JPH06289215A - 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 water-insoluble or slightly water-soluble compd. having at least one ethylenically unsaid. group and contg. a dissolved photopolymn. initiator and a dispersed pigment is emulsified in an aq. soln. of a water-soluble polymer contg. a water-soluble photo-crosslinking agent or a water-soluble polyvner having self-photocrosslinkable groups 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 useful as a color filter to be 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. Is.

[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. Generally, 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. However, there is a defect that the difference in the thickness of the colored image is likely to occur. Furthermore, some color filters may be heated in the manufacturing process, but the heat resistance of the dye itself,
Since light resistance and the like are generally low, there is a defect that fading occurs.

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 with 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, and many attempts have been made from the advantage that the heat resistance of the pigment is superior to that of the dye. Has been done. For example, JP-A-60-
As disclosed in JP-A-237403, JP-A-61-254906, JP-A-2-153353 and the like, a method of dispersing a pigment in a polyamide resin, a polyimide resin or an acrylic resin can be mentioned. 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 with 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. Furthermore, in a certain type of color filter, the color filter is exposed to a high temperature of 200 to 300 ° C. when performing vacuum deposition and formation of an overcoat layer in the manufacturing process, and thus partially saponified polyvinyl acetate which is a binder resin is used. Has a problem such as being colored.

[0007]

SUMMARY OF THE INVENTION The present invention is intended to solve all the drawbacks associated with 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, which can form a uniform transparent colored image, and a color filter using the same. 3) To provide a photosensitive resin composition for forming a transparent colored image 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 objects, the transparent colored image-forming photosensitive resin composition according to the present invention comprises a photopolymerization initiator dissolved and a pigment dispersed therein.
A water-insoluble or sparingly soluble compound having at least one ethylenically unsaturated group is a water-soluble polymer containing a water-soluble photocrosslinking agent and a water-soluble polymer containing a photocrosslinkable group having photocrosslinkability by itself. It is characterized in that it is emulsified in an aqueous solution of a water-soluble polymer selected from organic polymers.

The present invention also provides a color filter produced using this transparent colored image-forming photosensitive resin composition. Conventionally, JP-A-58-7646 and JP-A-59
No. 33302, JP-A No. 62-288632, JP-A No. 2-187402, etc., 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 a colored aqueous resin emulsion and colored fine particles can be obtained by suspension heating polymerization in an aqueous medium. However, in any case, they were used for paints or toners, and were merely used for coloring or hiding.

The transparency of the dried film of the colored aqueous resin emulsion prepared 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. Therefore, it has been considered that a colored aqueous resin emulsion containing the above-mentioned pigment is unsuitable as a material for an already colored photosensitive resin for color filter applications in which high transparency of the film is required.

However, the present inventors have found that the transparency of the dry film of the colored aqueous resin emulsion containing the above-mentioned pigment is unexpectedly high, and can be sufficiently used as a material for color filters. It was The reason for this is that even if the pigment is incompletely dispersed in the compound having an ethylenically unsaturated group, it can be emulsified with a protective colloid agent that emulsifies the compound having an ethylenically unsaturated group. As the compound having a group is emulsified, at the same time, the pigment is also completely dispersed in the compound having an ethylenically unsaturated group, so that the transparency is considered to be increased. 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.

In the present invention, when a compound having an ethylenically unsaturated group in which a pigment is dispersed is emulsified in an aqueous solution in which a protective colloid agent is present, the compound having an ethylenically unsaturated group in which the pigment is dispersed is emulsified. It has been further found that the emulsification so that the particle size of is less than or equal to the wavelength of the incident light further enhances the transparency of the obtained dry film, and is therefore preferable.

That is, the inventors of the present invention, in an emulsion aqueous solution of the compound having an ethylenically unsaturated group in which the pigment is dispersed, make the particle diameter of the compound having an ethylenically unsaturated group in which the pigment is dispersed incident If it is less than or equal to the wavelength of light, it is found that the transparency of the obtained dry film is further enhanced, and the photopolymerization initiator is dissolved in a compound having an ethylenically unsaturated group in which the pigment is dispersed,
By forming a transparent colored image using a photosensitive resin in which an emulsion aqueous solution of a compound having an ethylenically unsaturated group in which this pigment is dispersed and a photocrosslinking agent are combined,
The inventors have found that the above objects can be achieved, and completed the present invention.

