JPH05127017A - Production of color filter - Google Patents

Abstract

PURPOSE:To form a color filter by simple operations by previously applying a colorless photosensitive resin liquid on a transparent filter substrate, then laminating this substrate on a laminated sheet. CONSTITUTION:The same filter substrate 6 is subjected to the repetition of the stage for laminating the laminated sheet 4 provided with the photosensitive resin layer 2 contg. coloring agents on one surface of a transparent base sheet 1 in such a manner that the photosensitive resin layer 2 comes into contact with the transparent filter substrate 6, the stage for bringing a positive or negative film 7 having prescribed patterns into tight contact with this laminated substrate 6 and subjecting the film to exposing with UV rays, a stage for peeling the base sheet 1, and the stage for removing the unexposed parts of the photosensitive resin layer 2 transferred to the transparent filter substrate 6 by a developer. The colorless photosensitive resin liquid 5 is previously applied on the transparent filter substrate 6 and thereafter, the laminated sheet 4 is laminated thereon in such a case. Further, one of the prescribed patterns is the pattern having the shape to cover the boundary lines of the respective patterns constituted of the three primary colors of light.

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 an optical color filter used in color televisions, liquid crystal displays, cameras and the like. More specifically, it relates to a method for producing a high-quality color filter capable of forming a pattern generally called a stripe filter or a matrix filter by a simple operation.

[0002]

2. Description of the Related Art A color filter is one in which three or more kinds of fine strips (stripes) of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass, or fine pixels are fixed in length and width. It consists of ones arranged in an array. The width of the stripe is a few microns, and the pixels of the matrix are a few hundreds to 200 microns, and they are arranged in a predetermined order for each hue. Therefore, regarding the manufacturing method of the color filter,
Various methods have been proposed in the past, but the methods have not been fully satisfactory because of poor productivity and insufficient quality.

The method of forming a fine stripe pattern by printing is transfer by ink cohesive failure in principle, and therefore fine irregularities are formed on the surface of each color filter layer, resulting in poor smoothness. In addition, as a method of solving such a defect, first, a dyeable photosensitive substance is applied to a substrate such as glass, then pattern exposure of one filter color is performed, and then the unexposed portion is washed in a developing process. A method has also been proposed in which the operation of taking and dyeing the remaining pattern portion with a dye of the filter color is sequentially repeated for all filter colors. However, this method has a drawback that it is time-consuming and inferior in productivity. Further, since a dye is used, it has a problem in light resistance and heat resistance.

Further, a transparent support sheet such as a polyethylene terephthalate film is coated with a photosensitive material which is colored in advance in each filter color to prepare a colored sheet, each sheet is subjected to a predetermined pattern exposure, and then the unexposed portion is washed off. A method of manufacturing a color filter by sequentially transferring the obtained patterns of respective colors onto a substrate such as glass so as to have a predetermined arrangement has also been proposed. However, in this method as well, the polyethylene terephthalate film coated with a photosensitive material shrinks due to the difference between exposed and unexposed areas of ultraviolet light, or the expansion and contraction of the polyethylene terephthalate film due to development or subsequent drying, Due to the thin film, handling was inconvenient and there was a problem that registration was difficult. In addition, due to the expansion and contraction of the film, a large screen filter is likely to cause a large misalignment between the front end and the rear end.

[Problems to be Solved by the Invention]

The present invention solves the above-mentioned drawbacks of the prior art and provides a method for manufacturing a color filter of high quality at low cost with a simple operation.

[0006]

SUMMARY OF THE INVENTION According to the present invention, a laminated sheet having a photosensitive resin layer containing a colorant provided on one surface of a transparent support sheet is laminated on a transparent filter substrate so that the photosensitive resin layer is in contact with the transparent filter substrate. The step of adhering a positive or negative film having a predetermined pattern to the laminated substrate and exposing to ultraviolet light, the step of peeling the supporting sheet, the unexposed portion of the photosensitive resin layer transferred to the transparent filter substrate In the method of manufacturing a color filter in which the step of removing the
This is a method for producing a color filter, which comprises applying a colorless photosensitive resin liquid to a transparent filter substrate in advance, and then laminating it onto a laminated sheet.

