JPH06348010A - Photopolymerizable colored resin composition for color filter - Google Patents

Abstract

PURPOSE:To form the color filter superior in heat and weather resistance and high in sensitivity without forming an oxygen shielding film by incorporating a photopolymerizable compound, a specified tetra(t-butyl peroxy carbonyl) benzophenone compound, a sensitizing dye and a pigment. CONSTITUTION:The colored resin composition comprises the photopolymerizable compound, 3,3',4,4'-tetra(t-butylperoxycarbonyl)-benzophenone compound represented by the formula, the sensitizing dye, and the pigment, and when needed, a binder polymer, a solvent, and the like. This photopolymerizable resin is embodied by a photocross-linkable or photopolymerizable monomer or oligomer, such as mono- or polyol (meth)acrylate; a polyurethane acrylate obtained by allowing the reaction product of polyol and a compound having 2 isocyanate groups to react with (meth)acrylic acid; and an epoxy (meth) acrylate resin obtained by the reaction product of an epoxy resin and (meth) acrylate; and the like.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerizable composition for a color filter.

[0002]

2. Description of the Related Art A color filter mounted on a liquid crystal display device, a solid-state image pickup device or the like has a RGB color filter on a transparent substrate such as glass or plastic or an opaque substrate such as silicon.
Created by forming the primary colors. Conventionally, as a method of manufacturing this color filter, a dyeing method, a printing method, an electrodeposition method,
There is a pigment dispersion method and the like. The dyeing method can produce high-definition color filters with good spectral characteristics. However, since natural polymers such as casein and fish glue or water-soluble polymers such as PVA and dyes are used as colorants, they have weather resistance and heat resistance. Is bad and has a drawback that the process is long. The printing method is
Although there is no problem in terms of cost, there is still a problem in smoothness, and it is unsuitable for the production of a highly fine pattern. The electrodeposition method has a problem in driving the liquid crystal because a color filter is formed on the electrodes. Further, since the RGB matrix patterns that can be produced are limited, the adoption is limited. The pigment dispersion method is a method of obtaining a colored image by dispersing a pigment in a photosensitive resin, coating it on a substrate, drying it, exposing it to light, and developing it. This is a method that is excellent and has improved the above-mentioned problems. This light curing system
It has a drawback that radicals are obstructed by ambient oxygen, resulting in extremely low sensitivity. Therefore, usually, during exposure, replace the system with nitrogen or an inert gas,
Alternatively, as in Japanese Patent Laid-Open No. 4-164901, a method of further coating an oxygen barrier film such as polyvinyl alcohol on the photosensitive layer has been adopted, and in both cases, the number of steps is increased and the productivity is lowered. As described above, a photocurable resin composition containing a pigment having a sufficiently high sensitivity even without an oxygen barrier film has not been obtained by conventional techniques.

[0003]

The present invention provides a highly sensitive photopolymerizable colored resin composition for color filters by using a specific photoinitiator.

[0004]

The present invention provides a color containing a photopolymerizable compound, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, a sensitizing dye and a pigment. The present invention relates to a photopolymerizable colored resin composition for filters. 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone is a compound represented by the formula (1).

[Chemical 1]

The photopolymerizable colored resin composition for a color filter of the present invention contains a photopolymerizable compound, a compound represented by the above formula (1), a sensitizing dye and a pigment and, if necessary, a binder polymer, It is composed of components such as solvent. Examples of photopolymerizable compounds that can be used include photocrosslinkable or photopolymerizable monomers, oligomers and prepolymers such as ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, pentaerythritol. Esters of acrylic acid or methacrylic acid of monohydric or polyhydric alcohols such as triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate; polyhydric alcohol and monobasic acid or polybasic acid Polyester acrylate or polyester methacrylate obtained by reacting acrylic acid or methacrylic acid with a polyester prepolymer obtained by condensation of Polyurethane acrylate or polyurethane methacrylate obtained by reacting an all-group and a compound having two isocyanate groups with acrylic acid or methacrylic acid; obtained by reacting an epoxy resin with acrylic acid or methacrylic acid Examples thereof include epoxy acrylate or epoxy methacrylate resin.

