

The colored photosensitive transfer material used in the present invention is described in JP-A-4-208940 and Japanese Patent Application No. 2-2.
38286, Japanese Patent Application No. 3-9292, Japanese Patent Application No. 3-120223, Japanese Patent Application No. 3-15322.
It is possible to use those described in No. 7, etc.,
Particularly preferred in the method of the present application is Japanese Patent Application No. 3-153.
No. 227.

The color filter to be corrected may be prepared by essentially any known method, but preferably, the surface of the transparent substrate is exposed at the defective portion. No. 16407, a pigment-dispersed photosensitive resin is applied, dried and formed on a transparent substrate by repeating exposure and development; one formed by using the colored photosensitive transfer material described in the above publication; It is preferable to use a general printing method. However, a type in which the surface of the transparent substrate is not exposed in the defect portion, for example, a type formed by the method described in JP-A-3-282404 and Japanese Patent Application No. 2-238286 may be used. Even in the dyeing method, if it is a type in which the non-dyed portion is removed by the development as described in JP-A-1-293304, by applying the method of the present application, a color filter excellent in flatness is provided. preferable.

When the defective portion of the color filter to be corrected of the present application is the exposed portion of the transparent substrate, Japanese Patent Application No. 3-8.
If the substrate processing method described in the specification of No. 4037 is applied, excellent adhesion of the colored photosensitive transfer material of the present application can be realized.

As the colored photosensitive transfer material used in the method of the present invention, an alkali-soluble thermoplastic resin layer, a separation layer, and a colored photosensitive resin layer are provided in this order on a temporary support,
A colored photosensitive transfer material characterized in that the adhesive force between the thermoplastic resin layer and the temporary support is the smallest is particularly preferable and will be described in detail below.

The temporary support of the photosensitive transfer material is composed of a flexible material that has a releasability that is perfect with the thermoplastic resin layer, is chemically and thermally stable, and is flexible. A thin sheet such as Teflon, polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or a laminate thereof is preferable.
The thickness of the temporary support is appropriately 5 μm to 300 μm, preferably 20 μm to 150 μm.

As the organic polymer substance used for the thermoplastic resin layer, an organic high-molecular substance having a softening point of about 80 ° C. or less by the Viker Vicat method (specifically, a polymer softening point measuring method by the American material test method AST MSD ASTM D1235) is used. It is preferably selected from molecular substances. The reason for this is that by using a polymer with a low softening point, when the transfer sheet is transferred onto the uneven substrate by heat and pressure, the unevenness of the base is completely absorbed, and the transfer is performed without any residual air bubbles. is there. When a polymer having a high softening point is used, it is necessary to transfer at a high temperature, which is a practical disadvantage. From this point of view, the organic polymer used for the thermoplastic resin layer has a softening point of about 80 ° C. according to the Vicat method.
The following, preferably 60 ° C. or lower, particularly preferably 5
It is 0 ° C. or less. Those having a softening point of 80 ° C. or lower include saponified products of ethylene and acrylic acid ester copolymers, saponified products of styrene and (meth) acrylic acid ester copolymers, vinyltoluene and (meth) acrylic acid ester copolymers. It is preferable to select at least one of a saponified product, a poly (meth) acrylic acid ester, and a saponified product such as a (meth) acrylic acid ester copolymer such as butyl (meth) acrylate and vinyl acetate. "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Council,
Softening point is about 80 ° C (issued October 25, 1968)
Among the following organic polymers, those soluble in an alkaline aqueous solution can be used. Examples of the resin soluble in the alkaline aqueous solution include known polymer binders used for the alkali-soluble photopolymerizable resin. A copolymer of (meth) acrylic acid and a (meth) acrylic acid alkyl ester (wherein the alkyl group is a methyl group, an ethyl group, a butyl group, etc.), poly (meth) acrylic acid, styrene and maleic anhydride A copolymer of a saturated dibasic acid anhydride, and a reaction product of the polymer with an alcohol,
Examples include a reaction product of cellulose with a polybasic acid anhydride.
Among the above polymers, those which are particularly preferably used as the binder of the present invention are styrene / maleic anhydride copolymers, methyl methacrylate / methacrylic acid / methacrylic acid 2 described in JP-A-60-258539. -Ethylhexyl / benzyl methacrylate quaternary copolymer, JP-B-5
Styrene / maleic acid mono-n-butyl ester copolymer described in JP-A-5-38961, JP-B-54-259.
No. 57 styrene / methyl methacrylate / ethyl acrylate / methacrylic acid quaternary copolymers, benzyl methacrylate / methacrylic acid copolymers described in JP-A-52-99810, JP-B-58- No. 12577 specification acrylonitrile / 2-ethylhexyl methacrylate / methacrylic acid terpolymer, and methyl methacrylate / ethyl acrylate / acrylic acid terpolymer described in JP-B-55-6210. And styrene / maleic anhydride copolymer partially esterified with isopropanol.

Even in an organic polymer substance having a softening point of 80 ° C. or higher, various plasticizers compatible with the polymer substance are added to the organic polymer substance so that the actual softening point becomes 80 ° C. or lower. It is also possible to lower it. Further, in order to adjust the adhesive force with the temporary support in these organic polymer substances, various polymers, supercooling substances, adhesion improvers or surfactants, within a range where the actual softening point does not exceed 80 ° C, It is possible to add a release agent and the like. Specific examples of preferable plasticizers include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate,
Mention may be made of dibutyl phthalate, tricresyl phosphate and cresyl diphenyl phosphate biphenyl diphenyl phosphate.

