JPH06289214A - Photosensitive resin composition for forming transparent colored image and color filter - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin compsn. for forming a transparent colored image capable of producing a color filter with a fine pattern free from local drop-out of color and excellent in various characteristics such as light and heat resistance by a simple producing process. CONSTITUTION:A compd. having an ethylenically unsaid. group is emulsion- polymerized or suspension-polymerized in water in the presence of a pigment and the resulting colored fine particles are dispersed in a photosensitive resin compsn. to obtain the objective photosensitive resin compsn. for forming a transparent colored image.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition for forming a transparent colored image and a color filter formed using the same. The color filter obtained by using the photosensitive resin composition of the present invention is particularly used as a color filter mounted on a color liquid crystal display device, a color facsimile, a three-tube type and a single-tube type color video camera, a solid color video camera and the like. It is useful.

[0002]

2. Description of the Related Art Color filters used in color solid-state image pickup devices (for example, image pickup ICs such as CCD, CID, BBD) and color liquid crystal display devices, which are in great demand as VTR cameras, are colored in two or more hues. It is formed by providing a fine region on a solid-state image sensor or a transparent substrate. In general, a photosensitive resin composition capable of forming a transparent colored image is used for coloring a fine region with two or more colors having different hues.

Conventionally, in order to form two or more transparent colored images with a photosensitive resin, for example, gelatin,
A photosensitive resin prepared by adding a dichromate, a diazo compound or the like as a photosensitizer to a natural or synthetic polymer substance such as casein, glue or partially saponified polyvinyl acetate is provided on a substrate to form a mordant layer. . This mordant layer is exposed to ultraviolet light through a mask having a pattern of a predetermined shape, then developed and dyed with a desired dye to form a first colored image. Next, on this first transparent colored image,
After forming a transparent dye-proof resin film made of a hydrophobic resin in order to prevent dye migration, a second transparent colored image is formed in the same manner as the formation of the first transparent colored image. By repeating the above operation, a transparent colored image colored in two or more colors is formed on the support.

However, according to the above-mentioned method, since it is necessary to form a dye-proof resin film for each dyeing process of each color, the manufacturing process is extremely complicated, and unevenness is caused by the dye-proof resin film. There are drawbacks such that the film thickness of the colored image tends to differ. Further, some color filters may be heated in the manufacturing process, but since the dye itself generally has low heat resistance and light resistance, there is a drawback that fading occurs.

Further, as another simplest method for manufacturing a color filter, there is a method of forming by printing, but there is a limit in positional accuracy and dimensional accuracy, and a high-precision and high-fineness color filter is required. It cannot be manufactured. Therefore, as a promising method for overcoming these problems, there is a method of forming a color filter with a photosensitive resin which is colored with a pigment in advance. Compared to the dyeing method, this method does not require the formation of a dye-proof resin film for each color, so the manufacturing process is short and simple,
In addition, many attempts have been made due to advantages such as heat resistance of pigment being superior to that of dye. For example, JP-A-60-23
7403, JP-A-61-254906, JP-A-2-
Polyamide resin, such as disclosed in 153353,
Examples thereof include a method in which a pigment is dispersed in a polyimide resin or an acrylic resin. However, in general, it is difficult to disperse a pigment at a high concentration and with good stability, and the pigment particles settle or reaggregate over time. Further, even if a dispersant is added to improve the dispersibility, the adhesion between the support and the colored image is deteriorated due to the influence of the dispersant, and the water resistance, solvent resistance and chemical resistance of the colored image are deteriorated. Problem easily occurs.

Further, JP-A-60-129738, JP-A-60-129739, and JP-A-60-129707.
As disclosed in No. etc., a method of forming a colored image by dispersing a pigment in water-developable partially saponified polyvinyl acetate has been studied, but in this case also, the dispersibility of the pigment becomes a problem, The pigment particles settle down, the particles re-aggregate over time, the pigment is partially partially saponified, and it is difficult to disperse it with polyvinyl acetate. There are defects such as formation, and a uniform colored image cannot be obtained. Even if a dispersant is added to improve the dispersibility, problems such as poor adhesion between the support and the colored image are likely to occur due to the influence of the dispersant. Further, in a certain type of color filter, the color filter is exposed to a high temperature of 200 to 300 ° C. during the vacuum deposition and the formation of the coater coat layer in the manufacturing process. Therefore, the partially saponified polyvinyl acetate binder resin is used. Has a problem such as being colored.