The sensitizing dye is preferably a styryl compound, specifically 2- (p-dimethylaminostyryl).
Quinoline, 2- (p-diethylaminostyryl) quinoline, 4- (p-dimethylaminostyryl) quinoline, 4
-(P-diethylaminostyryl) quinoline, 2- (p
-Dimethylaminostyryl) -3,3'-dimethyl-3
H-indole, 2- (p-diethylaminostyryl)
-3,3'-Dimethyl-3H-indole, 2- (p-
Diethylaminostyryl) benzoxazole, 2-
(P-Diethylaminostyryl) benzthiazole, 2
Examples thereof include 2- (p-dimethylaminostyryl) benzimidazole and 2- (p-diethylamino) benzimidazole. Particularly preferable examples include 2- (p-dimethylaminostyryl) benzoxazole and 2- (p-dimethylaminostyryl) benzoxazole.
-Dimethylaminostyryl) benzthiazole. Coumarin compounds are also effective as sensitizing dyes, and specifically, 7-diethylamino-4-methylcoumarin, 4,6-dimethylamino-7-ethylaminocoumarin, 3- (2'-benzthiazolyl) -7- Diethylaminocoumarin, 3- (2'-benzimidazolyl) -7
-N, N'-diethylaminocoumarin, 7-diethylaminocyclopenta (c) coumarin, 7-amino-4-trifluoromethylcoumarin, 7-dimethylamino-4-
Trifluoromethylcoumarin, 1,2,4,5,3H,
6H, 10H-tetrahydro-8-trifluoromethyl (1) benzopyrano- (9,9a, 1-gh) quinolidin-1-one, 7-ethylamino-6-methyl-4-trifluoromethylcoumarin, 1,2 , 4, 5, 3H, 6
H, 10H-Tetrahydro-9-carbetoxy (1) benzopyrano (9,9a, 1-gh) -quinolizine-10
-One, 7-ethylamino-4-trifluoromethylcoumarin and the like, and particularly good ones include

[Chemical 2]

[Chemical 3]

[Chemical 4] And so on. The sensitizing dye is a photopolymerizable compound,
It is preferably used within the range of 0.5 to 10% by weight.

The pigment preferably has a particle diameter of 1/2 or less of the wavelength of the filtered light in order to filter visible light, more preferably a pigment having an average number particle diameter of 200 nm or less dispersed therein. . As a blue pigment, a phthalocyanine pigment, etc., as a red pigment, an anthraquinone pigment, etc.
As the green pigment, a halogenated phthalocyanine-based pigment is mentioned as a preferable example, and these may be used alone or in combination of two or more kinds. A carbon-based pigment is preferable as the black matrix pigment. It is preferable to use a pigment prepared by dispersing the pigment into fine particles in an organic solvent using a dispersant or a resin, the photopolymerizable compound described above, the compound represented by the formula (1), and It is preferably used in the range of 10 to 30% by weight with respect to the photosensitive liquid consisting of a dye, a solvent and a polymer used as necessary.

If necessary, a polymer for forming a film is required, and any polymer can be used as long as it is compatible with the photopolymerizable compound. It is preferably used in a range of 1 to 10 times by weight. For example, polyacrylic acid ester or its partial hydrolyzate; polyvinyl acetate or its hydrolyzate; polystyrene; polyvinyl butyral; polyvinyl chloride; polyvinylpyrrolidone; a photopolymer of styrene and maleic anhydride or a half ester thereof; acrylic acid. A copolymer selected from the group of monomers such as acrylic acid ester, methacrylic acid, methacrylic acid ester, acrylamide, and acrylonitrile is used. Further, a polymer in which an acryloyl group or a methacryloyl group which is a photosensitive group is introduced into these polymers can also be used, and examples thereof include a polymer in which a photosensitive group is introduced into a half ester compound of a styrene-maleic anhydride copolymer. It is possible to further increase the sensitivity. Among these, those having an acidic group such as a carboxyl group are capable of aqueous development and are more preferable in terms of economy and safety as compared with organic solvent development.

The resin composition according to the present invention is made into a solution at the time of use, and the solvent used dissolves the photopolymerizable compound, the compound represented by the formula (1), the sensitizing dye and the polymer. It is a component and preferably has a high boiling point and a high vapor pressure in order to improve the smoothness of the color filter film. For example,
Methylene glycol monomethyl ether, methylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and their acetyl compounds, methyl cellosolve, ethyl cellosolve, etc. As a preferable example. The amount of the solvent varies depending on the required viscosity, but it is preferably about 10 to 100 times the weight of the photopolymerizable compound.

The photopolymerizable colored resin composition for a color filter obtained by mixing the above-mentioned components can exert a main function as a composition for a color filter, but a polymerization inhibitor for further improving the stability over time, You may use additives, such as a smoothing agent, for providing the uniformity at the time of application.

The photopolymerizable composition of the present invention can be obtained by mixing the above-mentioned components while optionally dispersing and treating. The resulting mixture is preferably filtered (or pressure filtered) using a filter having a pore size of 1 μm or less to make particles uniform and to remove foreign substances.