The thickness of the thermoplastic resin layer is preferably 6 μm or more. The reason for this is that the thickness of the thermoplastic resin layer is 5 μm.
This is because it is impossible to completely absorb the unevenness of the base having a thickness of 1 μm or more when the value is below. The upper limit is about 100 μm or less, preferably about 50 μm in view of developability and production suitability.
μm or less.

Depending on the transfer conditions of the photosensitive transfer material, the thermoplastic resin may squeeze out into the surroundings during transfer and contaminate the permanent support. In order to prevent this contamination, among the above-mentioned thermoplastic resins, those that dissolve in an alkaline aqueous solution are preferable. This is because if it dissolves in an alkaline aqueous solution, it can be easily removed by the subsequent treatment.

In the present invention, the alkaline aqueous solution is a dilute aqueous solution of an alkaline substance, and also includes a solution obtained by adding a small amount of an organic solvent miscible with water. Suitable alkaline substances are alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide), alkali metal carbonates (eg sodium carbonate, potassium carbonate), alkali metal bicarbonates (sodium hydrogen carbonate, potassium hydrogen carbonate), Alkali metal silicates (sodium silicate, potassium silicate) Alkali metal metasilicates (sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides (eg, Tetramethylammonium hydroxide) or trisodium phosphate. The concentration of the alkaline substance is 0.
The amount is 01% to 30% by weight, and the pH is preferably 8 to 14.

Suitable water-miscible organic solvents are 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, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone. The concentration of water-miscible organic solvent is 0.1% by weight
It is 30% by weight. Further, a known surfactant can be added. The concentration of the surfactant is 0.01% by weight to 1
0% by weight is preferred.

Any known separation layer may be used as long as it has a low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution. For example, JP-A-46-
2121 and Japanese Patent Publication No. 56-40824, polyvinyl ether / maleic anhydride polymers, water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, Of polyvinylpyrrolidone, various polyacrylamides, various water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various water-soluble salts of starch and the like, styrene / maleic acid Copolymers, maleate resins and combinations of two or more of these.

Particularly preferred is a combination of polyvinyl alcohol and polyvinylpyrrolidone. The polyvinyl alcohol preferably has a saponification rate of 80% or more, and the content of polyvinylpyrrolidone is 1% of the solid content of the separation layer.
The amount is preferably from wt% to 75 wt%, more preferably from 1 wt% to 60 wt%, even more preferably from 10 wt% to 50 wt%. If it is less than 1% by weight, sufficient adhesion to the photosensitive resin layer cannot be obtained, and if it exceeds 75% by weight, the oxygen blocking ability is lowered. The thickness of the separation layer is very thin, about 0.1-5μ
m, especially 0.5 to 2 μm. If it is less than about 0.1 μm, the oxygen permeability is too high, and if it exceeds about 5 μm, it takes too much time during development or removal of the separation layer.

The colored photosensitive resin layer preferably becomes soft or tacky at a temperature of at least 150 ° C. or lower,
It is preferably thermoplastic. Most of the layers using known photopolymerizable compositions have this property, but some of the known layers can be further modified by the addition of thermoplastic binders or compatible plasticizers. . In the present invention, as a material for the photosensitive resin layer, all known photosensitive resins described in, for example, JP-A-3-282404 can be used. Specific examples include a photosensitive resin layer containing a negative type diazo resin and a binder, a photopolymerizable composition, a photosensitive resin composition containing an azide compound and a binder, and a cinnamic acid type photosensitive resin composition. Of these, photopolymerizable resins are particularly preferable. The photopolymerizable resin contains a photopolymerization initiator, a photopolymerizable monomer and a binder as basic constituent elements.

As the photosensitive resin, there are known one which can be developed with an alkaline aqueous solution and one which can be developed with an organic solvent. From the viewpoints of preventing pollution and ensuring labor safety, an alkaline aqueous solution developable resin is preferable. . The alkali developing solution for the photosensitive resin layer is a dilute aqueous solution of an alkaline substance, but also includes a solution containing a small amount of an organic solvent miscible with water. Suitable alkaline substances, suitable water-miscible organic solvents, types and concentrations of surfactants are the same as those described above. However, the processing solution for the thermoplastic resin layer and the developing solution for the photosensitive resin layer do not have to be the same, and may have different prescriptions.

The developing solution can be used as a bath solution or a spray solution. In order to remove the uncured portion of the photopolymerizable light-shielding material layer, methods such as rubbing with a rotating brush or a wet sponge in the developing solution, and irradiation with ultrasonic waves can be combined. Usually, the liquid temperature of the developing solution is preferably around room temperature to 40 ° C. It is also possible to include a water washing step after the development processing.

A coloring material such as a pigment or a dye is added to the photosensitive resin layer. All coloring materials should be dispersed substantially uniformly in the photosensitive resin layer and have a particle size of 5 μm or less, preferably 1 μm or less. When creating a color filter, 0.5
Those having a particle size of less than or equal to μm are particularly preferable.