[0007]

SUMMARY OF THE INVENTION The present invention is to solve all of the drawbacks of the prior art as described above.
It has the following purposes. 1) When two or more colored transparent colored images such as color filters are provided adjacently on a support, it is not necessary to form a transparent dye-proof resin film for each color, Therefore, the present invention provides a photosensitive resin composition for forming a transparent colored image, which has a simplified manufacturing process, and a color filter using the same.

2) To provide a photosensitive resin composition for forming a transparent colored image in which a pigment is stably dispersed in a high concentration and which can form a homogeneous transparent colored image, and a color filter using the same. 3) To provide a photosensitive resin composition for transparent colored image formation capable of forming a transparent colored image excellent in heat resistance and light resistance, and a color filter using the same.

[0009]

In order to achieve the above object, the transparent colored image-forming photosensitive resin composition of the present invention comprises a compound having an ethylenically unsaturated group in the presence of a pigment. The colored fine particles obtained by emulsion polymerization or suspension polymerization in water are dispersed in the photosensitive resin composition.

Conventionally, JP-A-58-7646 and JP-A-5-
9-33302, JP-A-62-288632, JP-A-2-187402 and the like, a pigment is dispersed in a compound having an ethylenically unsaturated group, and this composition is prepared in the presence of a protective colloid agent. It is known that colored aqueous resin emulsions and colored fine particles can be obtained by suspension heating polymerization in an aqueous medium. But in both cases,
They were used for paints or toners, and were merely intended for coloring and hiding.

The transparency of the colored aqueous resin emulsion and the dried film of the colored fine particles obtained by the above method was considered to be low because the dispersibility of the pigment in the compound having an ethylenically unsaturated group was incomplete. . for that reason,
It has been considered that the colored aqueous resin emulsion and the colored fine particles in which the above-mentioned pigment is incorporated are unsuitable as a material for the colored photosensitive resin for use in a color filter in which high transparency is required for the film.

However, the inventors of the present invention have unexpectedly high transparency of the dried film of the colored aqueous resin emulsion and the colored fine particles in which the above-mentioned pigment is incorporated, and thus are sufficiently used as materials for color filters. Found to get. The reason for this is that even a pigment that is incompletely dispersed in a compound having an ethylenically unsaturated group can be emulsified with a protective colloid agent that emulsifies the compound having an ethylenically unsaturated group. It is considered that the transparency is increased because the pigment is completely dispersed in the compound having an ethylenically unsaturated group at the same time as the compound having a is emulsified. Alternatively, it is considered that the ethylenically unsaturated compound itself in which the pigment is incompletely dispersed has a fine particle size to such an extent that high transparency is obtained.

However, the inventors of the present invention further enhance the transparency of the obtained dry film by setting the particle diameters of the aqueous resin emulsion and the coloring fine particles in which the above-mentioned pigment is incorporated, to the wavelength of the incident light or less. In addition to the above, the inventors have found that the above object can be achieved by forming a color filter using a photosensitive resin composition in which colored fine particles are dispersed, and have completed the present invention.

That is, in the transparent colored image-forming photosensitive resin composition of the present invention, a pigment is dispersed in a compound having an ethylenically unsaturated group, and emulsion polymerization or suspension polymerization is carried out to prepare emulsion particles. Obtained by dispersing the colored fine particles obtained by fixing the pigment in the photosensitive resin. By using this, pigment aggregation and sedimentation are prevented, high dispersion stability is obtained, and color fading etc. It is possible to form a color filter having a uniform transparent colored image with no color.

Further, in the present invention, it was also found that the following effects can be obtained because the pigment particles are completely contained in the continuous polymer coating layer. 1. It is possible to prevent color fading of the pigment due to light, and obtain a color filter having excellent light resistance. 2. A color filter can be obtained which can prevent the electrostatic charge of the pigment and is not affected by static electricity.