That is, in the photosensitive resin composition useful in the present invention, a pigment is dispersed in a compound having an ethylenically unsaturated group, and the compound having the ethylenically unsaturated group is added in the presence of a protective colloid agent. , By emulsifying in water,
It is obtained by encapsulating the pigment in the emulsion particles, whereby aggregation and sedimentation of the pigment can be prevented and high dispersion stability can be obtained. Further, upon irradiation with light, the pigment is fixed in a compound having an ethylenically unsaturated group which is polymerized and cured by a photopolymerization initiator to form a color filter having a uniform transparent colored image without color fading. can do.

Further, in the transparent colored image formed by the photosensitive resin composition of the present invention, since the pigment particles are completely included in the continuous polymer coating layer, the polymer film prevents fading due to light and the pigment It was also found that the effect of preventing charging can be obtained. In addition, the document “Emulsion Polymerization of Vinyl Acetate”, APP
As shown in LIED SCIENCE PUBLISHERS, when partially saponified polyvinyl acetate is used as a protective colloid for emulsion polymerization or suspension polymerization, a compound having an ethylenically unsaturated group and an acetic acid residue of partially saponified polyvinyl acetate are There is some cross-linking due to chemical or physical grafting. The photopolymerization initiator in the emulsion aqueous solution obtained by emulsifying the compound having an ethylenically unsaturated group, in which the photopolymerization initiator in the invention is dissolved and the pigment is dispersed, by using partially saponified polyvinyl acetate as a protective colloid agent. When polymerizing a compound having an ethylenically unsaturated group, the compound having an ethylenically unsaturated group and the acetic acid residue of partially saponified polyvinyl acetate are chemically or physically grafted to cause some crosslinking. It is thought that By this grafting,
Compared with the case where the partially saponified polyvinyl acetate is simply dissolved and released in water, the partially saponified polyvinyl acetate grafted with a compound having an ethylenically unsaturated group has improved heat resistance, It turned out that it has an effect that could not be expected conventionally. Furthermore, Japanese Patent Publication No.
As disclosed in JP-A No. 4 and JP-A-63-81101, emulsification is carried out by using a partially saponified polyvinyl acetate derivative having a reactive unsaturated group as an emulsifier.
During the photopolymerization of a compound having an ethylenically unsaturated group with a photopolymerization initiator, the grafting ratio with a compound having an ethylenically unsaturated group of partially saponified polyvinyl acetate having a reactive unsaturated group increases, It was found that the heat resistance increased. In addition, since the partially saponified polyvinyl acetate derivative having a reactive unsaturated group itself has an emulsifying action on a compound having an ethylenically unsaturated group, almost no surfactant is used or a relatively small amount is used. It was also found that a stable water-soluble emulsion was obtained by the above method, and thus the obtained transparent colored image had good adhesion, water resistance, solvent resistance, chemical resistance and the like.

A high-quality color filter can be obtained by producing a transparent colored image using the photosensitive resin composition having these excellent characteristics. In the present invention, the pigment is contained in the compound having an ethylenically unsaturated group in advance. 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, indathuron-based, anthrapyrimidine-based, flavasuron-based, perylene-based, perinone Examples thereof include condensed polycyclic pigments including pigments such as pigments, quinophthalone pigments, phthalone pigments, thioindigo pigments, indigo pigments, dioxazine pigments, anthraquinone pigments, xanthene pigments, methine pigments, and other metal complex pigments. Examples of inorganic pigments include milori blue, iron oxide, cobalt violet, manganese violet, ultramarine blue, navy blue, cobalt blue,
Cerulean blue, viridian, emerald green,
Cobalt green etc. can be mentioned, and from these 1
One kind or two or more kinds can be appropriately selected and used.

