JPH08136724A - Production of color filter and color filter - Google Patents

Abstract

PURPOSE: To provide a producing method for color filter capable of producing a color filter without causing defective a picture having defect such as void and to provide the color filter. CONSTITUTION: In the producing method for color filter in which a photosensitive film for the color filter on which (a) a transparent supporting body film, (b) a colored photosensitive resin layer and (c) a protective film are laminated in this order is stuck on a substrate for the color filter while peeling the protective film and then exposure and development are executed and the sticking is executed while applying heat by using a roll having >=60mm diameter and a rubber layer having <=5 deg. Shore hardness at its outmost layer.

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 and the like and a color filter.

[0002]

2. Description of the Related Art A color filter has a pattern of two or more kinds of extremely different stripes or mosaics which are different in hue from each other on a surface of a color filter substrate such as an optically transparent glass at regular intervals. , Parallel or crossed side by side. 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 methods for manufacturing color filters have been proposed. For example, the screen printing method can form a low-cost color filter. Also,
A method using a photolithography technique, that is, a transparent film formed on a color filter substrate is irradiated with ultraviolet light through a predetermined negative mask, and after removing an unexposed portion,
There is a method of dyeing while forming a dye-proof layer.

As an improvement of the above-mentioned method, a step of applying a colored solution type photosensitive resin composition on a substrate, drying it, exposing it to light and developing it to form a pattern of one color, and also for other colors Similarly, there is a method of repeating the process to form a color filter. In addition, a multicolor fine film using a transparent support film and a photosensitive film composed of a colored photosensitive resin layer, which are generally used for etching resists, plating resists, solder resists, etc. at the time of manufacturing printed wiring boards, are used. There is known a method for manufacturing a color filter that can easily form a stripe-shaped or mosaic-shaped pattern with high accuracy.

According to this manufacturing method, a photosensitive film comprising a support film and a photosensitive resin layer colored in one color is attached on a transparent substrate so that the colored photosensitive resin layer faces the substrate. A color filter is manufactured by repeating the steps of combining, exposing to form a predetermined pattern, and peeling and developing the support film to form a multicolor pattern.

For example, a photosensitive resin composition of a photosensitive film obtained by applying a photosensitive resin composition containing one hue colorant to a transparent support film and drying it is transferred onto a transparent plate, There is known a method of forming a pattern by exposing and developing it through a mask having a predetermined pattern (JP-A-61-99102). A method of forming a pattern by exposing and developing this film through a mask having a predetermined pattern, and then transferring the film onto a transparent plate to form a pattern of a color filter (JP-A-61-99103). ) And this film by thermocompression bonding on a transparent plate,
There is known a method of forming a transparent colored image pattern by exposing through a mask having a predetermined pattern, peeling off the support film, and developing it (Japanese Patent Laid-Open No. 63-187203). Further, a method of forming a color filter pattern using a photosensitive film having a polyvinyl acetate copolymer adhesive formed on a colored photosensitive resin layer in the same manner as in JP-A-63-187203 ( JP-A-2-2462
No. 4) is known.

However, when laminating the photosensitive film for forming the pattern of the second color and the photosensitive film for forming the pattern of the third color, entrapment of air bubbles occurs and white defects and the like occur. There is a problem that a fine image cannot be obtained and a high quality color filter cannot be obtained.
Therefore, increase the bonding pressure and increase the temperature to 16
It has been attempted to carry out at 0 ° C or higher, but the life of the laminator used for bonding has been shortened.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a color filter manufacturing method and a color filter capable of manufacturing a color filter free from image defects such as white spot defects. It is a thing.

[0008]

The present invention provides a photosensitive film for a color filter in which (a) a transparent support film, (b) a colored photosensitive resin layer and (c) a protective film are laminated in this order, In the method for producing a color filter in which (c) a protective film is attached to a substrate for a color filter while peeling it off, and then exposed and developed, a rubber having a diameter of 60 mm or more and an outermost layer having a Shore hardness of 50 ° or less is used. The present invention relates to a method for producing a color filter, which is performed while heating using a layered roll, and a color filter produced by the production method.

Examples of the transparent support film (a) in the present invention include Tetron film GS series and M5R series polyester films manufactured by Teijin Limited, and Mylar film D series polyester films manufactured by DuPont. The thickness of the transparent support film is 2
It is preferably 10 μm. If it is less than 2 μm, it tends to be difficult to produce a photosensitive film for a color filter, and if it exceeds 10 μm, it is
The pattern (pixel) already formed, that is, the first color or the second color in the case of red, blue, and green, has poor followability and tends to be a pixel defect.