3. When the colored fine particles are dispersed in the photosensitive resin composition, a dispersant such as a surfactant can be easily dispersed with little use, and a color filter not affected by the dispersant can be obtained. 4. Adsorption on the surface of the colored fine particles does not occur, and the solution viscosity of the photosensitive resin composition is suppressed to a low level. Therefore, it is possible to increase the concentration of the colored fine particles and obtain a photosensitive resin composition for forming a color filter with high color density. To be

5. It is possible to obtain a photosensitive resin composition for forming a color filter, which is stable for a long period of time without aggregation of colored fine particles, and can be easily redispersed even when the colored fine particles settle. A high quality color filter can be obtained by using the photosensitive resin composition containing colored fine particles having these excellent characteristics.

In the present invention, the pigment is contained in a polymer from a compound having an ethylenically unsaturated group. The pigment used may be either organic or inorganic, but it is desirable that it has excellent heat resistance, light resistance and solvent resistance. Examples of organic pigments include azo-based, phthalocyanine-based, benzimidazolone-based, quinacridone-based, isoindolinone-based, pyranthrone-based, dibrom zanzanthrone-based, indasulone-based, anthrapyrimidine-based, flavasuron-based, perylene-based, perinone System, quinophthalone system,
Examples thereof include phthalone-based, thioindigo-based, indico-based, dioxazine-based, anthraquinone-based, xanthene-based, methine-based, azomethine-based pigments and condensed polycyclic pigments including other metal complex-based pigments. Examples of inorganic pigments include milori blue, iron oxide, cobalt purple, manganese purple, ultramarine blue, dark blue, cobalt blue, cerulean blue,
Viridian, emerald green, cobalt green and the like can be mentioned, and one or more can be appropriately selected and used from these.

These organic and inorganic pigments have a particle size of 0.7 μm from the viewpoints of light transmittance, uniformity of the film surface and the like.
m or less, preferably 0.1 μm or less, which is sufficiently small for the wavelength of visible light. next,
The compound having an ethylenically unsaturated group is a compound having one or more ethylenically unsaturated groups in the molecule, and examples thereof include alkyl acrylates (eg, methyl acrylate, ethyl acrylate, butyl acrylate). , 2-ethylhexyl acrylate, etc.), methacrylic acid alkyl esters (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid-2)
-Ethylhexyl), epoxy acrylates (including methacrylate), urethane acrylates (including methacrylate), polyether acrylates (including methacrylate), polyester acrylates (including methacrylate), acrylic acid, methacrylic acid, acrylic acid Glycidyl, glycidyl methacrylate, allyl acrylate, allyl methacrylate, itaconic acid, acrylamide, methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, methacrylic acid Hydroxypropyl, N-methylol acrylamide, N-
Methylol methacrylamide, acrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyltoluene, vinylpyridine, 2-hydroxy-3-phenoxypropyl acrylate, p-nonylphenoxyethyl acrylate, 1,6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 2-hydroxy-1-acryloxy-3-methacryloxypropane, 3-butylene glycol dimethacrylate, 2,2-bis [4 (acryl Oxy-polyethoxy) phenyl] propane,
2,2-bis [4 (methacryloxy-polyethoxy)
Phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane triacrylate,
Examples thereof include tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, and the like. These are used alone or in combination of two or more kinds. be able to.

However, the colored fine particles polymerized by the combination of a so-called monofunctional compound having one ethylenically unsaturated group in the molecule and a pigment have a low cross-linking density in the particles and thus have a low film forming temperature. In some cases, particles are fused with each other during film formation by drying, the redissolvability in water is lowered, and the unexposed portion cannot be completely removed by development, and a color may remain. On the other hand, the crosslink density in the particles is appropriately increased by a combination of so-called polyfunctional compounds and monofunctional compounds having two or more ethylenically unsaturated groups in the molecule or a combination of polyfunctional compounds, that is, The colored fine particles having a high film-forming temperature have advantages that they do not form a film by fusion of particles during drying, have good redispersibility, and do not cause a problem of poor development.

The content ratio of the pigment is the weight (A) of the pigment and
The weight ratio (B) of the compound having an ethylenically unsaturated group is A: B = 1: 99 to 80:20, preferably A: B.
= 10: 90 to 60:40, and this content ratio is determined in consideration of the spectral characteristics of the pigment and the coloring density of the pigment. To obtain colored fine particles, first,
A pigment-containing compound having an ethylenically unsaturated group is prepared. Preparation of the compound having an ethylenically unsaturated group containing a pigment, the pigment is added to the compound having an ethylenically unsaturated group, after stirring and mixing, sufficiently using a homomixer, ball mill, roll mill, sand grinder, etc. And then remove the one having a large particle size with a filter. A small amount of dispersant may be used at the time of dispersion. Pigment particle diameter is visible light wavelength (0.4μ
It is preferable to disperse the pigment so that it is smaller than 0.5 .mu.m to 0.7 .mu.m).
It is preferably 3 μm or less and the blue pigment is 0.2 μm or less.