Examples of suitable pigments or dyes are: Victoria Pure Blue BO (C.I.42
595), auramine (C.I.41000), fat black HB (C.I.26150), monolight yellow GT (C.I. pigment yellow), permanent yellow GR (C.I. pigment). Yellow 1
7), Permanent Yellow HR (C.I. Pigment Yellow 83), Permanent Carmin FBB (C.I.
I. Pigment Red 146), Hoster Balm Red ESB (CI Pigment Violet 19),
Permanent Ruby FBH (CI Pigment Red 11) Fastel Pink B Supra (CI Pigment Red 81) Monastral First Blue (CI Pigment Blue 15), Monolite
First Black B (CI Pigment Black 1) and carbon. Further suitable pigments for forming a color filter include C.I. I. Pigment Red 97, C.I. I. Pigment Red 122, C.I. I.
Pigment Red 149, C.I. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I.
I. Pigment Red 180, C.I. I. Pigment
Red 192, C.I. I. Pigment Red 215,
C. I. Pigment Green 7, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 15:
1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 22, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64 can be mentioned.

The photosensitive resin layer has a thin cover sheet on the side facing the support in order to protect it from contamination and damage during storage. The cover sheet may be made of the same or similar material as the temporary support, but it must be easily separated from the photosensitive resin layer. Suitable covering sheet materials are, for example, silicone paper, polyolefins or polytetrafluoroethylene sheets. The thickness of the cover sheet is preferably about 5 to 100 μm. Particularly preferred is a polyethylene or polypropylene film having a thickness of 10 to 30 μm.

In the photosensitive transfer material used in the present invention, a thermoplastic resin layer solution is applied on a temporary support and dried to form a thermoplastic resin layer, and then the thermoplastic resin layer is dissolved on the thermoplastic resin layer. A solution of the separation layer material composed of a non-solvent is applied and dried, and then the photosensitive resin layer is applied by a solvent that does not dissolve the separation layer and dried. Alternatively, a photosensitive resin layer is provided on another covering sheet, and both the thermoplastic resin layer and the sheet having the separation layer on the temporary support are mutually attached so that the separation layer and the photosensitive resin layer are in contact with each other. A temporary support having a thermoplastic resin layer is prepared by laminating or as another covering sheet, and the thermoplastic resin layer is
It is advantageously manufactured by laminating the photosensitive resin layer on the cover sheet and the separation layer of the sheet composed of the separation layer.

Instead of the temporary support provided with the thermoplastic resin layer by coating, a two-layer or multi-layer sheet in which a thermoplastic resin sheet and a temporary support sheet are adhered can be used. As the thermoplastic resin sheet, the above-mentioned material for the thermoplastic resin layer can be used, but in this case, a polyethylene film or a polypropylene film is particularly preferable. As a method of providing a polyethylene or polypropylene film sheet on the temporary support, polyvinyl acetate on the temporary support,
A method of applying an adhesive layer by coating and drying a solution of polyvinyl chloride, epoxy resin, polyurethane, natural rubber, synthetic rubber, etc., and laminating polyethylene, polypropylene film, etc. on this under pressure and heating, ethylene / acetic acid An adhesive composed of a mixture of vinyl copolymer, ethylene / acrylic acid ester copolymer, polyamide resin, petroleum resin, rosins, and waxes is heated and melted to be applied on a temporary support, and immediately thereafter, a polyethylene or polypropylene film. And the like, polyethylene, polypropylene, and the like in a molten state, extruded into a film by an extruder, and in the molten state, a temporary support is pressure-bonded and laminated.

If the temporary support is peeled off after the photosensitive resin layer of the photosensitive transfer material is adhered on the permanent support, the film and the human body may be electrified, and unpleasant electric shock may occur. Due to this charging, dust may be attracted from the surroundings to form an unexposed portion in the subsequent exposure process, which may cause a pinhole. Therefore, in the photosensitive transfer material used in the present invention, in order to prevent charging, a conductive layer is provided on at least one surface of the temporary support so that the surface electric resistance is 10 ¹³ Ω or less, or It is preferable to use a support that has conductivity and has a surface electric resistance of 10 ¹³ Ω or less.

To give conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method of kneading fine particles of a metal oxide or an antistatic agent is suitable. As the metal oxide, zinc oxide, titanium oxide,
At least one crystalline metal oxide selected from tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide,
And / or fine particles of a complex oxide thereof. Examples of the antistatic agent include alkyl phosphate salts as anionic surfactants (for example, Electrostripper A manufactured by Hanaoshi Soap Co., Ltd., Elenone No. 19 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., betaine series surfactants as an amphoteric surfactant). For example, Amogen K manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. and the like are polyoxyethylene fatty acid ester-based nonionic surfactants (for example, Nitsusan Nonion L manufactured by NOF CORPORATION) and polyoxyethylene alkyl. Ether type (for example, Emulgen 106, 120, 147, 420 of Kao Soap Co., Ltd.)
220, 905, 910, Nitsusan Nonion E manufactured by NOF CORPORATION, etc.) are useful. In addition, nonionic surfactants such as polyoxyethylene alkylphenol ether type, polyhydric alcohol fatty acid ester type, polyoxyethylene sorbitan fatty acid ester type and polyoxyethylene alkylamine type are used.