The photopolymerizable colored resin composition of the present invention can be used as a color filter, for example, as follows. That is, the above-mentioned solvent to the photopolymerizable composition of the present invention, a coating solution by adding additives as necessary, spin coating, roll coating, bar coater coating,
A coating film having a thickness of 0.2 to 100 μm is obtained by coating the substrate by spray coating, printing coating or the like and drying. Through the photomask for the purpose of this coating, ultra high pressure mercury lamp, high pressure mercury lamp, metal halide lamp, far ultraviolet lamp,
It is exposed and cured using a light source such as a visible light laser. Next, this light-irradiated coating film is treated with an aqueous alkali solution (an aqueous solution of an alkali metal carbonate such as sodium carbonate, an alkali metal hydroxide such as sodium hydroxide, a base such as an organic alkali such as tetramethylammonium hydroxide), By exposing it to running water or shower water of organic solvents (organic halides such as trichlorethylene, perchlorethylene, methylene chloride, ketones such as methyl isobutyl ketone, cyclohexanone, and esters such as ethyl cellosolve acetate), and then washing with water The uncured part is dissolved and developed. This process can be repeated for each color to obtain a color filter.

[0013]

EXAMPLES The present invention will be described in more detail with reference to the following examples. In the examples, “parts” means “parts by weight”. Production Example 1 100 g of styrene-maleic anhydride copolymer was placed in a flask.
(SMA 1000, Mn: 1600, manufactured by Arco Chemical,
St / MA: 1), after charging 52 g (0.40 mol) of 2-hydroxyethyl acrylate, 210 g of propylene glycol monomethyl acetate was added, and 100
The temperature was raised to 0 ° C. and the mixture was stirred for 16 hours. Then, 31.8 g (0.20 mol) of glycidyl methacrylate was added together with 90 g of propylene glycol monomethyl acetate, and the mixture was further stirred for 12 hours to obtain a polymer. The obtained resin had a weight average molecular weight of 28,000 (Mw / Mn: 3.6
6), an acid value of 100 and a colorless polymer were obtained.

Example 1 A photosensitive solution having the composition shown in Table 1 was prepared.

[Table 1] Red, green, etc., added to the photosensitizing solution having the composition shown in Table 1, respectively.
Blue and black pigment pastes were prepared as follows.

To 50 parts of each color pigment shown in Table 2, 2.5 parts of sol sperse (dispersing agent) and 4 parts of polyvinylpyrrolidone are used.
In addition to 7.5 parts, 50 parts of propylene glycol monomethyl ether was added to prepare the pigment paste shown in Table 2. This pigment paste is added to the above-mentioned photosensitive liquid for each color arrangement.
Were mixed in an amount shown in (1) and passed through a 1 μm filter with a pressure filter to obtain a photopolymerizable resin composition for a color filter.

[0016]

[Table 2]

[0017]

[Table 3]

Each of the resulting photopolymerizable resin compositions of each color is applied onto a smooth glass substrate with a spin coater,
It was dried at 75 ° C for 5 minutes. The coating film thus obtained was passed through a negative mask using a parallel light type exposure machine HMW-590 (illuminance: 4.5 mW / cm ² ) manufactured by Oak Co., Ltd.
It was exposed at 00 mJ / cm ² and developed for 60 seconds in running water of a 3 wt% triethanolamine aqueous solution to obtain a pattern of each color. Table 4 shows the film thickness of each color pattern thus obtained.

[0019]

[Table 4] When this pattern was subjected to a heat resistance test at 250 ° C. for 3 hours, no change in each color was observed and no change in weight was observed.

Example 2 A photopolymerizable resin composition for a color filter was prepared in the same manner as in Example 1 except that the compositions shown in Table 5 were used as the photosensitive liquid.

[Table 5]

Comparative Example 1 A photopolymerizable composition for a color filter was prepared in the same manner as in Example 1 except that the composition shown in Table 6 was used as a photosensitive liquid.

[Table 6]

Table 7 shows the light energy required to form an image equivalent to that of Example 1 using the photopolymerizable composition for a color filter thus obtained. Light energy is measured by Oak Manufacturing thin UV photometer UV-3
50 was used. The resolution value in Table 7 indicates the minimum line and space value to be resolved.

[0023]

[Table 7]

[0024]

The photopolymerizable colored resin composition for a color filter according to the present invention has a simple process, high resolution, excellent heat resistance and weather resistance, and is a highly sensitive color without an oxygen barrier film. It becomes possible to manufacture a filter.

Claims (2)

[Claims] 1. A photopolymerizable compound, 3,3 ′, 4,4′-
A photopolymerizable resin composition for a color filter, which comprises tetra (t-butylperoxycarbonyl) benzophenone, a sensitizing dye and a pigment. 2. The photopolymerizable resin composition for a color filter according to claim 1, wherein the sensitizing dye is a styryl compound.