Next, emulsion polymerization or suspension polymerization is carried out by a conventional method using the compound having an ethylenically unsaturated group containing the above pigment. Examples of useful polymerization initiators include benzoyl peroxide, cumene hydroperoxide, succinic acid peroxide, lauroyl peroxide, peroxides such as hydrogen peroxide, and 2,2′-
Azo compounds such as azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-amidinopropane) dihydrochloride, ammonium persulfate, potassium persulfate, etc. And a redox catalyst such as a combination of the persulfate compound and a reducing sulfoxy compound, a combination of a perchloric acid compound and a reducing sulfoxy compound, and the like.

The protective colloid used herein has a saponification degree of 70 to 99 mol% and a polymerization degree of 300 to 40.
And partially saponified polyvinyl acetate derivatives having a reactive unsaturated group as disclosed in JP-A-63-81101. Other useful as a protective colloid agent include, for example, gelatin, casein, collagen, starch,
Starch derivative, gum arabic, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose,
Examples include polyacrylamide, polyacrylic acid, and water-soluble nylon, and protect water-soluble polymers having reactive unsaturated groups and thiol groups as disclosed in JP-B-44-25794 and JP-A-59-187005. It can be mentioned as a colloid.

Depending on the case, the protective colloid such as the water-soluble polymer and one or more kinds of interfaces selected from anionic surfactants, cationic surfactants, amphoteric surfactants or nonionic surfactants. You may polymerize using an activator together. Furthermore, without using a protective colloid such as the water-soluble polymer, it is selected from an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant.
One or more surfactants may be used as emulsion stabilizers for polymerization.

However, if a large amount of these surfactants is used, the water resistance of the transparent colored image and the adhesiveness to the support are adversely affected, so it is desirable to use a relatively small amount even if used. The suspension polymerized as described above can be filtered, and the residue can be washed and dried to obtain colored fine particles.

Next, a photosensitive resin composition is prepared using the obtained colored fine particles. As the photosensitive resin used in the present invention, a compound having a photosensitive group in the molecule and a compound to which photosensitivity is imparted by a combination with a photocrosslinking agent are used. Specifically, the following compounds are used. (A) Water-soluble photosensitive resin having a photosensitive group Polyvinyl alcohol resin, polyvinyl alcohol derivative resin such as polyvinyl alcohol / stilbazolium resin, and the like. (B) Oil-Soluble Photosensitive Resin Having Photosensitive Group Photocrosslinkable photosensitive resin such as cinnamic acid type, photodegradable crosslinked type photosensitive resin such as bisazide type, photodegradable polarity change type photosensitive resin such as o-quinonediazide type Resin etc. (C) A combination of the following (a) binder resin and (b) a photocrosslinking agent (a) binder resin (i) animal protein system such as gelatin, casein, mulled (ii) carboxymethyl hydroxyethyl cellulose,
Cellulosics such as hydroxyethyl cellulose, hydroxypropyl cellulose, and methyl cellulose (iii) polyvinyl alcohol, polyvinylpyrrolidone,
Polyvinyl methyl ether, polyacrylic acid, polyacrylamide, polydimethylacrylamide and copolymers thereof, and alkali developable acrylic acid ester-methacrylic acid copolymer and methacrylic acid ester-
Vinyl polymerization system such as methacrylic acid copolymer (iv) Ring-opening polymerization system such as polyethylene glycol and polyethyleneimine (v) Condensation system such as water-soluble nylon (vi) Butyral resin, styrene-maleic acid copolymer, chlorine Polyethylene or chlorinated polypropylene,
Oil-soluble resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, acrylic resins, polyamides, polyesters, phenolic resins, polyurethane resins, etc. (b) Photocrosslinking agents Dichromate, chromium Acid salts, diazo compounds, bisazide compounds, etc.