The colorants used in the present invention are four colors of red, green and blue, which are called three primary colors of light, and black of the black matrix portion. As the colorant, either a dye or a pigment can be used, but from the viewpoint of heat resistance and light resistance,
Pigments dominate. Examples of such pigments include C.I. I.
Pigment Red 97,122,149,168,1
77,180,192,215 etc. can be illustrated.

In addition, C.I. I. Pigment Green 7,
36, C.I. I. Pigment Blue 15,15: 1,1
5: 4, 15: 6, 22, 60, 64, C.I. I. Pigment Black 7 and the like can be exemplified.

The photosensitive resin used in the present invention is one which is cured by polymerization, crosslinking reaction and the like caused by ultraviolet irradiation and adheres to a color filter substrate such as glass. Also,
The photocured part is insoluble in the developing solution.

There are two types of photosensitive resins, a radical polymerization type having a polymerizable double bond and a cationic polymerization type having an epoxy group. Examples of the radical polymerization type photosensitive resin include OH group and CO in a part of the resin structure.
A base polymer having at least one reactive group such as OH group or its anhydride, NH ₂ group and epoxy group, and an unsaturated compound having reactivity with these groups, for example, (meth) acrylic acid, cinnamic acid N -Methylol, acrylamide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, isocyanate ethyl (meth) acrylate, glycidyl (meth) acrylate and the like can be mentioned.

As the base polymer, alkyd resin, saponified vinyl chloride / vinyl acetate copolymer, polyvinyl alcohol, urethane polymer, vinyl vinegar maleic acid copolymer, amino resin, polyamide, epoxy resin, acrylic copolymer, cellulose derivative, maleated Polybutadiene etc. can be illustrated. In addition, a diallyl (iso) phthalate polymer having an unsaturated double bond in the resin skeleton and the like can be preferably used.

Further, polymerizable unsaturated monomers and oligomers which enhance the crosslinking reactivity of these photosensitive resins may be mixed and used. Examples of such monomers and oligomers include polyols, poly (meth) acrylates, epoxy acrylates, phthalic acids, pyromellitic acids, reaction products of polyacids such as phosphoric acid and triisocyanuric acid, and hydroxy (meth) acrylates, triallyl. Aryl compounds such as isocyanurate and diallyl (iso) phthalate can be used.

A photopolymerization initiator and a sensitizer are added in order to polymerize or crosslink the photosensitive resin with ultraviolet rays.
As the photopolymerization initiator, benzophenone, orthobenzoyl methyl benzoate, 2,4 diethylthioxanthone,
2-Methyl-1- [4- (methylthio) phenyl] -2
-Morpholinopropanone-1, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propane-1-
On, 4,4-bisdiethylaminobenzophenone and the like can be used.

In addition to this, when considering storage stability, a small amount of a polymerization inhibitor may be added.

Examples of the cationic polymerization type photosensitive resin having an epoxy group include bisphenol type epoxy resin, novolac type epoxy resin, alicyclic epoxy resin,
Various epoxy compounds such as those obtained by epoxidizing an unsaturated resin with peracetic acid, copolymers of glycidyl (meth) acrylate and other vinyl monomers, and the like can be mentioned.
In addition to these, vinyl cyclohexene dioxide, bis (3,4-epoxycyclohexyl) adipate, neopentyl glycol diglycidyl ether, phenyl glycidyl ether, sorbitol glycidyl ether, glycidyl (iso) phthalate, 1,3-diglycidyl- Liquid or solid low molecular weight epoxy compounds such as 5,5-dimethylhydantoin, triglycidyl isocyanurate, glycidyl phthalimide, hydroquinone diglycidyl ether, and bisphenol S diglycidyl ether, compounds that react with epoxy groups, for example,
Alcohol and amino compounds can be used together.
As an initiator for polymerization of an epoxy compound,

[0015] (In the formula, Z is a phenyl group or a phenylene group, and X is PF ₆ , Sb ₆ , or BF _6. ) A compound can be used as a catalyst. Further, the radical polymerization type and cationic polymerization type photosensitive resins described above can be mixed and used.

