JPH08211222A - Production of color filter - Google Patents

Abstract

PURPOSE: To enable exposure and development for a single photosensitive resin layer without requiring a base film as an oxygen-preventing film, to continuously peel a base film after a transfer process so that cutting of a transfer film or production of dust due to cutting can be prevented by using a transfer film containing a photosensitive resin layer having oxygen-trouble-resistance. CONSTITUTION: In this method of producing a color filter, color pixels are formed by transferring a photosensitive resin film colored in one color to a transparent substrate such as a transparent plastic or glass substrate and then forming a pattern by a photolithographic method. In this method, a film having oxygen-trouble-resistance is used for the photosensitive resin film. Also, a transfer film comprising a base film, cushion layer and photosensitive resin film colored in one color and having resistance against failure caused by oxygen is continuously supplied from a roll state onto a transparent substrate and laminated. After lamination, the base film and the cushion layer of the transfer film are peeled without cutting.

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 color liquid crystal display device or the like.

[0002]

2. Description of the Related Art Liquid crystal display (hereinafter abbreviated as LCD)
Taking advantage of its thinness, small size, and low power consumption, is currently used for display parts of watches, calculators, TVs, personal computers and the like. Furthermore, in recent years, color LCDs have been developed and OA / AV
It has begun to be used in many applications such as navigation systems and viewfinders mainly for devices, and the market is expected to expand rapidly in the future.

A color filter for displaying an LCD in color is R (red) on a substrate 2 such as a glass plate on which a BM (black matrix) 1 having a grid pattern is formed.
Color pixel 3 consisting of G (green) and B (blue) (approximately 100 x 1
(00 × 2 μm), and a transparent overcoat layer (OC) 4 is formed thereon. Reference numeral 5 is a polarizing plate, and 6 is an ITO electrode.

A color LCD has a color filter 7 as an LC.
The display screen can be colored by being installed inside D and transmitting the backlight light to the color filter. 8 is an alignment film, 9 is a liquid crystal, 10 is a seal material, 11 is a top coat layer, 12 is an ITO electrode, 13 is a substrate such as a glass plate, 14
Is a polarizing plate.

At present, color filters are mainly manufactured by the dyeing method. However, in this method, it is necessary to repeat the process of applying a transparent photosensitive resin on a glass substrate, forming pixels by drying, exposing and developing, dyeing with a dye, and then forming a color mixing prevention layer three times. Therefore, the number of steps is large and the cost is high. Further, since a dye is used as a colorant, there is a drawback that the reliability (weather resistance / heat resistance), which is an important subject of the color filter, is deteriorated.
Therefore, some color filters using a pigment as a colorant have been proposed, and among them, there are an electrodeposition method, a printing method, and a photolithography method (photolithography method).

However, the electrodeposition method requires the formation of an electrode pattern (1) the degree of freedom of the pattern is small,
(2) The cost is high, and the printing method has problems that (1) it is difficult to align a large-sized substrate and the resolution is low, so it is difficult to miniaturize, and (2) the flatness of the pattern is poor. The photolithography method is considered to be the mainstream. A liquid resist and a film are considered for the photolithography method. In the liquid resist, color pixels are formed by applying a varnish in which a pigment is dispersed in a photosensitive resin on a glass substrate with a spinner, drying, exposing, and developing. On the other hand, the film is a varnish formed into a film like the photosensitive film for printed boards, and after being laminated on a substrate, color pixels are formed by exposure and development.

[0007]

Film Transfer Method The transfer film used in the color filter manufacturing method has a three-layer structure of a base film, a photosensitive resin layer containing a pigment, and a cover film. At the time of use, the cover film is peeled off, and the two layers of the photosensitive resin layer and the base film are transferred onto the substrate glass. Since the conventional photosensitive resin causes oxygen damage, the upper base film cannot be peeled off until the end of exposure. On the other hand, since the transfer film is supplied by a continuous roll, it is necessary to cut the film after transfer. Since color filters are usually manufactured in a high-level clean room, film cutting is accompanied by dust generation and adversely affects the manufacturing process.
The present invention is a color suitable for a continuous process in a clean room.
A method for manufacturing a filter is provided.

