JPH08304620A - Production of color filter - Google Patents

Abstract

PURPOSE: To obtain excellent adhesion property in a simple production process by laminating a color resin layer to a photopolymerizable transparent adhesive layer on a temporary supporting body while the adhesive layer is not hardened, and then exposing the adhesive layer in this state to harden. CONSTITUTION: A photopolymerizable transparent adhesive layer formed on a temporary supporting body is laminated with a transparent substrate by pressing and heating and the temporary supporting body is peeled. Then one color resin layer of three colors having a specified pattern formed is laminated to the photopolymerizable transparent adhesive layer by pressing and heating by using a laminator or the like. Then the transparent substrate is exposed to harden the photopolymerizable transparent adhesive layer. Then a temporary supporting body of the color resin layer is peeled. Thus, by hardening the photopolymerizable transparent adhesive layer, the adhesion property between the transparent substrate and the color resin layer can be improved, while the adhesion property of the photopolymerizable transparent adhesive layer in the area where no color resin layer is formed is lost.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, the following method has been used to manufacture a color filter. Dyeing method: A glass plate is coated with gelatin, polyvinyl alcohol, or the like, and immersed in a dye solution for dyeing. Printing method: In JP-A-6-11611, when resin ink is printed on a glass plate by flat plate offset printing, the resin ink filled in the image area formed on the rubber sheet is transferred to the cylindrical surface of the rotary blanket. A method of transferring this ink to a glass plate after repeating the operation a plurality of times is described. Pigment Dispersion Method: Japanese Patent Application Laid-Open No. 61-254905 discloses a substrate and a film body made of a polyimide containing an organic pigment in which a solution in which a pigment is dispersed in polyimide is directly coated on the substrate to form a pattern by photolithography. , A color filter comprising a film body made of non-colored polyimide formed on the film body. Also, Japanese Patent Laid-Open No. 4-212116
Japanese Unexamined Patent Publication (Kokai) No. 1 describes a method of directly applying or transferring an alkaline aqueous solution of a photosensitive coloring resin without using a photoresist, exposing and developing the same to form a pattern.

[0003]

The dyeing method has a problem in reliability because it is easily discolored by temperature and humidity.
The manufacturing process is complicated.

The printing method described in Japanese Patent Laid-Open No. 6-11611 uses a resin ink in the color filter manufacturing process, and thus has environmental problems and handling problems due to organic solvents.

According to the pigment dispersion method described in JP-A-61-254905, heat resistance and long-term stability are good,
Although cost reduction is also possible, the color resist manufacturing process is relatively complicated because the colored layer and the photoresist layer are directly applied to the substrate and dried, and the organic solvent is used as the resin solvent, which is environmentally and easy to handle. There's a problem.

Further, according to the method described in Japanese Patent Application Laid-Open No. 4-212161, the manufacturing process is simpler than the case where a resist is used, and when the transfer method is used, an organic solvent is not used and the process is dry. There is an advantage. However, when it is attempted to use a pigment-dispersed photosensitive coloring resin, there is a limit to the selection of the pigment in order to maintain good sensitivity and resolution, and depending on the blending amount of the pigment, sufficient resolution is not obtained. However, there is a problem in that the adhesiveness to the substrate is poor. If the amount of ultraviolet irradiation is increased in order to solve these problems, the exposure time becomes longer and the productivity deteriorates.

The present invention solves the above-mentioned conventional problems, is a simple dry process, has a high pattern accuracy, has good adhesion between a substrate and a colored pattern layer, and has a high productivity. The purpose is to provide.

[0008]

A method for producing a color filter according to the present invention as set forth in claim 1, wherein a photopolymerizable transparent adhesive layer formed on a temporary support is transferred to a transparent substrate and the temporary support is peeled off. , A photopolymerizable transparent adhesive is obtained by irradiating ultraviolet rays from the transparent substrate side of the laminate formed by transferring the pattern of the colored resin layer formed on another temporary support onto the photopolymerizable transparent adhesive layer. It is characterized in that the agent layer is cured.

According to a second aspect of the present invention, there is provided a method for producing a color filter, wherein a photopolymerizable transparent adhesive layer formed on a temporary support is transferred to a transparent substrate, the temporary support is peeled off, and another temporary support is formed. On a photosensitive colored resin sheet of a plurality of colors formed by forming a photosensitive colored resin layer composed of at least an alkali-soluble organic high molecular polymer, a photopolymerizable unsaturated compound, a photopolymerization initiator and a colorant on the above. Laminate each protective film,
After exposing through a negative film having a predetermined pattern drawn on the protective film surface, peeling the protective film and developing to obtain a plurality of colored pattern layers, which are then applied to the photopolymerizable transparent adhesive layer. It is characterized in that the photopolymerizable transparent adhesive layer is cured by being transferred to, and irradiated with ultraviolet rays from the transparent substrate side.

The present invention will be described in detail below. Transparent Substrate In the present invention, transparent glass is generally used, but other transparent plastic films, or S on the surface thereof, is used.
An iO ₂ film or a transparent electrode film formed of In ₂ O ₃ , ITO or the like can also be used.

