JPH07140313A - Production of color filter - Google Patents

Abstract

PURPOSE:To provide the process for production of color filters which are formed with fine patterns of multiple colors having a uniform thickness and high accuracy on a substrate with the good follow-up characteristic of a photosensitive film and workability and have excellent heat resistance. CONSTITUTION:This process for production of the color filters comprise forming the multicolor patterns by repeating (i) a stage for sticking the photosensitive film consisting of a base film and a photosensitive resin layer colored to one color on a transparent substrate in such a manner that the colored photosensitive resin layer faces the substrate, (ii) a stage for forming the prescribed patterns by exposing and (iii) a stage for peeling the base film and developing the photosensitive film. The color filters are formed as a stripe shape in the sticking stage described above. The feed direction of the photosensitive film is set at a direction parallel with the longitudinal direction of the pixels of the stripe shape of the first color at the time of sticking of the second and subsequent colors.

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.

[0002]

2. Description of the Related Art A color filter is an optically transparent substrate, such as glass, having two or more kinds of very fine stripe-like or mosaic-like patterns with different hues, which are arranged in parallel or parallel to each other. It is a crossed arrangement. It is necessary for these patterns to arrange hues in a predetermined order at predetermined intervals and to form a uniform layer with little thickness unevenness, and various color filter manufacturing methods have been proposed. For example, the screen printing method can form a low-cost color filter. Further, a method using a photolithography technique, that is, a method of irradiating a transparent film formed on a color filter substrate with ultraviolet rays through a predetermined negative mask to remove an unexposed portion, and then dyeing while forming a stain-proof layer is available. is there.

As an improved method of the above-mentioned method, a colored solution type photosensitive resin composition is applied on a substrate and dried,
There is a method of forming a color filter by exposing and developing to form a pattern of one color and repeating this process for other colors in the same manner. In addition, it is generally used as an etching resist, a plating resist, a solder resist, etc. at the time of manufacturing a printed wiring board. There is known a method for producing a color filter which can easily and highly accurately form a multicolor fine stripe-shaped or mosaic-shaped pattern using a photosensitive film composed of a base film and a photosensitive resin layer. A step of laminating a photosensitive film consisting of a base film and a photosensitive resin layer colored in one color on a transparent substrate so that the colored photosensitive resin layer faces the substrate, and exposing to form a predetermined pattern The step of allowing and the step of peeling off and developing the base film are repeated to form a multicolor pattern to manufacture a color filter. For example, a layer of a photosensitive resin containing a colorant of one hue is applied to a support and dried, and the layer of the photosensitive resin of the photosensitive film is transferred onto a transparent plate, and then a mask of a predetermined pattern is used. A method of exposing and developing to form a pattern (Japanese Patent Laid-Open No. 61-
99102). Method for carrying out alkali development (JP-A-2-239205) Method using water-soluble base film (JP-A-2-271301) Also, the film is exposed and developed through a mask having a predetermined pattern to form a pattern. After being formed, a method for forming a color filter pattern by transferring the pattern onto a transparent plate (Japanese Patent Laid-Open No. 61-99103 and 63-665).
No. 03) and this film are heat-pressed onto a transparent plate and exposed through a mask having a predetermined pattern,
A method of forming a transparent colored image pattern by peeling off the base film and developing it (JP-A-63-187203, JP-A-2-244005), and a method in which polyvinyl acetate Using a photosensitive film constituting a polymer adhesive, the method is disclosed in JP-A-63-187203.
There is known a method for forming a pattern of a color filter (Japanese Patent Laid-Open No. 24-24624) by a method similar to that of Japanese Patent Laid-Open Publication No. 24-24624. Further, a method of forming a color filter using a photosensitive film is disclosed in Japanese Patent Laid-Open No. 3-160454,
JP-A-3-111802, JP-A-2-15180
5, JP-A-4-212161, JP-A-4-212161
No. 301602, Japanese Patent Laid-Open No. 5-2107, etc.