[0008]

The present invention is a transfer film suitable for a continuous process and a color filter manufacturing method using the transfer film. That is, in the color filter manufacturing method by the film transfer method, it is a method of supplying a transfer film suitable for mass production and a continuous process, and a color filter manufacturing method using these.

The present invention is a method of manufacturing a color filter in which a colored pixel is formed by transferring a photosensitive resin film colored in one color onto a transparent substrate such as a transparent plastic or glass substrate and forming a pattern by a photolithography method. In the method, a film having oxygen resistance is used as the photosensitive resin film, which is a method for producing a color filter.

Further, according to the present invention, a base film, a cushion layer, and a transfer film in which a photosensitive resin film colored in one color having oxygen resistance is sequentially laminated are laminated on a transparent substrate to form a base film for the transfer film. Manufacture of a color filter characterized in that the cushion layer is peeled off, and a colored pixel is formed a predetermined number of times to form a pattern by a photolithography method of exposing and developing a photosensitive resin film colored in one color having oxygen resistance, which is exposed and developed. Is the law.

Further, according to the present invention, a transfer film obtained by successively laminating a base film, a cushion layer, and a photosensitive resin film colored in one color having an oxygen damage resistance on a transparent substrate is continuously supplied in a roll form. After lamination, the base film of the transfer film and the cushion layer are continuously peeled off without cutting after the lamination is completed, for example, the color filter is peeled off by continuously winding the roll film of the base film of the transfer film and the cushion layer after the lamination is completed. Is a manufacturing method of.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a transfer film for producing a color filter containing a colored photosensitive resin layer having oxygen resistance which is suitable for a continuous process in a clean room is used. The transfer film for producing a color filter containing a colored photosensitive resin layer having oxygen resistance is preferably a laminate of a base film, a cushion layer, a colored photosensitive resin layer and a cover film in order, and a permanent support. After adhering the colored photosensitive resin layer to the transparent substrate which is, it can be peeled off at the interface between the cushion layer and the colored photosensitive resin layer,
After the base film and the cushion layer are peeled off, the colored resin pattern can be formed on the transparent substrate, which is a permanent support, by exposing through a photomask or the like and developing. As a result, when transferring the photosensitive resin layer,
Prevents transfer defects and deterioration of image flatness due to unevenness due to already formed pixels or a black matrix on the permanent support, and the cushion layer is well peeled from the colored photosensitive layer, and after development, the pixel A color filter having good flatness can be obtained.

As the base film, one that is chemically and thermally stable and can be formed into a sheet or plate can be used. Specific examples include polyolefins such as polyethylene and polypropylene, polyvinyl halides such as polyvinyl chloride and polyvinylidene chloride, cellulose derivatives such as cellulose acetate, nitrocellulose and cellophane, polyamides, polystyrene, polycarbonate and polyimides. . Of these, particularly preferred is biaxially stretched polyethylene terephthalate, which is excellent in dimensional stability and permeability. Base film thickness is 6-1
00 μm is preferable. When the thickness is 6 μm or less, the surface roughness of the laminating roll or the like during laminating is adjusted to the underlying cushion layer,
This is because the surface of the colored photosensitive resin layer may be roughened by being transferred to the colored photosensitive resin layer.

The colored photosensitive resin layer is a photosensitive resin composition in which a pigment is dispersed and is used in the form of a film.
Examples of the photosensitive resin include (1) acid value of 20 to 30
0, a resin having a weight average molecular weight of 1,500 to 200,000, (2) a monomer having at least one photopolymerizable unsaturated bond in the molecule, and (3) a photosensitive resin composition containing a photoinitiator is used. To be

(1) The resin having an acid value of 20 to 300 and a weight average molecular weight of 1,500 to 200,000 is not particularly limited as long as the acid value and the weight average molecular weight are within this range. A typical example thereof is a copolymer of a carboxyl group-containing polymerizable monomer such as acrylic acid, methacrylic acid or itaconic acid and a polymerizable monomer such as acrylic acid ester, methacrylic acid ester or styrene.