Photopolymerizable Transparent Adhesive Layer The photopolymerizable transparent adhesive composition used in the present invention comprises at least (a) 100 parts by weight of an organic polymer and (b) 10 to 250 of a photopolymerizable unsaturated compound. And (c) 0.1 to 20 parts by weight of a photopolymerization initiator.

(A) Organic high molecular weight polymer: As the organic high molecular weight polymer, those having a softening temperature of 150 ° C. or lower are preferable. For example, polyolefin, a copolymer of polyolefin and α, β-unsaturated carboxylic acid. And resins crosslinked with metal ions thereof, polyvinylidene chloride and its copolymers, polyacrylonitrile, poly-N-vinylcarbazole, polyvinyl alcohol or poly-N-vinylpyrrolidone, copolyesters, copolyamides, copolymers Polyurethane, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, styrene-isoprene copolymer, butyl rubber, polyacrylic resin, polyester resin, polyamide resin (nylon) and the like are used.

Among the above, an organic high molecular polymer composed of α, β-unsaturated ethylenic monomer is particularly preferable.
Examples of the α, β-unsaturated ethylenic monomer include the following. Styrenes: styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
pn-hexylstyrene, pn-octylstyrene, p-methoxystyrene, p-phenylstyrene,
3,4-dimethylchlorostyrene and the like.

Vinylnaphthalenes such as α-vinylnaphthalene: Ethylene, propylene, butylene or C _{5 to} C ₃₀ and higher α-olefins: Vinyl halides: vinyl chloride, vinyl bromide, vinylidene chloride, fluorinated Vinyl etc.

Vinyl esters: vinyl acetate, vinyl propionate, vinyl butyrate, etc. (Meth) acrylic acid esters: methyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-octyl (meth) acrylate, (meth) Lauryl acrylate, 2-ethylhexyl (meth) acrylate, 2-chloroethyl (meth) acrylate, methyl α-chloro (meth) acrylate, phenyl (meth) acrylate,
Dimethylaminoethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate and the like.

Vinyl ethers: vinyl methyl ether, vinyl ethyl ether and the like. Vinyl ketones: vinyl ethyl ketone, vinyl ethyl ketone, etc. N-vinyl compound: N-vinylpyrrole, N-vinylpyrrolidone, N-vinylindole and the like.

Unsaturated carboxylic acid: (meth) acrylic acid,
Crotonic acid, maleic acid (anhydride), fumaric acid, itaconic acid, etc. (Meth) acrylonitrile, (meth) acrylic acid amides.

The above-mentioned monomers can be used alone or in a copolymerized form, so that the obtained organic high molecular polymer exhibits desired physical properties (softening point, glass transition point, elastic modulus, flexibility, etc.). Adjust the blending ratio. Such an organic high molecular polymer can be easily obtained by those skilled in the art by an arbitrary method such as a radical polymerization method in an organic solvent.

When the weight average molecular weight of the organic high molecular weight polymer becomes small, so-called cold flow easily occurs,
When it is rolled and stored, the resulting resin layer is wrinkled and cannot be used. On the other hand, if it becomes large, it becomes difficult to dissolve in a solvent for coating, the viscosity becomes high and the coating becomes difficult. Therefore, about 10,000 to 2,000,000 is appropriate, and preferably 50,000 to 1,000,000.

(B) Photopolymerizable unsaturated compound The photopolymerizable unsaturated compound used in the present invention is a compound represented by the following general formula and a polymerization reaction initiated by an actinic ray such as an ultraviolet ray or a usable ray. It is a photopolymerizable monomer that can be cured.

[0021]

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In (1), R ₁ represents a divalent monovalent hydrogen group, and is a monovalent hydrogen group composed of a linear, branched, alicyclic or aromatic moiety, for example, an ethylene group or a propylene group. , Neopentyl group and the like. X also represents a divalent monovalent hydrogen group, and is a monovalent hydrogen group composed of a linear, branched, alicyclic or aromatic moiety, for example,
Hexamethylene group, tolylene group, isophorone group and the like can be mentioned.

M is an integer of 5 to 100, n is an integer of 1 to 15, and A is selected from the following (2), (3) and (4).

[0024]

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[0025]

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[0026]

[Chemical 4]

(However, R ₂ , R ₃ and R ₄ represent hydrogen or a methyl group.)

As the method for producing the unsaturated compound shown in (1), any method may be adopted. For example, the disisocyanate and the diol are mixed and reacted at a ratio matching the composition ratio of the desired compound, and the terminal is terminated. After forming a urethane oligomer having an isocyanate group, a (meth) acrylate having a hydroxyl group is added and reacted with an isocyanate group at the end. At this time, if necessary, the reaction may be carried out by dissolving in an organic solvent such as ethyl acetate, methyl ethyl ketone or toluene, and a catalyst such as dibutyl tin laurate may be added. The weight average molecular weight of this compound is preferably 10,000 or less, more preferably 8,000 or less, because the amount of unsaturated groups relatively decreases and the photocurability deteriorates (photosensitivity decreases) as the weight average molecular weight increases. .