When a conductive layer is provided on the temporary support,
The conductive layer can be appropriately selected from known ones and used. Particularly, as the conductive substance, ZnO, TiO 2 can be used.
₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO,
A method of incorporating fine particles of at least one crystalline metal oxide selected from BaO and MoO ₃ and / or a composite oxide thereof is preferable because it exhibits conductivity that is not affected by humidity. The volume resistance of the fine particles of the crystalline metal oxide or the composite oxide thereof is preferably 10 ⁷ Ω · cm or less, and particularly preferably 10 ⁵ Ω · cm or less.

The particle size is 0.01 to 0.7 μm.
m, particularly preferably 0.02 to 0.5 μm. A method for producing fine particles of a conductive crystalline metal oxide and a composite oxide thereof is described in detail in JP-A-56-143430. A method of producing fine particles by firing and performing heat treatment in the presence of a heteroatom for improving conductivity, a second method of coexisting a heteroatom for improving conductivity when producing metal oxide fine particles by firing, Third, there is a method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing the metal fine particles by firing. Examples of containing different kinds of atoms are Al, In, etc. for ZnO, Nb, Ta, etc. for TiO2, Sb, N for SnO2.
b, halogen elements and the like. The addition amount of the heteroatom is preferably in the range of 0.01 to 30 mol%, 0.1 to 1
0 mol% is particularly preferred. The amount of conductive particles used is 0.
05g / m ² ~20g / m ² selfishness, 0.1g / m ² ~1
0 g / m ² is particularly preferred.

As a binder for these conductive layers,
Cellulose esters such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinylidene chloride, vinyl chloride, styrene, acrylonitrile, vinyl acetate, alkyl (alkyl groups C1 to C4 ) A homopolymer containing acrylate, vinylpyrrolidone or the like, a copolymer, a soluble polyester, a polycarbonate, a soluble polyamide or the like can be used. In dispersing the conductive particles in these binders, a dispersion liquid such as a titanium-based dispersant or a silane-based dispersant may be added. Further, it does not matter even if a binder crosslinking agent or the like is added.

As the titanium-based dispersant, US Pat.
69,192, 4,080,353, and the like, titanate-based coupling agents, Plane Act (trade name: manufactured by Ajinomoto Co., Inc.), and the like. Examples of known silane-based dispersants include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. It is commercially available from Shin-Etsu Chemical Co., Ltd. as a "silane coupling agent". Examples of the binder crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, epoxy crosslinking agents and the like.

The preferred conductive layer in the present invention is obtained by dispersing conductive fine particles in a binder and providing it on a support, or by subjecting the support to an undercoating treatment and depositing conductive fine particles thereon. Can be provided. In the present invention, when the conductive layer is provided on the surface of the support opposite to the photosensitive resin layer, a hydrophobic polymer layer is further formed on the conductive layer in order to improve the scratch resistance. Is preferably provided. In this case, the hydrophobic polymer layer may be applied in the form of a solution or an aqueous latex dissolved in an organic solvent, and the applied amount is 0.05 g / m 2 in dry weight.
^It is preferably about ^{2 to 1} g / m ² .

Examples of the hydrophobic polymer include cellulose ester (eg, nitrocellulose, cellulose acetate), vinyl polymers containing vinyl chloride, vinylidene chloride, vinyl acrylate and the like, and polymers such as organic solvent-soluble polyamide and polyester. . A slipping agent for imparting slipperiness, for example, an organic carboxylic acid amide described in JP-A-55-79435 may be used in this layer, and a matting agent or the like may be added. There is no problem. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer of the present invention is not substantially affected.

When an undercoat layer is provided, it is disclosed in JP-A-51-1.
35526, U.S. Pat. Nos. 3,143,421 and 3,
586, 508, 2,698,235, 3,5
67,452 and the like, vinylidene chloride-based copolymers, and diolefin-based copolymers such as butadiene as described in JP-A-51-114120, U.S. Pat. No. 3,615,556 and the like. Combined, JP-A-51-584
69, etc., glycidyl acrylate or glycidyl methacrylate containing copolymers, polyamide epichlorohydrin resins, such as those described in JP-A-48-24923, JP-A-50-395.
A maleic anhydride-containing copolymer as described in No. 36 and the like can be used.

Further, JP-A-56-82504, JP-A-56-143443, JP-A-57-104931,
JP-A-57-118242, JP-A-58-62647
The conductive layers described in JP-A No. 60-258541 and the like can also be appropriately used.

When the electroconductive layer is contained in the same or different plastic raw material as the temporary support film and coextruded at the same time when the temporary support film is extruded, the electroconductivity is excellent in adhesion and scratch resistance. Since the layer can be easily obtained, it is not necessary to provide the above-mentioned hydrophobic polymer layer or undercoat layer in this case, which is a particularly preferred embodiment of the conductive layer in the present invention. When applying the conductive layer, a usual method such as roller coating, air knife coating, gravure coating, bar coating, or curtain coating can be adopted.