(2) Monomers having at least one photopolymerizable unsaturated bond in the molecule include, for example, methyl methacrylate, benzyl methacrylate, butoxyethyl methacrylate, butoxyethyl acrylate, butoxytriethylene glycol acrylate, ECH (epichlorohydrin). Modified butyl acrylate, dicyclopentanyl acrylate, EO (ethylene oxide) modified dicyclopentenyl acrylate, N, N-dimethylaminoethyl methacrylate, ethyldiethylene glycol acrylate, 2-ethylhexyl acrylate, glycerol methacrylate, heptadecafluorodecyl acrylate, 2-hydroxy Ethyl methacrylate, caprolactone-modified 2-hydroxyethyl acrylate, isobornyl acrylate , Methoxydipropylene glycol acrylate, methoxylated cyclodecatriene acrylate, phenoxyhexaethylene glycol acrylate, EO modified phosphate acrylate, caprolactone modified tetrahydrofurfuryl acrylate, EO modified bisphenol A diacrylate, ECH modified bisphenol A diacrylate, bisphenol A Dimethacrylate, 1,4-butanediol diacrylate, 1,3-
Butylene glycol diacrylate, diethylene glycol dimethacrylate, glycerol dimethacrylate, neopentyl glycol diacrylate, EO modified phosphoric acid diacrylate, ECH modified phthalic acid diacrylate, polyethylene glycol 400 diacrylate,
Polypropylene glycol 400 dimethacrylate, tetraethylene glycol diacrylate, ECH modified 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, EO modified phosphate triacrylate,
EO-modified trimethylolpropane triacrylate, P
Acrylates such as O (propylene oxide) modified trimethylolpropane triacrylate, tris (methacryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, etc. Methacrylate and the like are included. These monomers are used alone or in combination of two or more.

(3) Examples of the photoinitiator include benzophenone, N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, benzyl and 2,2-diethoxy. Acetophenone, benzoin, benzoin methyl ether,
Benzoin isobutyl ether, benzyl dimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-1-propane, t-butylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, 1,4-naphthoquinone , 9,10-phenanthraquinone, 1,2-benzanthraquinone, 1,4-dimethylanthraquinone, 2-phenylanthraquinone, 2-
(O-chlorophenyl) -4,5-diphenylimidazole dimer and the like. These photoinitiators are used alone or in combination of two or more.

As the pigment, there are inorganic pigments and organic pigments. Generally, except for black carbon black, graphite, etc., organic pigments are used because of their rich color tone. As the organic pigment, for example, azo type, phthalocyanine type,
Examples include indigo type, anthraquinone type, perylene type, quinacridone type, methine / azomethine type, isoindolinone type and the like.

The organic solvent used in the production of the colored photosensitive resin is not particularly limited, and examples thereof include ketone type organic solvents (acetone, methyl ethyl ketone, cyclohexanone, etc.), cellosolve type organic solvents (methyl cellosolve, ethyl cellosolve, butyrate). Locellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyrocellosolve acetate, etc., glycol organic solvent (ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether, triethylene glycol dimethyl ether, propylene glycol) Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Recall monobutyl ether, propylene glycol monomethyl ether acetate),
Alcohol-based organic solvents (methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, 3-methyl-3-methoxybutanol, etc.), aromatic organic solvents (benzene, toluene, xylene, etc.), 3-
Methyl-3-methoxybutyl acetate, N-methyl-
2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, tetrahydrofuran, dioxane, ethyl acetate and the like can be mentioned. These are used alone or in combination of two or more. Such a colored photosensitive resin film of the present invention is a film having oxygen resistance and can be exposed by peeling off the cushion layer, so that a colored resin pattern having excellent resolution can be obtained.

The cushion layer can be formed into a sheet,
It is not tacky at room temperature and has a film smoothness of 0.05μ.
It is preferably m or less. Also, the hardness at the temperature of laminating the colored photosensitive resin film on the transparent substrate (JISK
6301) is more preferably 80 degrees or less. The reason for this is that if the hardness is too high, the pressure does not penetrate into the edge part of the image pattern formed on the transparent substrate, bubbles enter, and the thickness of the photosensitive layer transferred to the edge part becomes large, resulting in a flat image. This is because it impairs sex. Further, the film thickness of this layer is preferably thicker than the film thickness of the photosensitive layer, and at least twice the thickness is required. The thickness of the colored photosensitive resin film is 1.5
In the case of μm, it is preferably 3 μm or more.