These organic and inorganic pigments have a particle size of 0.7 μm from the viewpoints of light transmittance, film surface uniformity, and the like.
m or less, preferably 0.1 μm or less, which is sufficiently small with respect to 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,
For example, alkyl acrylates (eg, methyl acrylate, ethyl acrylate, butyl acrylate,
Acrylic acid-2-ethylhexyl, etc.), methacrylic acid alkyl esters (eg, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid-
2-ethylhexyl, etc.), epoxy acrylates (including methacrylate), urethane acrylates (including methacrylate), polyether acrylates (including methacrylate), polyester acrylates (including methacrylate), acrylic acid, methacrylic acid, acrylic Glycidyl acid, glycidyl methacrylate,
Allyl acrylate, Allyl methacrylate, Itaconic acid,
Acrylamide, methacrylamide, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate,
Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 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
(Acryloxy-polyethoxy) phenyl] propane, 2,2-bis [4 (methacryloxy-polyethoxy) phenyl] propane, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetramethylolmethane tetraacrylate, dipentaerythritol hexaacrylate ,butadiene,
Isoprene, chloroprene, vinyl chloride, vinyl bromide,
Examples thereof include vinylidene chloride, vinylidene fluoride and the like, and these can be used alone or in combination of two or more kinds.

However, an emulsion obtained by dispersing a pigment in a so-called monofunctional compound having one ethylenically unsaturated group in the molecule and emulsifying the monofunctional compound is a monofunctional compound after photocuring. Since the crosslink density in the particles of the functional compound is low, the adhesiveness, water resistance, solvent resistance, chemical resistance and the like of the obtained transparent colored image may be reduced. On the other hand, when a so-called polyfunctional compound having two or more ethylenically unsaturated groups in the molecule is used as the particle component of the emulsion,
Since the crosslink density in the emulsion particles after photocuring is high, there is an advantage that the obtained transparent colored image has good adhesiveness, water resistance, solvent resistance, chemical resistance and the like.

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. 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. It is preferable to disperse the pigment so that the particle diameter of the pigment is smaller than the wavelength of visible light (0.4 μm to 0.7 μm).
The green pigment is preferably 0.3 μm or less, and the blue pigment is preferably 0.2 μm or less.

As the photopolymerization initiator to be dissolved in the compound having an ethylenically unsaturated group, azobisisobutyronitrile, benzoin alkyl ether, thioacridone,
Benzyl, N- [alkylsulfonyloxy] -1,8
-Direct cleavage of naphthalene dicarboximide, 2,4,6-tris (trichloromethyl) -s-triazine, α, α-dimethoxy-α-morpholinomethylthiophenylacetophenone, 2,4,6-trimethylbenzoylphosphine oxide, etc. Type initiators, benzophenone, thioxanthone, quinone, thioacridone, 9-phenylacridine, hydrogen abstraction type initiators such as 2,4-diethylthioxanthone, benzanthrone / triethanolamine, methylene blue / benzene sulfonate,
Examples include electron transfer type complex initiators such as triallyl imidazole dimer / Michler's ketone and carbon tetrachloride / manganese carbonyl.

Next, using a compound having an ethylenically unsaturated group in which a photopolymerization initiator in which a pigment is dispersed is dissolved, emulsification is performed in water in the presence of a protective colloid agent according to a conventional method.

The protective colloid used here is
There are (i) a water-soluble polymer having no photocrosslinkable group having photocrosslinkability by itself, and (ii) a watersoluble polymer having a photocrosslinkable group having photocrosslinkability by itself. Here, one or more water-soluble polymers selected from (i) may be used as a protective colloid, and one or more water-soluble polymers selected from (ii) may be used as a protective colloid. Alternatively, one or more water-soluble polymers selected from (i) and (ii) may be used in combination as a protective colloid. The following can be mentioned as specific examples of such water-soluble polymers. (I) Water-soluble polymer having no photocrosslinkable group having photocrosslinkability by itself, partially saponified polyvinyl acetate, partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch, starch derivative, Gum arabic, cellulose derivative, polyacrylamide, polyacrylic acid, water-soluble nylon, Japanese Patent Publication No. 4
Water-soluble polymers having reactive unsaturated groups and thiol groups as disclosed in JP-A-4-25794 and JP-A-59-187005, and sulfonic acid groups or carboxyl groups as disclosed in JP-A-59-213705. (Ii) a water-soluble polymer having a photocrosslinkable group having photocrosslinkability by itself, selected from styrylpyridinium salt compounds, styrylquinolinium salt compounds and N-methylolacrylamide 1 A partially saponified polyvinyl acetate, a partially saponified polyvinyl acetate derivative, gelatin, casein, collagen, starch, to which one or more photosensitive compounds have been added and condensed.
Starch derivative, gum arabic, cellulose derivative, polyacrylamide, polyacrylic acid, water-soluble nylon, partially saponified polyacetic acid having styryl compound residue as disclosed in JP-A-1-17283 and JP-A-2-160807. Vinyl derivative

