JPH06308311A - Production of color filter - Google Patents

Abstract

PURPOSE:To produce the color filter which is formed with fine patterns of multiple colors having a uniform thickness and high precision on a substrate with a good follow-up characteristic of a photosensitive film and good workability and has excellent heat resistance. CONSTITUTION:This process for production of the color filter consists in forming the multicolor patterns by repeating 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, a stage for forming prescribed patterns by exposing and a stage for peeling the base film and developing the resin layer. The sticking stage described above is executed under a reduced pressure.

Description

Detailed Description of the Invention

[0001]

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, which has two or more kinds of very fine stripe-like or mosaic-like patterns having different hues, which are arranged at regular intervals in parallel or parallel. 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, multicolor fine stripes or mosaics using a photosensitive film consisting of a base film and a photosensitive resin layer, which is generally used for etching resist, plating resist, solder resist, etc. at the time of manufacturing printed wiring boards. There is known a manufacturing method of a color filter which can easily form a pattern of 1. A process 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, 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 one hue colorant is applied to a support, and a layer of the photosensitive resin of a dried photosensitive film is transferred onto a transparent plate and exposed through a mask having a predetermined pattern. , A method of developing to form a pattern (JP-A-61-9)
9102). Further, a method of forming a pattern by exposing and developing this film through a mask having a predetermined pattern to form a pattern, and then transferring it onto a transparent plate to form a pattern of a color filter (Japanese Patent Laid-Open No. 61-99103). And a method of forming a transparent colored image pattern by heat-pressing this film onto a transparent plate, exposing through a mask having a predetermined pattern, peeling off the base film, and developing. 63-187203). Further, a photosensitive film comprising a polyvinyl acetate copolymer adhesive on a colored photosensitive resin is used.
A method for forming a color filter pattern by a method similar to that of Japanese Patent No. 187203 (Japanese Patent Laid-Open No. 24-6244)
It has been known.

[0004]

According to the conventional manufacturing method, when the second and subsequent layers are formed, the second and subsequent colored layers on the already formed colored layer are in direct contact with the colored layer. There is a step between and. 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 contact the base (transparent glass),
Also, 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,
It is peeled off together with the base film, and a portion where the colored layer does not adhere to the base is generated. 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. The present invention provides a method for manufacturing a color filter which eliminates the above-mentioned drawbacks, has good workability, and is capable of forming a highly precise multicolor fine pattern.

[0005]

According to the present invention, a photosensitive film comprising a base film and a photosensitive resin colored in one color is provided on a transparent substrate so that the colored photosensitive resin layer faces the substrate. In the method for producing a color filter in which the step of adhering to, the step of exposing to form a predetermined pattern and the step of peeling off and developing the base film are repeated to form a multicolor pattern, the step of adhering is performed under reduced pressure. The present invention relates to a color filter manufacturing method. In the present invention, the sticking of the photosensitive film on the substrate is performed under a reduced pressure, and the air layer is removed by the reduced pressure at a portion which is not in contact with the step to be bonded. The adhesion of the colored photosensitive resin layer according to the present invention is improved, the photosensitive resin layer is prevented from being peeled off from the substrate at the time of peeling the base film and at the time of development, and the followability of the film is improved.

The photosensitive film used in the present invention is a transparent base film, for example, a film such as polyethylene terephthalate, on which a photosensitive resin composition colored in one color is applied 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 matters 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 comprises an ethylenically unsaturated compound (a), a carboxyl group-containing film-forming polymer (b), a photopolymerization initiator or a photopolymerization initiator compound (c) and ( d) It preferably contains a pigment or dye (d), 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 α, β-unsaturated carboxylic acid to polyhydric alcohol, for example, trimethylolpropane di (meth) acrylate (methacrylate). Or acrylate, the same hereinafter), 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, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Examples thereof include butyl acrylate and 2-ethylhexyl (meth) acrylate, and urethane diacrylate compounds obtained by reacting trimethylhexamethylene diisocyanate with a dihydric alcohol and a divalent (meth) acrylic acid monoester. Is also 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.

The carboxyl group-containing film-forming polymer (component (b)) is, 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, especially 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 thermally reacts 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, and a negative mask having a predetermined pattern is placed on the base film on the surface of the colored photosensitive resin to expose it, and then the base film is removed. . Then, the unexposed portion is developed with a developing solution to form a colored pattern. This colored pattern forming step is repeated a predetermined number of times using photosensitive films of different colors to form a pattern of another color to obtain a color filter. Although the above-mentioned bonding step is performed under reduced pressure, a vacuum laminator is usually used. The degree of pressure reduction is preferably 5 mmHg or less from the viewpoint of adhesiveness. Usually, the feeding speed at the time of bonding is 0.1 to 15 m / min, and the roll pressure at the time of bonding is about 4 kg / cm ² . The roll temperature is preferably 80 ° C to 140 ° C. An example of the vacuum laminator is VACUUM L made by ANGER ELECTRONIC GMBH.
AMINATOR TYPE VCL and the like.