[0004]

In the conventional method for producing a color filter, when the second and subsequent layers are formed, the second and subsequent colored layers on the already formed colored layer are brought into direct contact with the substrate. A step is formed between the colored layer and the colored layer. This step difference is determined by the thickness (1 to 5 μm) of the colored layer already formed. Due to this step, the new colored layer does not come into contact with the base (transparent glass), and due to insufficient adhesion pressure, the adhesive strength becomes insufficient, the colored layer does not adhere to the base, and the base film is peeled off. , Peeled off with the base film,
There is a portion where the colored layer does not adhere to the base. Further, if exposed and developed as it is, there is a disadvantage that a portion where a colored image does not exist is exposed, and a desired color filter cannot be obtained. More specifically, in particular, when the color filter is composed of pixels of three primary colors (red, green, blue) in a striped pattern, the striped pixels of the first color are, for example, 2.0 μm in thickness, 70 μm in width, and spaced. 300μ
When a second colored layer is pasted on the transparent substrate having a thickness of m, there is unevenness of about 2.0 μm due to the front pixels, so that there is insufficient contact between the transparent substrate and the colored layer. Occurs, and there is a drawback that the second colored layer does not sufficiently follow this unevenness. The present invention provides a method for manufacturing a color filter which eliminates this drawback, has good workability, and is capable of forming a multicolor fine pattern with high accuracy.

[0005]

According to the present invention, there is provided (i) a transparent substrate on which a photosensitive resin layer colored with a photosensitive film comprising a base film and a photosensitive resin layer colored with one color is provided. And (ii) exposing to form a predetermined pattern, and (iii)
A method of manufacturing a color filter in which the step of peeling off the base film and developing is repeated to form a multicolor pattern, wherein in the step of laminating, the shape of the color filter is formed into a stripe shape, and when the second and subsequent colors are laminated. The present invention relates to a method of manufacturing a color filter, wherein the feeding direction of the photosensitive film is parallel to the longitudinal direction of the first-color striped pixels.

According to the present invention, the photosensitive film of the second and subsequent colors is satisfactorily followed by the unevenness due to the pixels. That is, by driving the pressure roll parallel to the longitudinal direction of the stripes and adhering the stripes, the film is sufficiently supplied to the step portion due to the unevenness of the front pixel, and the insufficient contact portion is eliminated. .

For example, when there is a step of 2 μm, an extra film length of 4 μm is required for each front pixel in order to follow the unevenness. In the A4 size, a film of 4 to 8 mm in the lateral direction is uneven. Consumed. This consumption amount can be accurately matched to the step due to the unevenness of the front pixel.

The photosensitive film used in the present invention is a transparent base film, for example, a film such as polyethylene terephthalate, coated with a photosensitive resin composition colored in one color and dried to form a colored photosensitive resin layer. It was formed. This colored photosensitive resin layer is uncured,
Since it is flexible and has an adhesive property, it is desirable that a protective film such as a polyethylene film is further laminated thereon to prevent external damage, adhesion of foreign matter, and the like. The colored photosensitive resin layer formed on the photosensitive film is attached on a transparent substrate while peeling off the protective film, and the base film on the surface of the colored photosensitive resin layer is removed after exposure through a negative mask having a predetermined pattern. It

The photosensitive resin layer colored in one color includes an ethylenically unsaturated compound (a), a carboxyl group-containing film-forming polymer (b), a photopolymerization initiator or a photopolymerization initiator compound (c) and a pigment. Alternatively, the dye (d) is preferably contained, and the layer thickness is preferably 0.5 to 15 μm.

The ethylenically unsaturated compound (component (a)) is, for example, a compound obtained by adding an α, β-unsaturated carboxylic acid to a polyhydric alcohol, such as trimethylolpropane di (meth) acrylate (methacrylate). Or acrylate, the same below), trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc .; containing glycidyl group Compounds obtained by adding α, β-unsaturated carboxylic acids to compounds, such as trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether di (meth) acrylate, etc .; polyvalent carboxylic acids such as anhydrous Compounds with Tal acid and a hydroxyl group and an ethylenically unsaturated group, ester of example β- hydroxyethyl (meth) acrylate; (meth)
Alkyl ester of acrylic acid (meaning methacrylic acid or acrylic acid, the same applies hereinafter), for example, (meth) acrylic methyl, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. And a urethane diacrylate compound obtained by reacting trimethylhexamethylene diisocyanate with a dihydric alcohol and a divalent (meth) acrylic acid monoester may also be used. You may use 2 or more types of these compounds. The blending amount of the component (a) is preferably 90 with the total amount of the components (a) and (b) being 100 parts by weight.
~ 50 parts by weight.