(D) (a) The above binder resin, the following (b) monomer or oligomer, and (c)
Combination with initiator (b) Monomer or oligomer Acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-
Hydroxypropyl methacrylate, vinyl acetate, N-vinylpyrrolidone, acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-
(1,1-Dimethyl-3-oxobutyl) acrylamide, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, methylenebisacrylamide, 1,3,5-triacryloyl-1,3,5
-Triazacyclohexane, pentaerythritol triacrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acryloyloxyethyl acid phosphate, styrene, vinyl acetate , Various acrylic acid esters, various methacrylic acid esters, acrylonitrile, etc. (C) Initiators (i) Photodegradable initiators such as azobisisobutyronitrile, benzoin alkyl ether, thioacridone, benzyl, N- [alkyl Sulfonyloxy]-
1,8-naphthalene dicarboximide, 2,4,6-
Tri (trichloromethyl) triazine etc. (ii) Hydrogen transfer type initiators such as benzophenone, anthraquinone, 9-phenylacridine etc. (iii) Electron transfer type complex initiators such as benzanthrone / triethanolamine, methylene blue / benzene Sulfinate, triallyl imidazolyl dimer /
Michler's ketone, carbon tetrachloride / manganese carbonyl, etc. In the present invention, colored fine particles are dispersed in the above-mentioned photosensitive resin to form a transparent colored image-forming photosensitive resin composition.

The photosensitive resin composition may have various constitutions depending on the combination, but from the viewpoint of prevention of environmental pollution and safety, the constitution which can be developed with water or an aqueous alkali solution is preferable. Further, in the constitutions of (a), (c) and (d), a compound having an ethylenically unsaturated group, as disclosed in Japanese Patent Application No. 3-341063,
It does not matter even if a water-soluble resin emulsion filled with a photosensitive pigment obtained by emulsion polymerization or suspension polymerization in water in the presence of a pigment is mixed and used.

Further, in some cases, an organic or inorganic pigment may be added to the photosensitive resin containing colored fine particles to adjust the coloring density and color tone. Incidentally, additives usually contained in this type of photosensitive resin composition, for example, an antifoaming agent, an anti-repellent agent, a preservative, a thermal polymerization inhibitor, a leveling agent and the like may be optionally added. Application of the photosensitive resin composition containing the colored fine particles prepared as described above to the support is carried out, for example, by a method such as a spin coating method, a roll coating method, a dipping method, a spray method, a printing method, or the like at the time of drying. The film thickness is about 0.1 to 10 μm, preferably about 0.5 to 3 μm. The coating film is dried using a hot air drier, a hot plate, etc., and after drying, a mask of a predetermined shape such as a dot pattern or stripe pattern is brought into close contact, and a xenon lamp, metal halide lamp, ultra-high pressure mercury lamp is passed through this mask. Pattern exposure using a light source such as. Then, the non-exposed areas may be selectively removed by spray development or immersion development with a developing solution such as water, an alkaline aqueous solution, an organic solvent. By repeating the same operation a plurality of times, transparent colored images of a plurality of colors can be provided on the support without forming a resin film for dye protection.

As the support, transparent glass, a transparent resin film, a metal plate, a ceramic plate, a solid-state image pickup device which is a photoelectric conversion device, or the like can be used. The transparent colored image may be formed directly on the support,
The transparent colored image may be indirectly formed on the support on which the black matrix is formed or on the support on which an intermediate layer such as an undercoat is provided. Furthermore, it does not matter if a cover coat layer is formed on the transparent colored image.

The transparent colored image thus obtained is
It has excellent heat resistance and light resistance.

[0032]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Example 1 Operation 1 As an organic pigment, 30 parts by weight of chromophthal blue 4GNP (blue pigment manufactured by Ciba-Geigy), 40 parts by weight of butyl acrylate, and 20 parts of 2-ethylhexyl acrylate were used.
By mixing with 1 part by weight and 10 parts by weight of 1,6-hexanediol diacrylate, the pigment particles were sufficiently dispersed so that the particle diameter of the pigment was 0.2 μm or less to obtain a blue pigment-containing oligomer.

Next, the blue pigment-containing oligomer 10
To 0 parts by weight, 0.5 parts by weight of 2,2'-azobisisobutylnitrile as a thermal polymerization initiator was added, and 5 parts by weight of a nonionic surfactant Emulgen 950 (manufactured by Kao Corporation, polyoxyethylene nonylphenyl ether). Was used to carry out suspension polymerization according to a conventional method. The suspension obtained by polymerization was filtered, and the residue was washed with water and dried to obtain colored fine particles.