Various dispersing means such as a three-roll mill, a two-roll mill, a sand mill and a kneader can be used to disperse the pigment and the dye in the photosensitive resin. Further, in order to improve the dispersion of these, a dispersion aid can be added as appropriate.
As such a dispersion aid, various surfactants, pigments or dye derivatives can be used. Such a dispersion aid is excellent in the dispersion of the pigment and has a great effect of preventing the reaggregation of the pigment after the dispersion, so that a color filter having excellent transparency can be obtained.

The photosensitive resin containing a colorant can be applied to the support sheet by using a gravure reverse coater, a lip coater, a knife coater, a microgravure coater or the like with the photosensitive resin liquid. The film thickness of the photosensitive resin layer after drying is 0.5 to 4 μm, preferably 1 to 2 μm.

The support sheet is preferably a plastic film having a thickness of 3.5 to 100 microns, and for example, a film of polyethylene terephthalate, triacetate, high density polyethylene or the like can be used.

When a protective sheet is provided to protect the coated surface of the photosensitive resin, a film having a thickness of 5 to 100 μm, such as polyethylene, polypropylene or polyethylene terephthalate treated with a release agent, is preferable. It should be noted that the adhesive force between the protective sheet and the photosensitive resin layer must be adjusted so as to be weaker than that of the support sheet.

Glass is generally used as the substrate of the color filter. Alternatively, a transparent plastic material can be used. The surface of the substrate such as glass is
In order to make the photosensitive resin adhere well, a treatment such as a coupling agent may be applied. For the application of the colorless photosensitive resin liquid to the transparent filter substrate in advance, the same photosensitive resin as described above can be used. However, it is not necessary to add a coloring agent such as a pigment, and it is better to have higher sensitivity than a layer of a photosensitive resin containing the coloring agent. The photosensitive resin liquid in this portion serves as a good adhesive portion between the glass substrate and the photosensitive resin layer containing the colorant. Therefore, it is not necessary to disperse the colorant in the photosensitive resin, so that the coating solution may be diluted and inexpensive. The application of the colorless photosensitive resin liquid is intended to improve the adhesiveness to the glass substrate, and is used as a thin film as possible in order not to reduce the transmittance of the photosensitive resin layer containing the colorant. .. The coating method is spray coating, spinner coating, or the like. A laminator is used to laminate a laminated sheet having a photosensitive resin containing a colorant on one surface of a support sheet on a transparent color filter substrate. In the stacking, it is preferable to apply heat of about 60 ° C., and it is performed uniformly so that bubbles and wrinkles do not enter.

A positive or negative film having a predetermined pattern is brought into close contact with the laminated substrates and exposed to ultraviolet rays. After UV exposure, peel the support sheet from the filter substrate. The filter substrate to which the photosensitive resin containing the colorant is attached is immersed in a developing solution to remove the uncured portion. The developing method can be appropriately selected depending on the kind of the photosensitive resin, and is performed using an alkali developing solution, an activator developing solution, a solvent developing solution or the like.

A colorless photosensitive resin solution is applied to the filter substrate thus developed, and a photosensitive resin containing a second colorant is applied to one surface of the supporting sheet. Repeat the operation of. It should be noted that one of the predetermined patterns may form a pattern having a shape that covers the boundary line of each pattern composed of the three primary colors of light, and in this case, this pattern is a pattern such as black that does not transmit light. To do. This pattern can also be provided for the first color in order to serve as a guide for designating the positions of the three primary color patterns of light.

The red, green, blue, and the filter substrate which has completed the edging of each pixel can be heated if necessary in order to further accelerate the polymerization of the photosensitive resin.