When a conductive layer is provided on the surface of the temporary support on the side where the thermoplastic resin layer is not provided, in order to increase the adhesive force between the thermoplastic resin layer and the support, the temporary support is coated with, for example, glow. Surface treatment such as discharge treatment, corona treatment, UV irradiation treatment, addition of phenolic substances such as cresol novolac resin and resorcin into the thermoplastic resin layer, polyvinylidene chloride resin, styrene butadiene rubber on the temporary support It is also possible to carry out an undercoating treatment with gelatin, gelatin, or a combination of these treatments. The surface of the thermoplastic resin layer of the temporary support does not need to be subjected to any special treatment, and appropriate adhesion and releasability can be realized. Further, in order to improve the slipperiness or prevent the disadvantageous adhesion of the photosensitive resin layer to the back surface of the temporary support, the back surface of the temporary support contains a known fine particle-containing slip composition and a silicone compound. It is also useful to apply a release agent composition or the like.

The steps of the defect correcting method of the color filter of the present invention are roughly as follows. First, the covering sheet of the photosensitive transfer material is removed, and the colored photosensitive resin layer is laminated on the color filter layer having a defect to be corrected under pressure, preferably heating. The photosensitive transfer material at this time is
A colored photosensitive transfer material is selected whose color should correct the defects. The size may be such that it completely covers the defective portion. A known laminator, a vacuum laminator, a tool such as an iron, which can be partially heated and pressed, and the like can be used for bonding, and an auto-cut laminator can be used to further improve productivity. After that, the temporary support is peeled off, or while the temporary support is attached, the range including the defective portion is exposed through the substrate of the color filter layer. At this time, since light is absorbed by each pixel on the substrate, substantially only the defective colored photosensitive layer is cured without using a special mask. Only the defective portion may be irradiated with a beam light source such as a laser, or may be exposed from the colored photosensitive resin layer side through a predetermined mask.

Even if the light is exposed without passing through a mask, the colored photosensitive transfer material existing on the pixels other than the defective portion or on the black matrix is shielded by the red, green, blue, black matrix, etc. Decrease. Therefore, even if the amount of exposure required to perform sufficient curing at the defective part is given,
The degree of curing of the colored photosensitive transfer material other than the defective portion is low and can be removed by the development treatment. However, if the exposure amount is increased more than necessary, even the portion shielded by the pixels will be hardened and development will not be possible, so the exposure amount must be adjusted to an appropriate range. The range of this exposure amount can be appropriately determined by those skilled in the art, but it is more preferable to use the following method.

In order to cure only the colored photosensitive resin layer substantially corresponding to the defective portion, the red formed on the substrate in the photosensitive wavelength region of the colored photosensitive resin layer used for correction,
The light transmittance of each pixel of green, blue and black matrix is 2
% Or less. In this case, the colored photosensitive resin layer on the pixel is not substantially cured, while the colored photosensitive resin layer in the defective portion is sufficiently cured, so that only the former can be easily processed by subsequent treatment, for example, development treatment. Can be removed. If the light transmittance exceeds 2%, the colored photosensitive resin layer on the pixel may be partially cured and difficult to remove.

In order to reduce the light transmittance of each pixel to 2% or less, for example, the following method can be used. The first is a method in which a light absorber is added to the composition of each pixel in advance. A known compound can be used as the light absorber. Specifically, benzophenone derivatives (Michler's ketone, etc.), merocyanine compounds, 2-benzoylmethylene-3-methyl-β-naphthothiazoline, metal oxides (titanium oxide, zinc oxide, etc.), benzotriazole compounds, coumarin compounds Etc. can be mentioned. Among them, those having good light absorption property and having a light absorption performance of 25% or more even after heat treatment at 200 ° C. or more are preferable, and specifically, titanium oxide, zinc oxide, benzotriazole compound, coumarin type. Compounds. Among these, coumarin compounds are particularly preferable from the viewpoint of both heat resistance and light absorption. Furthermore, it is also preferable that the coumarin-based compound does not inhibit the photopolymerization of these when a multicolor pattern is formed using the photopolymerizable composition. The above-mentioned heat treatment at 200 ° C. or more is performed in order to further harden the patterned pixels when necessary when the color filter is formed.

The coumarin compound is represented by the general formula (I):
The compound shown by (II) or (III) can be mentioned.

[0044]

[Chemical 1]

Here, R ₁ and R ₂ may be the same or different and represent hydrogen, amino group, dialkylamino group, monoalkylamino group, N-substituted aminoalkyl group, halogen or alkoxy group. 1 to 4 carbon atoms as alkyl and alkoxy
Are preferred. R ₃ : represents an alkyl group having 1 to 7 carbon atoms, preferably 1 to 4 carbon atoms. R ₄ and R ₅ may be the same or different and represent hydrogen or an alkyl group having 1 to 7, preferably 1 to 4 carbon atoms. R ₆ and R ₇ may be the same or different and each represent hydrogen, an alkyl group having 1 to 7 carbon atoms, preferably 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

Specifically, 7-{{4-chloro-6- (diethylamino) -s-triazin-2-yl} amino} -3-phenylcoumarin 7-{{4-methoxy-6- (diethylamino) -S-
Triazin-2-yl} amino} -3-phenylcoumarin 7-{{4-methoxy-6- (diethylaminopropylamino) -s-triazin-2-yl} amino} -3-
Phenylcoumarin N- (γ-dimethylaminopropyl) -N ′-{3-phenylcoumarinyl- (7)} urea 3-phenyl-7- (4′-methyl-5′-n-butoxy-benzotriazolyl -2) Coumarin etc. can be mentioned. Among these, 7-{{4
-Chloro-6- (diethylamino) -s-triazine-
2-yl} amino} -3-phenylcoumarin is particularly preferred.