The photopolymerizable monomer used as the photopolymerizable unsaturated compound is methyl (meth) acrylate, benzyl (meth) acrylate or the like (a).
Examples thereof include monofunctional monomers, acrylic monomers having two or more functional groups, and acrylate oligomers such as urethane and polyester.

The polyfunctional monomers include the following. As the bifunctional monomer, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, quinaethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Tetrapropylene glycol di (meth) acrylate, nonapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2,2-bis [4- (acryloxydiethoxy) phenyl] propane, 2,2-bis [ 4-
(Methacryloxydiethoxy) phenyl] propane and the like.

As trifunctional monomers, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, propylene oxide modified tri (meth) acrylate. Methylolpropane tri (meth) acrylate, propylene oxide-modified pentaerythritol tri (meth) acrylate, etc.

As the tetrafunctional monomer, pentaerythritol tetra (meth) acrylate, ethylene oxide-modified pentaerythritol tetra (meth) acrylate,
Propylene oxide-modified pentaerythritol tetra (meth) acrylate and the like.

As pentafunctional or higher functional monomers, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.

When the amount of the unsaturated compound (b) in the photopolymerizable transparent adhesive composition is small, the heat resistance after exposure is insufficient, and when it is large, cold flow easily occurs.
The blending amount is preferably 10 to 250 parts by weight, more preferably 3 parts by weight, based on 100 parts by weight of the organic polymer (a).
It is 0 to 200 parts by weight. These can be used alone or in combination of two or more.

(C) Photopolymerization Initiator As the photopolymerization initiator, any photopolymerization initiator may be used as long as it can polymerize the unsaturated compound (b) by an active ray such as an ultraviolet ray or a visible ray, and it can be activated by an ultraviolet ray. Are as follows. Sulfides: Sodium methyl dicarbamate sulfide, Tetramethyl thiuram monosulfide,
Diphenyl monosulfide, dibenzothiazoyl monosulfide, disulfide and the like. Thioxanthone derivatives: thioxanthone, 2-chlorothioxanthone, diethylthioxanthone, diisopropylthioxanthone and the like. Diazo compound: hydrazone, azoisobutyronitrile,
Benzenediazonium etc. Aromatic carbonyl compound: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzophenone, dimethylaminobenzophenone, Michler's ketone, benzylanthraquinone, t-butylanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-aminoanthraquinone, 2-chloroanthraquinone, benzyl dimethyl ketal, methylphenyl glyoxylate and the like. Acetophenone derivative: 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone, α-hydroxy-α, α-dimethyl-acetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxyacetophenone, etc. . Dialkylaminobenzoic acid esters: methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, butyl p-dimethylaminobenzoate, isopropyl p-dimethylaminobenzoate and the like. Peroxides: benzoyl peroxide, di-t-butyl peroxide, dicumyl peroxide, cumene hydroperoxide and the like. Acridine derivative: 9-phenylacridine, 9-p-
Methoxyphenylacridine, 9-acetylaminoacridine, benzacridine and the like. Phenazine derivative: 9,10-dimethylbenzphenazine, 9-methylbenzphenazine, 10-methoxybenzphenazine and the like. Quinoxaline derivative: 4,4,4-methoxy-2,3-
Diphenylquinoxaline and the like. 2,4,5-Triphenylimidazoyl dimer: halogenated ketone: acylated phosphorus compound: 2,4,6-trimethylbenzoyldiphenylphosphine oxide, pivaloyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphine oxide, Terephthaloyl-bis-diphenylphosphine oxide, 1-methyl-cyclohexylcarbonyldiphenylphosphine oxide, versiteyl-diphenylphosphine oxide, 4-methylbenzoyl-phenylphosphinic acid methyl ester, 2,
4,6-Trimethylbenzoyl-phosphinic acid diethyl ester and the like.

Further, as the one activated by visible light,
2-nitrofluorene, 2,4,6-triphenylpyrylium tetrafluoride salt, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 3,3-carbonylbiscoumarin, thio Examples include Michler's ketone.

If the amount of the photopolymerization initiator (c) in the photopolymerizable transparent adhesive composition is too small, the curing time becomes long, or
Alternatively, the image cannot be formed because it is not sufficiently cured. If the amount is too large, the cured resin will turn yellow or become brittle, so 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the above organic polymer (a). Further, although these photopolymerization initiators may be used alone, such as triethanolamine and dialkyl amino acid benzoates,
It is preferable to use it together with the initiation aid mainly composed of an amine compound because the curing speed becomes faster and the oxygen inhibition decreases.

(D) Other additives The following additives can be added to the photopolymerizable transparent adhesive composition. Solvent: Water Various alcohols; methanol, ethanol, n-propanol, isopropanol, cyclohexanol, ethylene glycol, glycerin and the like. Ketones; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, etc. Various hydrocarbons; n-hexane, benzene, toluene,
Xylene, cyclohexane, etc. Halogenated hydrocarbons; trichloroethane, trichloroethylene, dichlorobenzene, etc. Cellosolves; methyl cellosolve, ethyl cellosolve and the like. In addition, phenols, esters, nitrogen compounds, etc. These may be used alone or as a mixed solvent of two or more kinds.