As the carboxyl group-containing film-forming polymer (component (b)), for example, a copolymer of (meth) acrylic acid alkyl ester and (meth) acrylic acid:
Examples thereof include copolymers of (meth) acrylic acid alkyl ester, (meth) acrylic acid, and a vinyl monomer copolymerizable therewith. Examples of alkyl (meth) acrylates include methyl (meth) acrylate, (meth)
Examples thereof include ethyl acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. Further, as vinyl monomers copolymerizable with (meth) acrylic acid alkyl ester and (meth) acrylic acid, dimethylethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, diethyl (meth) acrylate 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, acrylamide, diacetone acrylamide, styrene, vinyltoluene and the like. Furthermore, polyesters such as terephthalic acid, isophthalic acid and sebacic acid containing (meth) acrylic acid as a copolymerization component, copolymers of butadiene and acrylonitrile, cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose and the like can also be used. .

By using the component (b), the coating properties and the film properties of the cured product are improved, and the compounding amounts of the component (a) and the component (b) are
The total amount of the components is 100 parts by weight, and preferably 10 to 50.
Parts by weight. If the blending amount is less than 10 parts by weight, the amount of ethylenically unsaturated compound increases, and the photosensitivity decreases, and if it exceeds 50 parts by weight, the photocured product tends to become brittle. Further, the weight average molecular weight of the component (b) is preferably 10,000 or more from the viewpoint of the coating property and the film strength.

Examples of the photopolymerization initiator or the photopolymerization initiator compound (component (c)) include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N. Aromatic ketones such as'-tetramethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone; benzoin methyl ether, benzoin Benzoin ether such as ethyl ether and benzoin phenyl ether; Benzoin such as methylbenzoin and ethylbenzoin; 2 (o
-Chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m
-Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer
(P-Methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl)-
5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5
-A 2,4,5-triarylimidazole dimer such as a diphenylimidazole dimer is used.

The blending amounts of the component (c) are the components (a) and (b).
The total amount of the components is preferably 0.1 to 1 with respect to 100 parts by weight.
0 parts by weight. If the content is less than 0.1 parts by weight, the photosensitivity will be insufficient, and if it exceeds 10 parts by weight, the light absorption on the surface of the composition will increase during exposure, and the internal photocuring will tend to be insufficient. There is.

As the pigment or dye (component (d)), a generally known coloring agent can be used, and a phase for the component of the photosensitive resin layer, particularly for the ethylenically unsaturated compound or the carboxyl group-containing film-forming polymer. It is selected in consideration of solubility, target hue, light transmittance and the like.
The blending amount of the component (d) is preferably 1 to 50 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b). If the blending amount is less than 1 part by weight, the coloring is insufficient, and if it exceeds 50 parts by weight, the light transmittance tends to decrease.

In the colored photosensitive resin layer, a melamine resin and / or an epoxy resin which reacts thermally with the carboxyl group of the carboxyl group-containing film-forming polymer in order to enhance the heat curing property, the (a) component and the (b) component. Total of 10
It is preferable to add 1 to 20 parts by weight to 0 parts by weight. Add these to 30 ~ 30 at 130 ~ 200 ℃
By heating for 60 minutes, the crosslink density of the colored layer is improved and the heat resistance is significantly improved.

When the substrate forming the color filter is a glass plate, it is preferable to use a glass plate previously treated with a silane coupling agent in order to improve the adhesion between the colored photosensitive resin layer and the glass plate. Further, the colored photosensitive resin layer may contain a silane coupling agent to improve the adhesion between the photosensitive resin layer and the glass plate.
In this case, the addition amount of the silane coupling agent is preferably 1 to 30 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b).

In the present invention, the color filter is manufactured as follows. First, a colored photosensitive resin layer formed on a photosensitive film is attached to a transparent substrate, a negative mask of a predetermined pattern is placed on the base film on the surface of the colored photosensitive resin layer, and the base film is removed. . Then, the unexposed portion is developed with a developing solution to form a colored pattern, and the step of forming this colored pattern is repeated a predetermined number of times using photosensitive films of different colors,
A color filter is obtained by forming a multicolor pattern, and the feeding direction of the photosensitive film is made parallel to the longitudinal direction of the stripe-shaped pixels of the first color when the second and subsequent colors are laminated.

[0019]

【Example】

Example 1 1) Production of Photosensitive Film To 206 parts by weight of a solution A in which the materials shown in Table 1 were uniformly dissolved, 35 parts by weight of the pigment of any one of Table 2, 5 parts by weight of melamine resin and 5 parts by weight of silane coupling agent were added. Each was added and dissolved to obtain a colored photosensitive resin layer coating solution.