The cushion layer is made of a material having a low adhesion to the colored photosensitive resin film in order to exhibit good releasability from the colored photosensitive resin film after transfer, or the cushion layer is composed of the colored photosensitive resin film and the cushion layer. Release treatment may be performed by coating a silicon compound or the like on the interface. It is also possible to apply the cushion layer to the base film in advance and to bond it to the colored photosensitive resin film to weaken the adhesion with the cushion layer.

Materials used for the cushion layer include polyolefins such as polyethylene and polypropylene, ethylene and vinyl acetate, ethylene and acrylate, ethylene copolymers such as ethylene and vinyl alcohol, polyvinyl chloride, vinyl chloride and vinyl acetate, Copolymer of vinyl chloride and vinyl alcohol, polyvinylidene chloride, polyvinylidene chloride copolymer, polystyrene, styrene copolymers such as styrene and (meth) acrylic acid ester, polyvinyltoluene, vinyltoluene and (meth) acrylic acid Selected from vinyltoluene copolymers such as esters, poly (meth) acrylic acid esters, copolymers of (meth) acrylic acid esters such as butyl (meth) acrylate and vinyl acetate, synthetic rubbers, cellulose derivatives, etc. At least one It is possible to use an organic polymer above.

The cover film of the transfer material of the present invention is preferably one which is chemically and thermally stable and can be easily peeled off from the photosensitive layer. Specifically, a thin sheet-like material such as polyethylene, polypropylene, polyethylene terephthalate, or polyvinyl alcohol having a high surface smoothness is preferable. Also included are those whose surface has been subjected to a release treatment in order to impart releasability.

[0024]

EXAMPLE A polyethylene terephthalate film having a thickness of 50 μm was used as a base film, and a cushion layer-forming solution coating solution having the following composition and a gravure roll were applied and dried on the film to a dry film thickness of 5 μm. An ethylene-ethyl acrylate copolymer resin film was formed to obtain a support having a cushion layer formed on a polyethylene terephthalate film as a base film. Cushion layer forming solution: Ethylene-ethyl acrylate copolymer resin 10 g (Mitsui-DuPont Polychemical, trade name EVAFL
EX-EEA-709, ethyl acrylate content 35
%) Toluene 100 g On the other hand, the following colored photosensitive resin layer dispersion is formed on a polypropylene film of 40 μm as a cover film by using a gravure roll to form a colored photosensitive resin layer to a dry film thickness of 1.5 μm. did. The formed colored photosensitive resin layer and the ethylene-ethyl acrylate copolymer resin cushion layer were bonded together to produce a transfer film for manufacturing a color filter in which a base film, a colored photosensitive resin layer, a cushion layer, and a cover film were sequentially laminated. . The red photosensitive dispersion was prepared as follows. The red dispersion is C.I.
I. Pigment Red 178 and C.I. I. Pig
ment Yellow 15 was mixed at a ratio of 8: 2, and a pigment derivative, a polymer, a solvent and the like were added and dispersed therein. To 3746.3 g of this red dispersion, 145.9 g of a copolymer consisting of methacrylic acid, ethyl acrylate and ethyl acrylate, 309.0 g of a monomer consisting of a plurality of maleic acid monoalkyl esters, and diethylene glycol monomethyl ether 35 as a solvent.
9.3 g, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 as a sensitizer
178.6 g of one-on was added. The mixture was redispersed for 90 minutes with a homomixer while being cooled with ice water. In order to remove undissolved components, the solution was pressure-filtered through a 1 μm mesh filter and provided as a photosensitive dispersion. Next, a glass substrate with a chrome film (film thickness 0.1 μm) (1.1 m
m × 200 mm × 300 mm, manufactured by Geomatec Co., Ltd.), using a roll laminator HLM1500 (manufactured by Hitachi Chemical Techno Plant Co., Ltd.) on a glass substrate on which a black matrix is formed, substrate temperature 100 ° C., roll temperature 100
° C., a roll pressure of 6 kg / cm ^2, at a speed of 0.5 m / min,
While the polypropylene film of the cover film of the transfer film for producing a color filter was peeled off, the colored photosensitive resin film was laminated so as to face the glass substrate. When the polyethylene terephthalate is peeled off from the glass substrate laminated in the order of glass substrate / colored photosensitive resin film / cushion layer / polyethylene terephthalate while being rolled off, the cushion layer is peeled off while being adhered to the polyethylene terephthalate film side. Only the colored photosensitive resin film remained. Then, through a predetermined negative mask, parallel light exposure machine MAP1200L
(Manufactured by Dainippon Screen Co., Ltd.) using 100 mJ / cm ²
Using an exposure and spray type developing device DVW911 (manufactured by Dainippon Screen Co., Ltd.), a developing solution is spray-developed at 25 ° C. for 60 seconds to remove an unexposed portion, and a clean oven CSO-402 (manufactured by Kusumoto Kasei). And heated to 150 ° C. and cured to form a colored pattern of one color. This coloring formation process was repeated using R, G, and B films in each order to form RGB pixel patterns.