Plasticizer: dioctyl phthalate, triethylene glycol diacetate, p-toluene sulfonamide, N-ethyltoluene sulfonamide and the like. Thermal polymerization inhibitor: hydroquinone, p-methoxyphenol, etc. In addition, UV absorbers, antioxidants, etc.

The photopolymerizable transparent adhesive layer can be obtained by applying the above-mentioned photopolymerizable transparent adhesive composition to a temporary support and drying it. Various materials can be used as the temporary support as long as they are chemically and thermally stable. For example, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyolefins such as polyethylene and polypropylene, polyvinyl halides such as polyvinyl chloride and polyvinylidene chloride, unstretched or stretched films such as polyamide, polyimide and polycarbonate. However, a biaxially stretched polyethylene terephthalate film, which is relatively inexpensive, easily available, and stable in mechanical and thermal properties, is particularly preferable.

Further, these temporary supports may be subjected to a mold release treatment in order to improve the releasability from the resin layer at the time of peeling. The release treatment can be performed by a known method,
A typical method is chemical treatment with a silicone-based or fluorine-based release agent.

When the photopolymerizable transparent adhesive composition on the temporary support is stored as a roll without being covered with a protective film, a release treatment is applied to the opposite surface on which the above composition is laminated. Is good. When using a protective film, the one used as the temporary support can be used as the protective film,
In order to improve the releasability of the protective film at the time of peeling, it is preferable to use a film having a release layer made of silicone or fluorine on the surface in contact with the adhesive composition layer.

Various methods such as a roll coater, a gravure coater, a comma coater, a blade coater, a knife coater, a kiss roll coater, a Mayer bar coater, and a die coater can be used to apply the photopolymerizable transparent adhesive composition to the temporary support. A coater or printing method can be adopted.

The drying temperature may be selected depending on the type of resin, solvent and temporary support to be used, but if it is too high, thermal strain or bubbles occur in the resin, and if it is too low, the amount of solvent remaining increases. Or the drying time will be very long, so 30 ~
180 ° C is preferred.

The thickness of the photopolymerizable transparent adhesive composition is not particularly limited, but if it is too thick, the exposure time becomes long and the transparency decreases. On the other hand, if it is too thin, sufficient adhesiveness cannot be obtained, so the range of 0.1 to 100 μm is preferable.

The colored resin used in the manufacturing method according to claim 1 will be described. Colored Resin Layer The conventionally known pigments and dyes can be used in the colored resin layer used in the present invention, but they are composed of a colorant and resin of any one color of red, green, blue and other colors, and at least the above three colors are used. Multiple colored resin layers are used. (A) Colorant Examples of red color include rhodamine B lake, cadmium red, red iron oxide, chrome vermillion, pyrazolone red, resole red, red lead, watching red, quinacridone red, and the like. Examples of green color include phthalocyanine green, emerald green, and Guinea green. Examples of blue include ultramarine blue, cobalt blue, cerulean blue, manganese blue, phthalocyanine blue, and the like.

If the blending amount of the colorant is too small, sufficient coloring cannot be obtained, and if the blending amount is too large, the coating film becomes brittle.
The amount is preferably 0.1 to 300 parts by weight with respect to 100 parts by weight of the resin.

(B) Resin As the resin, various thermoplastic and thermosetting natural resins and synthetic resins such as phenol resin, amino resin, epoxy resin, polyurethane resin, vinyl resin, acrylic resin, alkyd resin, unsaturated polyester are used. Resin, cellulose, rosin, etc. are mentioned, and these can be used individually or in mixture of 2 or more types.

(Other Additives) In addition to the above, various organic solvents, plasticizers, antioxidants, defoamers, leveling agents, cross-linking agents and the like may be added as required.

The above-mentioned colored resin composition is applied to 1 sheet of temporary support.
There are a method of preparing and using a plurality of colors that are applied over the entire surface with a color, or a method of applying and drying a desired pattern composed of a plurality of different colors on one temporary support by printing or the like. Laminate a protective film if necessary. To coat the entire surface of the temporary support with the colored resin composition, a roll coater, a gravure coater, a comma coater, a blade coater,
There is a method using various coaters such as a knife coater, a kiss roll coater, a Meyer bar coater, and a die coater. Further, printing is suitable for forming different pattern layers for each color. When the printing method is adopted, relief printing, intaglio printing, lithographic printing, gravure printing, offset printing, flexographic printing, screen printing, electrostatic printing, inkjet method and the like can be mentioned.

The thickness of the colored resin layer is not particularly limited, but if it is too thick, it becomes difficult to apply or dry, and if it is too thin, a sufficient color density cannot be obtained.
The range of 0 μm is desirable.