(B) The colored photosensitive resin layer contains the ethylenically unsaturated compound (A), the carboxyl group-containing film-forming polymer (B), the photopolymerization initiator (C) and the pigment or dye (D). It is preferable to contain, and the thickness is 0.5
It is preferable that the thickness is 5 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 (for example, trimethylolpropane di (meth) acrylate ( Mean acrylate or acrylate, the same below), trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.), Compounds obtained by adding α, β-unsaturated carboxylic acids to glycidyl group-containing compounds (for example, trimethylolpropane triglycidyl ether triacrylate, bisphenol A
Ester of diglycidyl ether di (meth) acrylate, etc., polyvalent carboxylic acid (eg, phthalic anhydride) and a compound having a hydroxyl group and an ethylenically unsaturated group (eg, β-hydroxyethyl (meth) acrylate) Compound, an alkyl ester of (meth) acrylic acid (meaning methacrylic acid or acrylic acid, the same applies hereinafter) (for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, etc.), a urethane diacrylate compound obtained by reacting trimethylhexamethylene diisocyanate with a dihydric alcohol and a divalent (meth) acrylic acid monoester. These compounds are used alone or in combination of two or more.
The compounding amount of the component (A) is preferably 50 to 90 parts by weight, with the total amount of the components (A) and (B) being 100 parts by weight. If the amount is less than 50 parts by weight, the photocured product tends to become brittle, and if it exceeds 90 parts by weight, the photosensitivity tends to be insufficient.

Examples of the carboxyl group-containing film property imparting polymer (component (B)) include, 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 the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
2-Ethylhexyl (meth) acrylate and the like can be mentioned. 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. Further, terephthalic acid, isophthalic acid, sebacic acid, and other polyesters containing (meth) acrylic acid as a copolymerization component, butadiene and acrylonitrile copolymers, cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose, etc., as component (B). It can be used by adding to.

By using the component (B), the coating properties and the film properties of the cured product are improved, and the blending amounts are the same as those of the components (A) and (B).
It is preferable that the total amount of the components is 100 parts by weight and 10 to 50 parts by weight. If the amount is less than 10 parts by weight,
Since the amount of ethylenically unsaturated compound increases, the photosensitivity tends to be insufficient, and when 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 (component (C)) include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone) and N, N'-tetramethyl-4. , 4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone and other aromatic ketones, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether Benzoin ether such as, benzoin such as methylbenzoin, 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- (p-methoxyphenyl) -4,5-diphenylimidazole dimer Body, 2, 4
-Di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl)-
A 2,4,5-triarylimidazole dimer such as 4,5-diphenylimidazole dimer or 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer is used. These compounds are used alone or in combination of two or more.

The blending amounts of the component (C) are the components (A) and (B).
It is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the components. If the amount is less than 0.1 part by weight, the photosensitivity tends to be insufficient, and if it exceeds 10 parts by weight, the light absorption on the surface of the composition increases during exposure, and the internal photocuring is insufficient. Tends to be.

As the pigment or dye (component (D)),
Known colorants can be used, and in particular, they are selected in consideration of the compatibility with the ethylenically unsaturated compound or the carboxyl group-containing film-forming polymer, the target hue, the light transmittance, and the like. The compounding 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 amount is less than 1 part by weight, the coloring tends to be 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 groups of the carboxyl group-containing film-forming polymer (B) in order to enhance the heat-curing property, is used as the component (A). It is preferable to add 1 to 20 parts by weight to 100 parts by weight of the component (B) in total. By adding these and heating, the crosslink density can be improved and the heat resistance can be improved. The heating temperature at this time is 130 to 2
The temperature is preferably 00 ° C. The heating time is 30 ~
It is preferably 60 minutes.

As the protective film (c) in the present invention, for example, a polyester film, a polyolefin film and the like are used, but from the viewpoints of price, flexibility, strength, hardness and the like, a polyolefin film is preferable, and a polyethylene film is particularly preferable. . Also, its thickness is
It is preferably 1.0 to 40 μm. If it is less than 10 μm, the handleability tends to be poor, and if it exceeds 40 μm, the cost tends to increase.

In the present invention, the color filter is manufactured as follows. First, the colored photosensitive resin layer is laminated (bonded) on the color filter substrate while peeling off the protective film, and a negative mask having a predetermined pattern is placed on the transparent support film on the surface of the colored photosensitive resin layer. After exposure by exposure, the transparent support film is removed. Then, the unexposed portion of the colored photosensitive resin layer 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 multicolored pattern to obtain a color filter.