The colored fine particles thus obtained were treated with a photosensitive polyamide resin, Lithocoat PA-1000 (manufactured by Ube Industries, Ltd.,
Polymer content 10%, solvent N-methyl-2-pyrrolidone)
Was dispersed so that the ratio of the colored fine particles to the polymer was 1: 2 to obtain a blue photosensitive resin composition. The resulting composition was stable over the long term. Then attached FIG.
A blue transparent colored image was prepared as shown in FIGS. First, the blue photosensitive resin composition 1 is applied onto the transparent glass substrate 2 so that the dry film thickness is 1 μm (FIG. 1).
After drying at 80 ° C. for 30 minutes, pattern exposure is performed with ultraviolet rays 4 through a mask 3 having a predetermined shape, and N-methyl-2
-Develop with pyrrolidone and dry (150 ° C, 30 minutes)
(FIG. 2) to form a blue transparent colored image 5 (FIG. 3). Adhesion between the formed blue transparent colored image and the glass substrate was good, and the image was uniform without local color loss.

The transmittance of the blue transparent colored image thus obtained was 75% at 460 nm and 5% at 620 nm. This blue transparent colored image at 250 ℃ 6
Even when heated for 0 minutes, its spectral transmittance characteristics hardly changed. Further, a light resistance test was carried out for 1000 hours using a xenon fade-o-meter, and only a very slight change such as a peak transmittance change of 5% or less and a peak wavelength shift of 5 nm or less was observed.

Procedure 2 Chromophtal green GFN (green pigment manufactured by Ciba-Geigy) was used as an organic pigment, and green colored fine particles were obtained in the same manner as in Procedure 1. Further, the green transparent colored image formed by using the green photosensitive resin composition prepared in the same manner as in the operation 1 has good adhesion and uniformity, and the transmittance is 75% at 540 nm and 3% at 640 nm. Met. Further, even if the green transparent colored image is heated at 250 ° C. for 60 minutes, its spectral transmittance characteristics are almost unchanged and are good.
The result of the light resistance test at 00 hours was also good.

Operation 3 As the organic pigment, chromophthal red A2B (red pigment manufactured by Ciba-Geigy) was used, and red colored fine particles were obtained in the same manner as in Operation 1. Further, the red transparent colored image formed by using the red photosensitive resin composition prepared in the same manner as in the operation 1 has good adhesion and uniformity, and the transmittance is 85% at 630 nm and 5% at 540 nm. Met. Further, even if the red transparent colored image is heated at 250 ° C. for 60 minutes, its spectral transmittance characteristic is almost unchanged and is good.
The result of the light resistance test at 00 hours was also good.

Operation 4 Using the blue, green and red photosensitive resin compositions prepared in Operations 1, 2 and 3, by repeating patterning, a three-color mosaic of blue, green and red was formed on the transparent glass substrate. Patterned transparent colored images 5, 6, 7
To form a color filter (FIG. 4). A transparent conductive film is formed on the obtained colored image and subjected to orientation treatment,
It was combined with a thin film transistor which becomes the counter electrode. Next, when liquid crystal was injected to assemble a cell and applied to a full-color liquid crystal display device, excellent characteristics were obtained.

Example 2 Operation 1 In the same manner as in Operation 1 of Example 1, blue colored fine particles were synthesized. 88 parts by weight of 5 parts by weight of the obtained blue colored fine particles
A blue photosensitive resin composition was prepared by dispersing 10 parts by weight of a photosensitive resin composition obtained by introducing 2 mol% of N-methyl-γ- (p-formylstyryl) -pyridinium salt into partially saponified polyvinyl acetate (degree of polymerization: 1700). I got a thing. The obtained blue photosensitive resin composition was stable for a long period of time.

Then, this blue photosensitive resin composition was applied onto a glass substrate in the same manner as in operation 1 of Example 1,
A blue transparent colored image was formed by exposing, developing with water and drying. The characteristics of the obtained image are shown in Example 1.
Was as good as that of the operation 1 of. Operation 2 A green transparent colored image was obtained in the same manner as in Operation 2 of Example 2 by using the green colored fine particles obtained by synthesis in the same manner as in Operation 2 of Example 1.