The second is a method of selecting an exposure wavelength for defect correction. That is, in the photosensitive wavelength region of the colored photosensitive resin layer that is brought into close contact with the defective portion, light having a wavelength at which the light transmittance of pixels of each color formed on the substrate is 2% or less is irradiated. Specifically, by exposing through an optical filter that cuts a wavelength region of 400 nm or more,
Since the degree of light shielding by the red, green, blue, and black matrix pixels, particularly the blue pixel, increases, the exposure amount can be increased and the defective portion can be sufficiently cured.

Third, a light-shielding layer having such characteristics on the back surface of the substrate in advance (for example, a layer containing the above-mentioned light absorber).
Is provided and is removed after exposure.

Then, the uncured portion of the photosensitive resin layer having a small exposure amount is removed. It is preferable to develop with a developing solution by a usual method, but it is also possible to remove mechanically. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. "Parts" represent parts by weight.

[0050]

【Example】

Example 1 A polyethylene terephthalate film temporary support having a thickness of 100 μm was coated with a coating liquid having the following formulation H1.
It was dried to provide a thermoplastic resin layer having a dry film thickness of 20 μm.

Thermoplastic resin layer formulation H1: Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) = 55 / 28.8 / 11.7 / 4.5, Weight average molecular weight = 90000) 15 parts by weight Polypropylene glycol diacrylate (average molecular weight = 822) 6.5 parts by weight Tetreethylene glycol dimethacrylate 1.5 parts by weight p-toluenesulfonamide 0.5 parts by weight benzophenone 1.0 parts by weight Methyl ethyl ketone 30 parts by weight

Next, the following formulation B1 was formed on the thermoplastic resin layer.
Applying a coating solution consisting of
An m-thick separation layer was provided.

Separation layer formulation B1: Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 130 parts by weight Polyvinylpyrrolidone (PVP manufactured by GAF Corporation, K-90) 60 parts by weight Fluorine-based surfactant (Asahi Glass Co., Ltd. Surflon S-131) 10 parts by weight Distilled water 3350 parts by weight

4 having the above-mentioned thermoplastic resin layer and separation layer
Photosensitivity of four colors of black (for Bl layer), red (for R layer), green (for G layer) and blue (for B layer), each having the formulation of Table 1 on one sheet of temporary support. Apply solution, dry,
A colored photosensitive resin layer having a dry film thickness of 2 μm was formed.

Table 1: Formulation of photosensitive layer R layer G layer B layer K layer ───────────────────────────────── --Benzyl methacrylate / 60.0 60.0 60.0 60.0 Methacrylic acid copolymer (molar ratio = 73/27 viscosity = 0.12) Pentaerythritol 43.2 43.2 43.2 43.2 Tetraacrylate Michler's ketone 2.4 2.4 2.4 2.4 2.4 2- (o-chlorophenyl 2.5 2.5 2.5 2.5 diphenylimidazole Dimer Irgacine Red BPT (Red) 5.4 --- --- --- Sudan Blue (Blue) --- 5.2 --- --- Copper Phthalocyanine (Green) --- --- 5.6 --- Carbon black (black) --- --- --- 5.6 Methyl cellosolve acetate 560 560 560 560 Methyl ethyl ketone 280 280 280 280

Further, a polypropylene (12 μm thick) covering sheet was pressure-bonded onto the photosensitive resin layer to prepare red, green, blue and black photosensitive transfer materials. The photosensitive wavelength of each photosensitive resin layer is 350 nm to 420 nm,
The main photosensitive wavelengths when an ultra-high pressure mercury lamp is used as an exposure light source are 365 nm (i line) and 405 nm (h line),
The light transmittances of the red, green and blue pixels are shown in the table below.

[0057]

Using this photosensitive transfer material, a color filter was prepared by the following method. A soda glass substrate (thickness: 1.1 mm, 30 cm × 40 cm) having a 2000 Å thick silicon oxide film on the surface was treated with an amino group-containing silane coupling agent (Shin-Etsu Chemical KBM60).
It was immersed in the 1% aqueous solution of 3) for 1 minute, washed with water and dried. On this glass substrate, the coating sheet of the red photosensitive transfer material was peeled off, and the photosensitive resin layer surface was pressurized (0.8 kg / c) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.).
m ² ), heating (130 ° C.) to bond them together, followed by peeling at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support. Next, a predetermined photomask (pixel size 40
μm × 200 μm) and exposed at an exposure dose of 50 mj / cm ² with an aligner having a 2 KW ultra-high pressure mercury lamp, and a CD (trade name of a developing solution manufactured by Fuji Hunt Electronics Technology Co., Ltd.) and water 1:10. The unnecessary portion was removed by spray development with a mixed aqueous solution, and a red pixel pattern was formed on the glass substrate. Then, on the glass substrate on which the red pixel pattern was formed, the green photosensitive transfer material was laminated in the same manner as above, peeled, exposed through a mask, and developed to form a green pixel pattern. The same process was repeated with blue and black photosensitive transfer materials to form a color filter on a transparent glass substrate. However, a black matrix mask was used during the exposure of the black photosensitive transfer material. The obtained color filter having a black matrix had no missing pixels and had good adhesion to the base.