Next, the photosensitive colored resin layer used in the manufacturing method according to claim 2 will be described. Photosensitive Colored Resin Layer The photosensitive colored resin layer used in the present invention comprises (a) 100 parts by weight of an alkali-soluble organic polymer, (b) 10 to 250 parts by weight of a photopolymerizable unsaturated compound, and (c) a light source. A sheet in which a photosensitive colored resin composition comprising 0.1 to 20 parts by weight of a polymerization initiator and 0.1 to 300 parts by weight of (d) a colorant is applied to a temporary support, dried, and a protective film is superposed thereon. It can be obtained by exposing a body as a body through a negative film on which a desired pattern is drawn, peeling off the protective film and developing.

(A) Alkali-soluble organic high-molecular polymer The alkali-soluble organic high-molecular polymer is one that is soluble or swellable in an alkaline aqueous solution, and is an α, β-unsaturated ethylenic single polymer containing a carboxyl group. 10 to 40
It is a copolymer having a weight average molecular weight of 20,000 to 500,000 containing 60% to 90% by weight of other α, β-unsaturated ethylenic monomer as a constituent component.

The α, β-unsaturated ethylene-based monomer containing a carboxyl group may be a monomer containing a carboxyl group and copolymerizable with the α, β-unsaturated ethylene-based monomer. For example, unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid may be mentioned. As the other α, β-unsaturated ethylenic monomer, the same ones as those described in (a) the organic high molecular weight polymer used in the photopolymerizable transparent adhesive layer can be used. .

When the amount of the α, β-unsaturated ethylenic monomer containing a carboxyl group in the constituents of the alkali-soluble organic polymer copolymer is too small, it becomes insoluble in the alkaline aqueous solution, and therefore development with the alkaline aqueous solution is carried out. However, if the amount is too large, the compatibility with the coating solvent or other components decreases and the developability also deteriorates. Therefore, the range is 10 to 40% by weight, preferably 15 to 35% by weight. The amount of other constituents is 60 to 90% by weight.

When the weight-average molecular weight of the alkali-soluble organic polymer copolymer becomes small, cold flow easily occurs, and when it is rolled and stored, the photosensitive coloring layer is wrinkled and cannot be used. On the other hand, if it becomes large, it becomes difficult to dissolve in an alkaline aqueous solution, and it is difficult to develop and the resolution is deteriorated. It is preferably 50,000 to 300,000.

(B) Photopolymerizable unsaturated compound The photopolymerizable unsaturated compound used in the photosensitive colored resin composition is the (b) photopolymerizable unsaturated compound used in the photopolymerizable transparent adhesive layer sheet. The same as those described in the compound can be used alone or in combination of two or more kinds. If the amount of the unsaturated compound in the photosensitive colored resin composition is small, the surface hardness after exposure will be insufficient, and if it is large, cold flow will easily occur. Therefore, the amount of the unsaturated compound is 100% by weight of the alkali-soluble organic polymer copolymer. The amount is preferably 10 to 250 parts by weight, and more preferably 30 to 200 parts by weight.

(C) Photopolymerization Initiator The photopolymerization initiator used in the photosensitive colored resin composition may be the same as the (C) photopolymerization initiator used in the photopolymerizable transparent adhesive layer sheet. If the compounding amount of the photopolymerization initiator is too small, the curing time becomes long, or the image cannot be formed because it is not sufficiently cured. If the amount is too large, the cured resin will turn yellow or become brittle, so 0.1 to 20 parts by weight is preferable with respect to 100 parts by weight of the alkali-soluble organic polymer copolymer.

(D) Coloring agent As the coloring agent, the one used in the manufacturing method described in claim 1 can be used, and the compounding amount thereof is also the same as in the case described in claim 1.

(E) Other additives If necessary, various solvents, plasticizers, thermal polymerization inhibitors, stabilizers, UV absorbers, antioxidants, etc. are added as diluents to the photosensitive colored resin composition. can do. Specific examples thereof include the same as (other additives) used for the photopolymerizable transparent adhesive layer sheet.

The above-mentioned photosensitive colored resin composition is applied to a temporary support and dried to laminate a protective film. As the material of the temporary support, the coating method, the drying conditions, the material of the protective film, and the like, those described for the photopolymerizable transparent adhesive layer sheet can be adopted. The thickness of the photosensitive colored resin composition is not particularly limited, but if it is too thick, the exposure time becomes long, and if it is too thin, sufficient color density cannot be obtained, so 0.1-100 μm is preferable.

The sheet thus obtained is exposed through a negative film on which a predetermined pattern is drawn, the protective film is peeled off and developed to develop a photosensitive colored resin on which a predetermined pattern is displayed. A layer is obtained. Here, exposure with a protective film provided prevents the sensitivity from decreasing due to oxygen inhibition.

The light source for exposure is not particularly limited, and any conventionally known light source can be used. For example,
An ultra-high pressure mercury lamp and a metal halide lamp are suitable. The developer used for development is not particularly limited, but an aqueous solution of sodium carbonate having a concentration of 0.5 to 5% by weight is preferable. The developing device used for the development may be a conventionally used one.