[0020]

[Table 1]

[0021]

[Table 2]

Cymel 300 (trade name of hexamethoxymethyl melamine, manufactured by Mitsui Toatsu Co., Ltd.) was used as the melamine resin, and K3M503 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent. The resulting solution was used as a polyethylene terephthalate film (Tetron film S manufactured by Teijin Ltd.) having a thickness of 6 μm.
6) A film having a uniform thickness was applied onto the above 6) and dried for 2 minutes in a dryer at 100 ° C., and a polyethylene film having a thickness of 30 μm was stuck as a protective film to obtain a photosensitive film. The thickness of the photosensitive resin layer after drying was 2 μm.

Next, after heating the base substrate for the color filter at 80 ° C. for 10 minutes, the colored photosensitive resin layer is rolled while peeling off the protective film of the photosensitive film obtained in (1) for the color filter. Lamination was performed at a temperature of 120 ° C., a roll pressure of 0.5 kg / cm ² , and a speed of 1.5 m / min.
Then, the exposure machine HMW-201B is passed through a negative mask of a predetermined pattern (corresponding to a pattern consisting of only 1 (red), 2 (blue) or 3 (green) in FIG. 1).
(3 kW, ultra-high pressure mercury lamp, manufactured by Oak Manufacturing Co., Ltd.), exposed to light, and then the polyethylene terephthalate film was removed.
The unexposed area was removed by spray developing with a 2 wt% Na ₂ CO ₃ aqueous solution at 0 ° C. for 10 to 20 seconds to form a colored pattern of one color. This colored pattern forming process is performed with red, blue,
Repeat using the photosensitive film of each color in the order of green,
When laminating the second color blue, the film was fed with the feeding direction of the film parallel to the red stripe pattern of the front pixels, and the same was performed for green to form the multicolor pattern shown in FIG. The exposure dose at this time was 50 mJ / cm ² for the red, blue and green photosensitive resin layers. An ultraviolet irradiator (lamp H5600L / 2,
After irradiating with ³ J / cm ² using Toshiba Denshi Co., Ltd., 150
It heated at 45 degreeC for 45 minutes, and obtained the color filter. The color filter thus obtained had orderly arranged red, blue and green patterns (a stripe pattern having a pixel width of 70 μm, a length of 150 mm, and an interval of 30 μm).

Comparative Example 1 A polyethylene terephthalate film having a thickness of 6 μm (manufactured by Teijin Tetron Film S
Using 6) as a base film, a photosensitive film having a 30 μm-thick polyethylene film laminated thereon as a protective film was prepared using the pigments red, blue and green, respectively. A red colored pattern was formed in the same manner as in Example 1, and then the pattern forming process was repeated using a photosensitive film of each color in the order of blue and green.
At this time, the stripe pattern and the film feeding direction were not parallel to each other, but were intersected at an angle of 30 degrees. A schematic view of the obtained multicolor pattern is shown in FIG. The film did not have sufficient followability, some wrinkles were generated on the film, and the followability was uneven. The first color red (1) pattern is 70 μm wide
However, in blue (2) and green (3), only a part of the pixel (230 μm) between the adjacent pixels of red and red was generated, and in particular, the red pixel was touched at 30 μm intervals. With the blue pixels present, only the width of 50 μm was reproduced, and the stripe of 70 μm width was not reproduced.

[0025]

According to the manufacturing method of the present invention, a color having excellent heat resistance, in which a highly precise multicolor fine pattern having a uniform thickness is formed on a substrate with good followability and workability of a photosensitive film. A filter can be manufactured.

[Brief description of drawings]

FIG. 1 is a diagram showing a pattern of a color filter obtained in an example of the present invention.

FIG. 2 is a diagram showing a pattern of a color filter obtained in a comparative example.

[Explanation of symbols]

 1 red 2 blue 3 green

Claims (1)

[Claims] 1. (i) A step of laminating a photosensitive film comprising a base film and a photosensitive resin layer colored in one color on a transparent substrate so that the colored photosensitive resin layer faces the substrate. A method for producing a color filter in which (ii) a step of exposing to form a predetermined pattern and (iii) a step of peeling off and developing the base film to form a multicolor pattern are repeated, A color filter characterized in that the color filter has a stripe shape, and the feeding direction of the photosensitive film is parallel to the longitudinal direction of the stripe-shaped pixels of the first color when the second color and the subsequent ones are laminated. Manufacturing method.