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 and nonionic surfactants. You may use together an active agent and emulsify. However, if a large amount of these surfactants is used,
Since the water resistance of the transparent colored image and the adhesion to the support are adversely affected, it is desirable to use a relatively small amount even if used.

Further, after the emulsification, one or more water-soluble polymers selected from the above (i) and (ii) may be added later, and the presence of partially saponified polyvinyl acetate as a protective colloid. A styrylpyridinium salt compound or styrylquinolinium salt is added to partially saponified polyvinyl acetate, which is a protective colloid, in a pigment-filled emulsion obtained by emulsion polymerization of a thermopolymerizable monomer or a thermopolymerizable oligomer in which a pigment is dispersed below. A photosensitive resin in which one or more photosensitive compounds selected from the compounds are subjected to addition condensation may be added.

Next, a photosensitive resin composition is prepared from a mixture of an emulsion of a compound having an ethylenically unsaturated group in which a pigment emulsified with a protective colloid agent such as the water-soluble polymer is dispersed and a diazo compound or a dichromate. Things are composed. However, when the water-soluble photosensitive polymer obtained by addition-condensing the photosensitive compound of the above (ii) is used as a protective colloid agent, the pigment-dispersed ethylene can be dispersed without mixing with the diazo compound or the dichromate. It is possible to use the emulsion of a compound having a polyunsaturated group alone as a photosensitive resin composition.

It is also possible to add an organic pigment or an inorganic pigment dispersed by a dispersant such as a surfactant to the photosensitive resin composition to adjust the coloring density and the like. . The present inventors initially expected that a transparent colored image-forming photosensitive resin composition excellent in water solubility could be obtained by only improving dispersion stabilization of the pigment.
However, when an emulsion of a compound having an ethylenically unsaturated group in which the pigment is dispersed is applied on a glass substrate, dried to form a film, and spray-washed, a normal spray-washed film forms a thin film on the entire surface of the substrate. Remained a colored residue. Further, as will be shown later in Examples, similar results were obtained even when a water-soluble photocrosslinking agent such as a diazo compound or dichromate was added. Therefore, as means for increasing the water solubility, the amount of the water-soluble polymer acting as a protective colloid of the emulsion and the post-addition of the water-soluble polymer to the emulsion were examined. However, adding a small amount of a water-soluble polymer as a protective colloid or a post-addition water-soluble polymer does not improve the water solubility, and adding a large amount of water-soluble polymer may reduce the color density of a transparent colored image. Become.

On the other hand, one or more photosensitive compounds selected from styrylpyridinium salts or styrylquinolinium salts were addition-condensed as a protective colloid of an emulsion of a compound having an ethylenically unsaturated group in which the above pigment is dispersed. Regarding the use of water-soluble polymers,
The present inventors had the following views. That is, in a water-soluble polymer in which a styrylpyridinium salt compound or a styrylquinolinium salt compound is addition-condensed, when the introduction ratio of the styrylpyridinium salt compound or the styrylquinolinium salt compound to the water-soluble polymer is increased, the viscosity is remarkably increased. The water solubility of the dry film tends to decrease. Therefore, when a water-soluble polymer obtained by addition condensation of a styrylpyridinium salt compound or a styrylquinolinium salt compound is used as a protective colloid of an emulsion of a compound having an ethylenically unsaturated group in which the pigment is dispersed, it is further obtained. It was thought that the water solubility of the dry film of the emulsion would deteriorate.