Method for producing color filter In the method for producing a color filter according to claim 1, after the photopolymerizable transparent adhesive layer formed on the temporary support is bonded to the transparent substrate while applying pressure and heat with a laminator or the like. Then, the temporary support is peeled off. The roll temperature of the laminator is determined by the heat resistance of the temporary support used, the softening temperature of the photopolymerizable transparent adhesive layer, etc., but is generally preferably in the range of 30 ° C to 200 ° C, and the pressure applied is 49 ° C to 49 ° C. 980 KPa (0.
5 to 10 kg / cm ² ) is suitable.

Next, a red color on which a predetermined pattern is formed,
Each of the green and blue colored resin layers or one colored resin layer in which a predetermined pattern of the above three colors is formed is attached to the photopolymerizable transparent adhesive layer while applying pressure and heat with a laminator or the like. . When using three colored resin layers having three colors formed on different temporary supports, the temporary supports are attached in order and the temporary supports are peeled off, and only the temporary support of the colored resin layers finally attached is peeled off. Leave without. This bonding may be performed under the same conditions as when bonding the photopolymerizable transparent adhesive layer to the transparent substrate.

Then, the photopolymerizable transparent adhesive layer is cured by exposing from the transparent substrate side. The light source for exposure may be one that has been conventionally used, and for example, an ultra-high pressure mercury lamp, a metal halide lamp or the like is preferably used. The irradiation amount is not particularly limited as long as the coating film is sufficiently cured, but if it is too small, the curing will be insufficient, and if it is too large, unexpected yellowing may occur.
00 mJ / cm ² is preferable.

Then, the temporary support for the colored resin layer is peeled off. By curing the photopolymerizable transparent adhesive layer, the adhesion between the transparent substrate and the colored resin layer is made strong, and at the same time, the adhesion of the photopolymerizable transparent adhesive layer in the portion where the colored resin layer is not formed There is no sex.

In the method for producing a color filter according to claim 2, the colored resin layer used in the second step according to claim 1 is at least an alkali-soluble organic high molecular polymer,
A photosensitive colored resin comprising a photopolymerizable unsaturated compound, a photopolymerization initiator and a coloring agent, a protective film is laminated on the photosensitive colored resin layer, and a negative film having a predetermined pattern is formed on the protective film. A colored pattern layer obtained by exposing through a film, peeling off the protective film and developing is used.

Here, the red, green, and blue colored resin layers each having a predetermined colored pattern layer formed on the temporary support are superposed on the photopolymerizable transparent adhesive layer, and pressed and heated by a laminator or the like. And stick together. Others are the same as those described in claim 1.

[0070]

According to the method of manufacturing a color filter of the first aspect, a dry process in which an organic solvent is not required in the process of forming a pattern on a transparent substrate is performed. Therefore, there is no environmental or handling problem due to the organic solvent. The photopolymerizable transparent adhesive layer on the temporary support is tacky in the uncured state, and when the colored resin layer is attached to this and exposed, the adhesiveness after curing is good, and the colored resin layer is not laminated. The part of the photopolymerizable transparent adhesive layer loses its tackiness.

In order to form a colored pattern on the photopolymerizable transparent adhesive layer, a pattern layer made of a colored resin previously formed on another temporary support is simply transferred by lamination or the like. Can be greatly simplified and productivity is improved. Furthermore, when a colored resin consisting of three colors of red, green and blue is printed on one temporary support to form a colored pattern layer, the photopolymerizable transparent adhesive layer is laminated only once. Therefore, the manufacturing process can be greatly simplified.

In the method for producing a color filter according to claim 2, since the colored pattern is formed by laminating a protective film on a photosensitive colored layer coated on a temporary support and exposing through the protective film, the sensitivity is lowered by oxygen inhibition. It can be prevented.

[0073]

[0074]

EXAMPLES Examples of the method for producing a color filter of the present invention will be described below. (Example 1) (a) Preparation of photopolymerizable transparent adhesive layer A polyethylene terephthalate film (manufactured by Teijin Ltd., trade name "S type", thickness 25 μm) was uniformly coated with the following photopolymerizable transparent adhesive composition using a comma coater. Applied to 100
It was dried at 0 ° C. for 1 minute to prepare a photopolymerizable transparent adhesive layer having a thickness of 10 μm. Another polyethylene terephthalate film (manufactured by Teijin Ltd., trade name “S-31 type”, thickness 25 μm) having one surface subjected to release treatment was attached to this photopolymerizable transparent adhesive layer, and wound into a roll.