[0017]

【Example】

Example 1 1) Production of photosensitive film Table 2 was added to 206 parts by weight of solution A in which the materials shown in Table 1 were uniformly dissolved.
35 parts by weight of any of the pigments, 5 parts by weight of a melamine resin and 5 parts by weight of a silane coupling agent are added,
It melt | dissolved and the photosensitive resin layer coating solution was obtained.

[Table 1]

[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 obtained solution was applied to a polyethylene terephthalate film (Tetron film S25 manufactured by Teijin Co., Ltd.) having a thickness of 25 μm to a uniform thickness and dried for 2 minutes in a dryer at 100 ° C. to obtain a polyethylene film having a thickness of 30 μm as a protective film. A film was attached to obtain a photosensitive film. The thickness of the photosensitive resin layer after drying was 2 μm. Next, the substrate for the color filter (transparent glass, Corning F
(727 thickness 1.0 mm) at 80 ° C. for 10 minutes, and then colored while peeling off the protective film of the colored photosensitive resin layer photosensitive film on the base substrate for the color filter under reduced pressure using a vacuum laminator. Roll the photosensitive resin layer at 120 ℃, roll pressure 4kg / cm ² , speed 1.5m
/ Min. The vacuum laminator used is A
NGER ELECTRONIC VACUM CAMINA made by GMBH
It was performed using a TOR TYPE VCL at a pressure of 5 mmHg. Exposure machine H through a negative mask of a predetermined pattern
After exposure with MW-201B (3 kW, ultra-high pressure mercury lamp, manufactured by Oak Manufacturing Co., Ltd.), the polyethylene terephthalate film was removed, and 1% was added with a 2 wt% Na ₂ CO ₃ aqueous solution at 30 ° C.
The unexposed area was removed by spray development for 0 to 20 seconds, and a colored pattern of one color was formed. This step of forming a colored pattern was repeated four times using the photosensitive films of respective colors in the order of red, blue, green and black to form the multicolor pattern shown in FIG. Exposure amount in the red, blue, 150 mJ / cm ² for green photosensitive resin layer for the photosensitive resin layer of black was 300 mJ / cm ^2. The resulting multicolor pattern was irradiated at 3 J / cm ² with an ultraviolet irradiation device (lamp H5600L / 2, manufactured by Toshiba Denshi Co., Ltd.) and then heated at 150 ° C. for 45 minutes to obtain a color filter. The resulting color filter had red, blue and green patterns arranged in an orderly manner, and the spaces between them were filled with black.

Comparative Example 1 A polyethylene terephthalate film having a thickness of 25 μm (manufactured by Teijin, Tetoron film) was prepared in the same manner as in Example 1.
S25) was used as a base film, and a 30 μm-thick polyethylene film as a protective film was laminated thereon to prepare a photosensitive film for each of the pigments red, blue, green and black. A red colored pattern was formed in the same manner as in Example 1 without providing a base layer, and then the pattern forming process was repeated three times using a photosensitive film of each color in the order of blue, green and black. It was A multicolor pattern similar to that of Example 1 was formed. A schematic view of the obtained multicolor pattern is shown in FIG. The pattern of red (1) of the first color was good, but in blue (2) and green (3), only a part of the pixel (325 μm) between the adjacent pixels of red and red was generated. , A blue pixel that is in contact with a red pixel at 25 μm intervals reproduces only a 50 μm width, and 125 μm × 125
The μm square was not reproduced. Black produced no pixels.

[0019]

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

[Brief description of drawings]

FIG. 1 is a screen 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 of the present invention.

[Explanation of symbols]

 1 red 2 blue 3 green 4 black

Claims (1)

[Claims] 1. A photosensitive film comprising a base film and a photosensitive resin layer colored in one color on a transparent substrate,
A color filter for forming a multicolor pattern by repeating a step of laminating a colored photosensitive resin layer so as to face the substrate, a step of exposing and forming a predetermined pattern, and a step of peeling off and developing the base film. 2. The method for manufacturing a color filter according to claim 1, wherein the laminating step is performed under reduced pressure.