[0024]

EXAMPLES The present invention will be described based on examples below. In the examples, "parts" means "parts by weight". Example 1 Preparation of photosensitive resin liquid Epicoat 1001 (manufactured by Shell Kagaku) 23 parts Epicron N-6 (manufactured by Dainippon Ink and Chemicals) 27 parts Dipentaerythritol hexaacrylate 30 parts Irgacure-907 3.8 parts Diethylthioxanthone 1.5 Parts Methyl ethyl ketone 250 parts Toluene 250 parts The photosensitive resin liquid blended in the above formulation was well dissolved to obtain a coating liquid. The above coating liquid was applied to a glass substrate with a spin coater.

Preparation of photosensitive resin liquid (red coating liquid) Epicoat 1001 (manufactured by Shell Chemical) 18 parts Epicron N-6 (manufactured by Dainippon Ink and Chemicals) 27 parts Dipentaerythritol Hexaacrylate 30 parts Irgacure-907 3.8 Part Methyl ethyl ketone 180 parts Toluene 180 parts Rionogen Red GD (CI Pigment Red 168 manufactured by Toyo Ink Manufacturing) 13.1 parts Rionogen Orange R (CI Pigment Orange 36 manufactured by Toyo Ink Manufacturing) 5.6 parts With the above formulation The blended photosensitive resin liquid was well dispersed to obtain a coating liquid. A 12 micron thick polyethylene terephthalate (hereinafter abbreviated as PET) film was coated with a micro gravure coater so that the film thickness after drying was 2 microns, dried with warm air at 60 ° C., and then subjected to mold release treatment. A 50 micron PET film (protective sheet) was laminated.

Preparation of photosensitive resin liquid (green coating liquid) Epicoat 1001 (manufactured by Shell Kagaku) 18 parts Epicron N-6 (manufactured by Dainippon Ink and Chemicals) 27 parts Dipentaerythritol hexaacrylate 30 parts Irgacure 907 3.8 Part Diethylthioxanthone 1.9 parts Methyl ethyl ketone 170 parts Toluene 170 parts Lionol Green 2YS (CI Pigment Green 36 manufactured by Toyo Ink Mfg. Co., Ltd.) 12.8 parts Rionogen Yellow 3G (CI Pigment Yellow 154 manufactured by Toyo Ink Mfg. Co., Ltd.) 4 .3 parts The photosensitive resin liquid blended in the above formulation was well dispersed to obtain a coating liquid.

Preparation of photosensitive resin liquid (blue coating liquid) Epicoat 1001 (manufactured by Shell Kagaku) 18 parts Epicron N-6 (manufactured by Dainippon Ink and Chemicals) 27 parts Dipentaerythritol hexaacrylate 30 parts Irgacure-907 3.8 Part Diethylthioxanthone 1.9 parts Methyl ethyl ketone 170 parts Toluene 170 parts Rionol Blue ES (CI Pigment Blue 15: 6 manufactured by Toyo Ink Manufacturing) 16.0 parts Rionogen Violet RL (CI Pigment Violet 23 manufactured by Toyo Ink Manufacturing) ) 4.0 parts The photosensitive resin liquid blended in the above formulation was well dispersed to obtain a coating liquid.

Preparation of photosensitive resin liquid (black coating liquid) Epicoat 1001 (manufactured by Shell Kagaku) 28 parts Lipoxy SP-1519 (manufactured by Showa High Polymer) 35 parts Aronix M-305 (manufactured by Toagosei Kagaku) 15 parts Hydroquinone 0 .05 parts Diethylthioxanthone 3 parts Irgacure-907 3 parts Methyl ethyl ketone 180 parts Toluene 180 parts Mitsubishi Carbon MA-7 (manufactured by Mitsubishi Kasei Co., Ltd.) 14.0 parts .. 12 μm thick PE for each coating liquid
The T film was coated with a microgravure coater so that the film thickness after drying was 2 μm, dried with hot air at 60 ° C., and laminated with a release-treated 50 μm PET film (protective sheet).