[0025]

EFFECTS OF THE INVENTION By using a transfer film for producing a color filter containing a photosensitive resin layer having oxygen resistance, a base film as an oxygen-inhibiting film is not required, and exposure / development by the photosensitive resin layer alone can be performed. It will be possible. Further, by continuously peeling off the base film immediately after the transfer step, it is possible to prevent the transfer film from being cut and dust accompanying it.

[Brief description of drawings]

FIG. 1 is a sectional view of a liquid crystal display.

[Explanation of symbols]

 1. BM (black matrix) 2. Glass substrate 3. Color pixel 4. Overcoat layer (OC) 5. Polarizing plate 6. ITO electrode 7. Color filter 8. Alignment film 9. Liquid crystal 10. Seal material 11. Top coat layer 12. ITO electrode 13. Glass substrate 14. Polarizer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koji Yamazaki, 14 Ii Minamikaigan, Ichihara City, Chiba Prefecture, Goi Plant, Hitachi Chemical Co., Ltd. (72) Inventor, Akira Sasaki, 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd., Ibaraki Laboratory (72) Inventor, Yoichi Kimura, 14 Ii Minami Coast, Ichihara City, Chiba Hitachi Chemical Co., Ltd., Goi Factory (72) Inventor, Yuji Kobayashi, 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture No. Hitachi Chemical Co., Ltd. Ibaraki Research Institute

Claims (4)

[Claims] 1. A method for producing a color filter, wherein a colored pixel is formed a predetermined number of times to form a pattern by a photolithography method in which a photosensitive resin film colored in one color is transferred onto a transparent substrate and exposed / developed. A method for producing a color filter, which comprises using a film having oxygen resistance as a film. 2. A transfer film in which a base film, a cushion layer, and a photosensitive resin film colored in one color having resistance to oxygen damage are sequentially laminated on a transparent substrate, and the transfer film base film and cushion layer are laminated. A method for producing a color filter, which comprises peeling and forming a colored pixel for forming a pattern a predetermined number of times by a photolithography method of exposing and developing a photosensitive resin film colored in one color having resistance to oxygen damage. 3. A transfer film in which a base film, a cushion layer, and a photosensitive resin film colored in one color having an oxygen damage resistance are sequentially laminated on a transparent substrate, and the transfer film is continuously supplied in a roll form for lamination. The method for producing a color filter according to claim 2, wherein after the lamination, the base film and the cushion layer of the transfer film are continuously peeled off without cutting. 4. A transfer film obtained by successively laminating a base film, a cushion layer, and a photosensitive resin film colored in one color having an oxygen damage resistance on a transparent substrate in a roll form and laminating the transfer film. The method for producing a color filter according to claim 2, wherein after the lamination, the base film and the cushion layer of the transfer film are peeled off while being continuously wound by a roll.