[Photopolymerizable transparent adhesive layer] 100 parts by weight of organic polymer (polymethylmethacrylate, manufactured by Sumitomo Chemical Co., Ltd., trade name "Sumipec L06" molecular weight 60,000) Photopolymerizable unsaturated compound 50 parts by weight Part (oligoester acrylate, Towa Gosei Co., Ltd., trade name "M-6100") Photopolymerizable unsaturated compound 50 parts by weight (oligoester acrylate, Towa Gosei Co., Ltd. trade name "M-8030") Photopolymerization initiation Agent 4 parts by weight (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BAS F, trade name "Lucirin TPO") Methyl ethyl ketone 330 parts by weight

(B) Preparation of Colored Resin Layer A polyethylene terephthalate film (manufactured by Teijin Ltd., trade name "S type", thickness 15 μm) was coated with the following colored resin composition by offset gravure to give three colors of red, green and blue. 1
Print each color in a predetermined mosaic pattern, 1 at 100 ℃
After drying for 3 minutes, three colored resin layers of different colors having a thickness of 1 μm were prepared. Onto this colored resin layer, another polyethylene terephthalate film (manufactured by Teijin Ltd., trade name “S-31 type”, thickness 25 μm) which had been subjected to release treatment on one side was laminated and wound into a roll.

[Colored Resin Composition] 100 parts by weight of organic polymer (methacrylate / butyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid, weight ratio = 31/31/13/25, weight average molecular weight = 10 000) Pigment Red pigment (quinacridone red) 10 parts by weight Blue pigment (copper phthalocyanine blue) 10 parts by weight Green pigment (phthalocyanine green) 10 parts by weight Solvent (methyl ethyl ketone) 400 parts by weight

(C) Preparation of color filter While peeling off the protective film of the photopolymerizable transparent adhesive layer, the layer was placed on a transparent glass substrate by using a laminator 1
After laminating at a rate of 1.2 m / min at 20 ° C. and a pressure of 5 kg / cm ² , the polyethylene terephthalate film of the temporary support was peeled off. Next, the colored resin layer (b) is red,
While peeling off the protective film in the order of green and blue, the protective film was laminated on the photopolymerizable transparent adhesive layer using a laminator under the same conditions as above. At the time of bonding, the temporary supports of the red and green colored resin layers were peeled off, but only the final blue temporary support was left.

Next, the entire surface of the transparent glass substrate is irradiated with ultraviolet rays having an intensity of 500 mJ / cm ² from the back side of the transparent glass substrate to cure the photopolymerizable transparent adhesive layer to form a photopolymerizable transparent adhesive sheet. It was made. Then, the temporary support used for the blue colored resin layer was peeled off to obtain a color filter in which a lattice-shaped pattern composed of three colors of red, green and blue was formed.

According to the above manufacturing method, the steps are simple,
Moreover, it is possible to manufacture color filters continuously,
It was excellent in productivity. The color filter obtained by this manufacturing method was satisfactory with no defects in any pattern. Further, the exposed surface of the photopolymerizable transparent adhesive layer was hardened and had no tackiness, and it was hard to be stained and easy to handle. Furthermore, even if the surface of the colored pattern layer was strongly rubbed with a finger, it did not come off.

Example 2 (a) The same photopolymerizable transparent adhesive layer as used in Example 1 was used. Three polyethylene terephthalate films (manufactured by Teijin Ltd., trade name "S type", thickness 15μ
m) was uniformly coated with the same three colored resin compositions used in Example 1 by a gravure coater,
It was dried at 100 ° C. for 1 minute to prepare three colored resin layers having a thickness of 1 μm and different in color. These three colored resin layers were laminated one by one on the photopolymerizable transparent adhesive layer by a laminator under the same conditions as in Example 1 while peeling off the protective film and the temporary support, and finally laminated. Only the temporary support of the adhesive resin layer was left without peeling.

Next, from the back side of the transparent glass substrate, the entire surface was irradiated with ultraviolet rays from an ultrahigh pressure mercury lamp under the same conditions as in Example 1 to cure the photopolymerizable transparent adhesive layer. Then, the remaining temporary support was peeled off to obtain a color filter in which a grid pattern was formed in three colors of red, green and blue.

The color filter manufacturing method and the obtained color filter in this example had the same effects and performances as in Example 1.

(Example 3) (a) The same photopolymerizable transparent adhesive layer as used in Example 1 was used. (B) Preparation of Photosensitive Colored Resin Layer Three polyethylene terephthalate films (manufactured by Teijin Ltd., trade name “S type”, thickness 15 μm) were uniformly coated with the following three colored photosensitive color resin compositions by a gravure coater. Coating, drying at 100 ℃ for 1 minute, thickness 1μ
Three photosensitive colored resin layers having different colors were prepared by m.

[Photosensitive colored resin composition] 100 parts by weight of an alkali-soluble organic polymer (methyl acrylate / methyl methacrylate / 2-ethylhexyl acrylate / methacrylic acid, weight ratio = 31/31/13/25, Weight average molecular weight 100000) Photopolymerizable unsaturated compound 67 parts by weight (trimethylolpropane triacrylate) Photopolymerization initiator 4 parts by weight (2,4,6-trimethylbenzoyldiphenylphosphine oxide, manufactured by BAS F, trade name) "Lucirin TPO") Pigment Red pigment (quinacridone red) 10 parts by weight Blue pigment (copper phthalocyanine blue) 10 parts by weight Green pigment (phthalocyanine green) 10 parts by weight Solvent (methyl ethyl ketone) 400 parts by weight

On this colored resin layer, another polyethylene terephthalate film (manufactured by Teijin Ltd., trade name "S-31 type", thickness 25 μm) which has been subjected to release treatment on one side as a protective film
m), and was wound into a roll.