The bonding is usually carried out by heating a colored photosensitive resin layer while heating it with a heatable roll called a hot roll. In this process, the diameter is 60
It is necessary to use a roll in which the outermost layer is a rubber layer having a Shore hardness of 50 ° or less with a thickness of mm or more. 2 if the diameter is less than 60 mm or the Shore hardness exceeds 50 °
When forming the patterns of the third and third colors, the followability of the colored photosensitive resin layer to the color filter substrate is poor,
Entrapment of air bubbles occurs and white spot defects and the like occur, so that a fine image cannot be obtained and a high-quality color filter cannot be obtained. The upper limit of the diameter of the roll is usually 150 mm, and the lower limit of the Shore hardness is usually 30 °. The material of the rubber is not particularly limited as long as it has heat resistance, but silicon rubber is usually used. The heating temperature is not particularly limited, but the heating temperature is preferably 100 to 160 ° C. If the temperature is less than 100 ° C., the colored photosensitive resin layer is not sufficiently softened, and air bubbles are apt to be involved.
If it exceeds 160 ° C., smoke from the colored photosensitive resin layer and unwanted thermal polymerization are likely to occur, and the life of the laminator tends to be shortened.

Further, it is preferable that the pressure applied by the roll at the time of bonding is 3 kg / cm ² or more. If this pressure is less than 3 kg / cm ² , the bonding tends to be insufficient. The laminating speed is 0.5-2.
It is preferably 0 m / min. If the laminating speed is less than 0.5 m / min, the productivity tends to be poor, and if it exceeds 2.0 m / min, sufficient heating cannot be performed and bubbles tend to be entrained.

The exposure can be performed using a contact or non-contact type exposure device such as a dedicated exposure device. As the lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a xenon lamp lamp, or the like that effectively radiates ultraviolet rays can be used.

Development can be carried out by a dip method, a spray method or the like, and the high pressure spray method is most suitable for achieving high resolution. The developing solution differs greatly between the solvent developing type and the alkali developing type. In the solvent developing type, it is general to use 1,1,1-trichloroethane, and in the alkali developing type,
It is common to use a 1% by weight aqueous sodium carbonate solution.

[0024]

The present invention will be described below with reference to examples. Example 1 To 211 parts by weight of a solution in which the materials in Table 1 were uniformly dissolved, 35 parts by weight of any of the pigments in Table 2 was added and dissolved to obtain a colored coating solution for a photosensitive resin layer.

[0025]

[Table 1]

[0026]

[Table 2]

Then, this solution was added to Teijin GS type 6μ.
An m-thick polyethylene terephthalate film (transparent support film (a)) was uniformly applied and dried in a hot air convection dryer at 100 ° C. for about 10 minutes to form a colored photosensitive resin layer (b). Then, a 30 μm thick polyethylene film was laminated as a protective film (c) to obtain a photosensitive film for a color filter. The film thickness of the colored photosensitive resin layer after drying was 1.8 μm.

Next, after heating the color filter substrate at 150 ° C. for 10 minutes, the outermost layer is a rubber layer having a diameter of 70 mm and a Shore hardness of 40 ° while peeling off the protective film of the color filter photosensitive film. The photosensitive resin layer was stuck together using a roll. The roll temperature at this time is 140
° C., a roll pressure of 5 kg / cm ^2, the rate was 1.0 m / min. Then, after exposing through a negative mask of a predetermined pattern with an exposure device HMW-201B (3 kW, ultra-high pressure mercury lamp, manufactured by Oak Manufacturing Co., Ltd.) to an exposure amount of 200 mJ / cm ² , the polyethylene terephthalate film was removed, and 3
The unexposed portion was removed by spray development with a 0.05% by weight Na ₂ CO ₃ aqueous solution at 0 ° C. for 15 seconds to form a color pattern of one color. This step of forming a colored pattern was repeated three times using the photosensitive films of respective colors in the order of red, blue and green to form a multicolored pattern.

The resulting multicolor pattern was heated at 150 ° C. for 45 minutes to obtain a color filter. When the appearance of the obtained color filter was visually observed, there was no image defect.

Comparative Example 1 The procedure of Example 1 was repeated, except that in the laminating step, a roll having a diameter of 50 mm and a rubber layer having a Shore hardness of 70 ° was used as the outermost layer. When the appearance of the obtained color filter was visually observed, many white spot defects due to air bubble entrapment were confirmed.

[0031]

According to the method of manufacturing a color filter of the present invention, soft rubber is pressed in a wide area,
Image defects due to entrainment of bubbles in the second and third colors can be prevented, and a high quality color filter can be manufactured.

Claims (3)

[Claims] 1. A photosensitive film for a color filter in which (a) a transparent support film, (b) a colored photosensitive resin layer, and (c) a protective film are laminated in this order on a substrate for a color filter (c). ) In the method for producing a color filter, which is performed by exposing while peeling off the protective film, and then developing, heating is performed using a roll having a rubber layer having a diameter of 60 mm or more and an outermost layer having a Shore hardness of 50 ° or less. A method of manufacturing a color filter, which is characterized in that 2. The method for producing a color filter according to claim 1, wherein the heating temperature for bonding is 100 ° C. or higher. 3. A color filter manufactured by using the method of manufacturing a color filter according to claim 1.