The characteristics of the obtained image are as described in operation 2 of Example 1.
It was as good as that. Operation 3 Using the red-colored fine particles obtained by synthesis in the same manner as in Operation 3 of Example 1, in the same manner as in Operation 1 of Example 2,
A red transparent colored image was obtained. The properties of the image obtained were as good as those of operation 3 of example 1.

Operation 4 A color filter was formed in the same manner as in Operation 4 of Example 1 using the blue, green and red photosensitive resin compositions prepared in Operations 1, 2 and 3 above. Then, when it was similarly applied to a full-color liquid crystal display device, excellent characteristics were obtained. Example 3 Operation 1 Methylmethacrylate: methacrylate = 93: 7
The copolymer (about 70,000 in weight average molecular weight) was synthesized according to a conventional method to obtain a binder resin.

Using the blue colored fine particles obtained by the operation of Example 1, a blue photosensitive resin composition was prepared with the following composition. Binder resin 60 parts by weight Trimethylolpropane triacrylate 30 parts by weight Tetraethylene glycol diacrylate 30 parts by weight Blue colored fine particles 60 parts by weight 2,4-diethylthioxanthone 2 parts by weight Ethyl p-dimethylaminobenzoate 1 part by weight Methyl ethyl ketone 200 parts by weight 200 parts by weight of toluene The obtained composition was stable for a long period of time.

Then, in the same manner as in the operation 1 of Example 1,
It was coated on a glass substrate, exposed, developed with a 0.5% aqueous solution of tetramethylammonium hydroxide, washed with water and dried to form a blue transparent colored image. The properties of the image obtained were as good as those of operation 1 of example 1. Operation 2 In the same manner as in Operation 2 of Example 1, the green transparent fine particles obtained by synthesis were used to prepare a green transparent colored image in the same manner as in Operation 1 of Example 3.

The properties of the image obtained were as good as those of operation 2 of example 1. Operation 3 Using the red-colored fine particles obtained by synthesis in the same manner as in Operation 3 of Example 1, a red transparent colored image was prepared in the same manner as in Operation 1 of Example 3. The characteristics of the obtained image are
It was as good as that of the operation 3 of Example 1.

Operation 4 Using the blue, green and red photosensitive resin compositions prepared in Operations 1, 2 and 3 above, a color filter was formed in the same manner as in Operation 4 of Example 1. Then, when it was similarly applied to a full-color liquid crystal display device, excellent characteristics were obtained.

[0047]

EFFECTS OF THE INVENTION According to the present invention, by using a photosensitive resin composition containing colored fine particles in which a pigment is fixed in the particles and excellent in dispersion stability, there is no local color loss.
It is possible to manufacture a color filter having a fine pattern having excellent light resistance and heat resistance characteristics by a simple manufacturing process.

Therefore, the present invention can be applied to a wide variety of devices requiring a color filter having good performance, and a color device having excellent characteristics can be manufactured.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a first step in an example of a process for producing a color filter using the transparent colored image-forming photosensitive resin composition of the present invention.

FIG. 2 is a cross-sectional view showing a second step in the above example of the manufacturing process of the color filter using the transparent colored image-forming photosensitive resin composition of the present invention.

FIG. 3 is a cross-sectional view showing a third step in the above example of the manufacturing process of the color filter using the transparent colored image-forming photosensitive resin composition of the present invention.

FIG. 4 is a cross-sectional view of a color filter made of the photosensitive resin composition for forming a transparent colored image of the present invention obtained in the above examples.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Transparent colored image forming photosensitive resin composition 2 ... Glass substrate 3 ... Photomask 4 ... Ultraviolet ray 5 ... Blue color filter pattern 6 ... Green color filter pattern 7 ... Red color filter pattern

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kyoichi Sato 27-2 Hiraide Industrial Park, Utsunomiya City, Tochigi Prefecture Oji Kako Co., Ltd. Product Research Center

Claims (2)

[Claims] 1. A compound having an ethylenically unsaturated group,
A photosensitive resin composition for forming a transparent colored image, wherein colored fine particles obtained by emulsion polymerization or suspension polymerization in water in the presence of a pigment are dispersed in a photosensitive resin composition. 2. A color filter, wherein a pattern of a plurality of colors obtained by photocrosslinking the photosensitive resin composition according to claim 1 is provided on a support.