In the same manner, when 100 color filters were prepared, three of these were found to have a defect in each pixel of the red, green and blue black matrix. 3 cm x in the area including the above-mentioned missing part
Using a photosensitive transfer material having a size of 10 cm and the same color as the missing portions, a photosensitive resin layer is placed on the color filter layer, the respective missing portions are attached using the laminator, and the temporary support is peeled off, The back surface of the substrate was exposed without passing through a mask. However, in this case, as shown in Table 2, the transmittance of the h-line of the blue pixel exceeds 2%, so that the Toshiba glass filter UVD36 is provided between the ultra-high pressure mercury lamp light source and the substrate.
C was installed to give an exposure of 100 mj / cm ² , followed by development. Red, green, blue, and black matrix pixels are formed in the missing pixels, and the filter characteristics such as transmittance and haze, flatness, and adhesion are substantially the same as the original non-defective pixel. Yes, it was confirmed that the correction was satisfactory.

Example 2 The same procedure as in Example 1 was carried out except that a photosensitive transfer sheet of each color was prepared according to the prescription of Table 3 below instead of the prescription of Table 1 of Example 1. The light transmittance of each pixel of the prepared photosensitive transfer sheet is shown in Table 4.

Table 3: Formulation of photosensitive layer R layer G layer B layer K layer ───────────────────────────────── --Benzyl methacrylate / 60.0 60.0 60.0 60.0 Methacrylic acid copolymer (molar ratio = 73/27, viscosity = 0.12) Pentaerythritol 43.2 43.2 43.2 43.2 Tetraacrylate 2- (p-methoxyphenyl) -2.0 2.0 2.0 2.0 4,6 -Bis (trischloromethyl) -s-triazine Irgasine Red BPT 5.4 --- --- --- Sudan Blue --- 5.2 --- --- Copper Phthalocyanine --- --- 5.6 --- Carbon Black --- --- --- 5.6 Zinc oxide 2.0 2.0 --- --- Methyl cellosolve acetate 560 560 560 560 Methyl ethyl ketone 280 280 280 280

[0062]

When the missing portion generated in the same manner as in Example 1 was corrected, the same good result as in Example 1 was obtained.

Comparative Example 1 A defect was repaired in the same manner as in Example 1 except that the Toshiba glass filter (UVD36c) was not installed at the time of exposure. The resin layer remained, making it difficult to use as a color filter.

Comparative Example 2 The procedure of Example 2 was repeated, except that a photosensitive transfer sheet of each color was prepared by the following formulation of Table 5 (formulation without zinc oxide) instead of the formulation of Table 3 of Example 2. went. The light transmittance of each pixel of the prepared photosensitive transfer sheet is shown in Table 6.

Table 5: Formulation of photosensitive layer R layer G layer B layer K layer ───────────────────────────────── --Benzyl methacrylate / 60.0 60.0 60.0 60.0 Methacrylic acid copolymer (molar ratio = 73/27, viscosity = 0.12) Pentaerythritol 43.2 43.2 43.2 43.2 Tetraacrylate 2- (p-methoxyphenyl) -2.0 2.0 2.0 2.0 4 , 6-Bis (trischloromethyl) -s-triazine Irgacine Red BPT 5.4 --- --- --- Sudan Blue --- 5.2 --- --- Copper Phthalocyanine --- --- 5.6- -Carbon black --- --- --- 5.6 Methyl cellosolve acetate 560 560 560 560 Methyl ethyl ketone 280 280 280 280

[0067]

The missing portion generated as in Example 1 was corrected, but when the same exposure amount as in Example 1 was applied, the i-line transmittance of the red pixel exceeded 2%. Development failure occurred. In addition, when the exposure amount was halved, no defective development occurred on the red image, but since the exposure amount was small, the repaired portion did not cure sufficiently and there was a step between the non-defective portion. It has happened.

Example 3 The same procedure as in Example 1 was carried out except that a photosensitive transfer sheet of each color was prepared according to the prescription of Table 7 below instead of the prescription of Table 1 of Example 1. The light transmittance of each pixel of the prepared photosensitive transfer sheet is as shown in Table 8.

Table 7: Formulation of photosensitive layer R layer G layer B layer K layer ───────────────────────────────── --Benzyl methacrylate / 60.0 60.0 60.0 60.0 Methacrylic acid copolymer (molar ratio = 73/27, viscosity = 0.12) Pentaerythritol 43.2 43.2 43.2 43.2 Tetraacrylate 2- (p-methoxyphenyl) -4,6-bis (trichlorme) 2.0 2.0 2.0 2.0 Chill) -s-Triazine Irgasine Red BPT 5.4 --- --- --- Sudan Blue --- 5.2 --- --- Copper Phthalocyanine --- --- 5.6 --- Carbon Black --- --- --- 5.6 7-((4-chloro-6- (diethylamino) -s-triazi 10.0 10.0 10.0 --- n-2-yl) amino) -3-phenylcoumarin methyl cellosolve acetate 560 560 560 560 Methyl ethyl ketone 280 280 280 280

[0071]