A black photosensitive resin coating surface from which the protective sheet had been peeled off and a glass substrate coated with a colorless photosensitive resin coating liquid with a spin coater were laminated with a laminator heated to 60 ° C. A negative film having a edging (black stripe) pattern was adhered onto a support sheet (12 micron PET) and exposed to ultraviolet light of 200 mj / cm ² . After the exposure, the supporting sheet was peeled off from the glass substrate and immersed in a developing solution to remove the unexposed photosensitive resin portion.

A glass substrate having a black matrix was coated with a colorless photosensitive resin coating liquid using a spin coater. The red photosensitive resin coated surface from which the protective sheet was peeled off and the glass substrate with the black matrix were laminated with a laminator at 60 ° C. Support sheet (12 micron PE
T) Attach a red pattern negative film on top of
UV exposure of mj / cm ² was performed. After the exposure, the supporting sheet was peeled off from the glass substrate and immersed in a developing solution to remove the unexposed photosensitive resin portion.

Then, green and blue patterns were formed by the same method to manufacture a color filter.

【The invention's effect】

According to the present invention, the displacement of the pattern due to the expansion and contraction of the thin PET film coated with the photosensitive material is eliminated. Also, the difficulty of registration when using a thin film is eliminated. Patterns can be superposed on each other by using a negative film whose position accuracy is fixed on a single fixed substrate such as glass. Therefore,
It is possible to provide a large color filter with absolute positioning accuracy. Further, since a pigment can be used, it has excellent light resistance and heat resistance. Also,
Since the pattern portion is formed by transferring the portion previously coated on the sheet, a smooth coating surface having a uniform film thickness is formed.

[Brief description of drawings]

1 to 9 are schematic views showing a method of manufacturing a color filter according to the present invention.

[0034]

FIG. 1 is a view showing a cross section of a laminated sheet.

[0035]

FIG. 2 is a diagram in which a colorless photosensitive resin layer is provided on a glass substrate.

[0036]

FIG. 3 is a plan view showing the protective sheet peeled off from the laminated sheet,
It is a figure which shows the formation of a pattern by exposing to ultraviolet light through a negative film after closely adhering to a colorless photosensitive resin layer.

[0037]

FIG. 4 is a diagram in which a protective sheet is peeled off after exposure.

[0038]

FIG. 5 is a diagram in which a first color is formed by developing.

[0039]

FIG. 6 is a view in which a colorless photosensitive resin layer is provided again.

[0040]

FIG. 7 is a diagram showing the formation of a pattern by peeling a protective sheet from a second-color laminated sheet, adhering it to a colorless photosensitive resin layer, and then exposing it to ultraviolet rays through a negative film.

[0041]

FIG. 8 is a diagram in which the protective sheet is peeled off after exposure.

[0042]

FIG. 9 is a diagram in which a second color is formed by developing.

[0043]

[Explanation of symbols]

 1 Transparent Support Sheet 2 Photosensitive Resin Layer 3 Protective Sheet 4 Laminated Sheet 5 Colorless Photosensitive Resin Layer 6 Glass Substrate 7 Negative Film 11 Transparent Support Sheet 12 Photosensitive Resin Layer 15 Colorless Photosensitive Resin Layer 17 Negative Film

Claims (2)

[Claims] 1. A step of laminating a laminated sheet having a photosensitive resin layer containing a colorant on one surface of a transparent support sheet on a transparent filter substrate so that the photosensitive resin layer is in contact with the transparent filter substrate,
A step of exposing a positive or negative film having a predetermined pattern to the laminated substrate and exposing it to ultraviolet light, a step of peeling the supporting sheet, and a developing solution for the unexposed portion of the photosensitive resin layer transferred to the transparent filter substrate. In a method of manufacturing a color filter in which the step of removing in step 1 is repeated for the same filter substrate, a transparent photosensitive filter substrate is previously coated with a colorless photosensitive resin liquid, and then laminated with a laminated sheet. Color filter manufacturing method. 2. The method of manufacturing a color filter according to claim 1, wherein one of the predetermined patterns is a pattern having a shape that covers a boundary line of each pattern composed of three primary colors of light.