Next, the above-mentioned photosensitive colored resin layer was cut into a certain size, and 500 mJ / c was cut by an ultra-high pressure mercury lamp through each negative film in the order of red, green and blue.
Irradiation with ultraviolet light having an intensity of m ² was performed. After that, the protective film of the photosensitive colored resin layer was peeled off, and developed with a 1% sodium carbonate aqueous solution at 30 ° C. to develop red, green, and blue.
I got a pattern.

(C) Preparation of Color Filter While peeling off the protective film of the photopolymerizable transparent adhesive layer, the photopolymerizable transparent adhesive layer was placed on a transparent glass substrate using a laminator at 120 ° C. and 5 kg / cm ² At the pressure of 1.
After bonding at a speed of 2 m / min, the polyethylene terephthalate film of the temporary support was peeled off. Next, the photosensitive colored resin layer (b) was laminated on the photopolymerizable transparent adhesive layer with a laminator under the same conditions as above while peeling off the protective film in the order of red, green and blue. At the time of bonding, the temporary supports of the red and green photosensitive colored resin layers were peeled off, but only the last blue temporary support was left without being peeled off. Next, from the back side of the transparent glass substrate, the entire surface was irradiated with ultraviolet rays from an ultrahigh pressure mercury lamp under the same conditions as in Example 1 to cure the photopolymerizable transparent adhesive layer. Then, the temporary support used for the blue colored resin layer was peeled off to obtain a color filter in which a lattice-shaped pattern composed of three colors of red, green and blue was formed.

The method for producing this color filter and the obtained color filter had the same effects and performances as in Example 1.

(Comparative Example) Example 3 was formed on a transparent glass substrate.
Of the same photosensitive colored resin composition as used in 1., the red resin was first uniformly applied with a roll coater and dried at 100 ° C. for 1 minute. Then, after irradiating with ultraviolet rays having an intensity of 500 mJ / cm ² through a predetermined negative film with an ultra-high pressure mercury lamp, it was developed with a 1% sodium carbonate aqueous solution at 30 ° C. to obtain a red colored pattern layer. For each of green and blue, form a colored pattern layer in the same manner,
Finally, a color filter in which three colors of red, green and blue were formed in a grid pattern was obtained.

When the surface of the colored pattern layer of the obtained color filter was strongly rubbed with a finger, a part of the pattern was peeled off. Further, according to this method, a coating solution containing a solvent has to be applied and dried for each color, which complicates the process and requires much labor, resulting in poor productivity.

[0092]

The method for producing a color filter of the present invention has the following effects because of the above constitution. According to the method for producing a color filter according to claim 1, the colored resin layer is attached in a state where the photopolymerizable transparent adhesive layer on the temporary support is uncured, and the state is exposed and cured in that state, which is excellent adhesion. Sex is obtained. Since the colored pattern can be obtained only by transferring the colored pattern layer formed on the temporary support to the photopolymerizable transparent adhesive layer, the manufacturing process is simplified and the productivity is improved. Furthermore, since no organic solvent is used, there are no environmental or handling problems. Further, when a colored resin consisting of three colors of red, green, and blue is printed on one temporary support to form a colored pattern layer, the lamination work on the photopolymerizable transparent adhesive layer is performed once. Well, the manufacturing process is greatly simplified.

According to the method for producing a color filter of claim 2, since a protective film is laminated on the photosensitive colored pattern layer formed on the temporary support, and this is exposed to light, the protective film reduces the sensitivity due to oxygen inhibition. It can be prevented.

Claims (2)

[Claims] 1. A photopolymerizable transparent adhesive layer formed on a temporary support is transferred to a transparent substrate to peel off the temporary support, and a pattern of a colored resin layer formed on another temporary support is described above. A method for producing a color filter, characterized in that the photopolymerizable transparent adhesive layer is cured by irradiating ultraviolet rays from the transparent substrate side of the laminate formed by transferring the photopolymerizable transparent adhesive layer. 2. A photopolymerizable transparent adhesive layer formed on a temporary support is transferred to a transparent substrate to peel off the temporary support, and at least an alkali-soluble organic polymer polymer on another temporary support. A photopolymerizable unsaturated compound, a photopolymerization initiator and a protective film is laminated on each of the protective films on a photosensitive colored resin sheet of a plurality of colors formed by forming a photosensitive colored resin layer consisting of a colorant, on the protective film surface. After exposing through a negative film having a predetermined pattern drawn, to obtain a plurality of colored pattern layers by peeling off and developing the protective film, transferred to the photopolymerizable transparent adhesive layer, A method for producing a color filter, which comprises curing the photopolymerizable transparent adhesive layer by irradiating ultraviolet rays from the transparent substrate side.