Using this photosensitive transfer material, a color filter was prepared by the following method. A soda glass substrate (thickness: 1.1 mm, 30 cm × 40 cm) having a 2000 Å thick silicon oxide film on the surface was treated with an amino group-containing silane coupling agent (Shin-Etsu Chemical KBM60).
It was immersed in the 1% aqueous solution of 3) for 1 minute, washed with water and dried. On this glass substrate, the coating sheet of the red photosensitive transfer material was peeled off, and the photosensitive resin layer surface was pressurized (0.8 kg / c) using a laminator (VP-II manufactured by Taisei Laminator Co., Ltd.).
m2), heating (130 ° C.) to bond them together, followed by peeling at the interface between the temporary support and the thermoplastic resin layer to remove the temporary support. Next, a predetermined photomask (pixel size 40
μm × 200 μm) and exposed at an exposure dose of 50 mj / cm 2 using an aligner having a 2 KW ultra-high pressure mercury lamp, and mixed 1:10 with CD (trade name of a developer manufactured by Fuji Hunt Electronics Technology Co., Ltd.) and water. An unnecessary portion was removed by spray development with an aqueous solution, and a red pixel pattern was formed on the glass substrate.

Then, on the glass substrate on which the red pixel pattern was formed, the green photosensitive transfer material was bonded in the same manner as above, peeled off, exposed through a mask and developed to form a green pixel pattern. The same process was repeated with blue and black photosensitive transfer materials to form a color filter on a transparent glass substrate. However, a black matrix mask was used during the exposure of the black photosensitive transfer material. The obtained color filter having a black matrix had no missing pixels and had good adhesion to the base. Table 9 shows the respective transmittances of i-line and h-line of red, green and blue pixels.
It was the street.

[0074]

In the same manner, when 100 color filters were prepared, three of them were found to have a defect in each pixel of the red, green and blue black matrix. 3 cm x in the area including the above-mentioned missing part
Using a photosensitive transfer material having a size of 10 cm and the same color as the missing portions, a photosensitive resin layer is placed on the color filter layer, the respective missing portions are attached using the laminator, and the temporary support is peeled off, The back surface of the substrate was exposed without passing through a mask. However, in this case, as shown in Table 9, the h-line transmittance of the blue pixel exceeds 2%, so that the Toshiba glass filter UVD36 is provided between the ultra-high pressure mercury lamp light source and the substrate.
C was installed to give an exposure of 100 mj / cm @ 2, followed by development. Red, green, blue, and black matrix pixels are formed in the missing pixels, and the filter characteristics such as transmittance and haze, flatness, and adhesion are substantially the same as the original non-defective pixel. Yes, it was confirmed that the correction was satisfactory.

Example 4 Example 1 The colored photosensitive layer having the formulation shown in Table 1 was mixed with 7-
{{4-Chloro-6- (diethylamino) -s-triazin-2-yl} amino} -3-phenylcoumarin was added so that the solid content was 8%. Example 1 using this
In the same manner as above, on the glass substrate (thickness 1.1 mm), R,
G and B color filters were produced. In this case, R,
Each pixel of G and B was subjected to heat treatment at 220 ° C. for 20 minutes to completely cure each pixel. I-line and h of each obtained color pixel
The line transmittance was as shown in Table 10.

[0077]

When the same evaluation as in Example 1 was performed below, the same good result was obtained.

Example 5 Instead of 7-{{4-chloro-6- (diethylamino) -s-triazin-2-yl} amino} -3-phenylcoumarin, 7-{{4-methoxy-6- ( The same operation as in Example 4 was performed except that diethylamino) -s-triazin-2-yl} -3-phenylcoumarin} was used. Here, the light transmittance of each color pixel is as shown in Table 11.

[0080]

The same evaluations as in Example 1 were performed below, and the same results as in Example 4 were obtained.

[0082]

The defect correction method of the color filter by the transfer method and the back exposure according to the present invention allows the defect to be easily corrected by a simple operation, and the flatness after the correction is excellent and the pixel quality is high. Therefore, the yield of color filter production can be greatly improved.

Claims (4)

[Claims] 1. A step of (1) forming red, green, blue and black matrix pixels on a substrate, and (2) coloring the same color as the missing pixel in a region including a missing part of any one of the above pixels. A step of bringing the colored photosensitive transfer material having a photosensitive resin layer into close contact, (3) exposing the area to which the colored photosensitive transfer material is in close contact through the substrate to form the colored photosensitive resin layer in the missing portion. A method of repairing defects in a color filter, which comprises a step of curing and (4) a step of removing an uncured portion of the colored photosensitive resin layer. 2. The thermoplastic resin layer according to claim 1, wherein the colored photosensitive transfer material is provided with an alkali-soluble thermoplastic resin layer, a separation layer and a colored photosensitive resin layer in this order on a temporary support. A method for correcting a defect in a color filter, which is a colored photosensitive transfer material having the smallest adhesive force between the temporary support and the temporary support. 3. The red, green, blue and black matrix pixel according to claim 1, wherein the red, green, blue and black matrix pixels contain a compound which is heat resistant and has a good light absorption property in a photosensitive wavelength region of the colored photosensitive resin layer. A characteristic color filter defect correction method. 4. The defect of a color filter according to claim 3, wherein the light transmittance of the red, green, blue and black matrix pixels in the photosensitive wavelength region of the colored photosensitive resin layer is 2% or less. How to fix.