However, when a transparent colored image is formed by a photosensitive resin composition comprising an emulsion in which a water-soluble polymer obtained by addition-condensing a styrylpyridinium salt or styrylquinolinium salt compound is used as a protective colloid, a transparent colored image is easily formed. Development was possible, and there was no residual color in the unexposed areas after development. Thus, the inventors of the present invention, as a protective colloid of an emulsion of a compound having an ethylenically unsaturated group in which the pigment is dispersed, a water-soluble polymer obtained by addition condensation of a styrylpyridinium salt compound or a styrylquinolinium salt compound. By using, the water solubility of the transparent colored image-forming photosensitive resin composition is improved, and therefore water development is possible in forming a transparent colored pattern of a plurality of colors such as a color filter, and the unexposed portion This has led to the discovery of effects such as complete removal by development and no color remaining on the glass substrate.

The photosensitive resin composition containing the pigment is applied to the support by, for example, a spin coating method, a roll coating method, a dipping method, a spray method, a printing method or the like so that the film thickness when dried is 0. 1 to 10 μm, preferably 0.5 to 3 μm. The coating film is dried with a hot air dryer,
This is performed with a hot plate or the like, and after drying, a mask having a predetermined shape such as a dot pattern or a stripe pattern is brought into close contact, and through this mask, pattern exposure is performed using a light source such as a xenon lamp, a metal halide lamp, or an ultrahigh pressure mercury lamp. Then, the non-exposed areas may be selectively removed by spray development or immersion development with a developing solution such as water or water / 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
Even if it is heated at 200 ° C. for several tens of minutes, its spectral transmittance characteristics hardly change, and it has excellent heat resistance. Incidentally, a general organic dyed image is largely discolored when heated at 200 ° C. for several tens of minutes. Further, under the condition that the nitrogen substitution is sufficiently performed, even if the transparent colored image is heated at 250 ° C. for several tens of minutes, its spectral transmittance characteristic hardly changes.

Also in light resistance, the fading phenomenon is improved by about 3 to 4 times as compared with the organic dyed image.

[0034]

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, 20 parts by weight of chromophthal blue 4GNP (blue pigment manufactured by Ciba-Geigy), 50 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 size of the pigment was 0.2 μm or less to obtain a blue pigment-containing oligomer.

Next, the blue pigment-containing oligomer 10
0.5 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator was added to 0 parts by weight, and N- was added to partially saponified polyvinyl acetate having an average degree of polymerization of 1700 and a degree of saponification of 88 mol% as a protective colloid agent. Methyl-γ- (p-formylstyryl) -pyridinium methosulfate was added to 110 parts by weight of a 10% by weight aqueous solution of a photosensitive resin into which 1.4 mol% was introduced, and emulsified according to a conventional method to obtain a blue photosensitive resin composition. I got a thing.

The particle diameter of the emulsion of the blue pigment-dispersed oligomer which is the synthesized blue photosensitive resin composition is 0.
It was 5 μm or less, the blue pigment particles were included in the emulsion particles, and the dispersion state of the emulsion particles was not changed over a long period of 3 months or more. Next, a blue transparent colored image was prepared as shown in FIGS. First, the blue photosensitive resin composition 1 is applied onto a transparent glass substrate 2 so as to have a dry film thickness of 1 μm (FIG. 1), and is pattern-exposed with ultraviolet rays 4 through a mask 3 having a predetermined shape, and development and After drying (FIG. 2), a blue transparent colored image 5 was formed (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 water-developability of the unexposed area was good, and no color remained on the glass substrate after development.

The blue transparent colored image thus obtained had a transmittance of 75% at 460 nm and 5% at 620 nm. This blue transparent colored image at 6 ° C at 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.

Operation 2 Chromophtal green GFN (green pigment manufactured by Ciba Geigy) was used as an organic pigment, and an emulsion of a green pigment-dispersed oligomer, which was a green photosensitive resin composition, was obtained in the same manner as in Operation 1. The emulsion particles were also stable for a long period of time as in the case of the operation 1.

A green transparent colored image formed by using the green photosensitive resin composition prepared in the same manner as in the operation 1,
The developability, adhesiveness, and uniformity were all good, and the transmittance was 75% at 540 nm and 3% at 640 nm. Further, even if the green transparent colored image is heated at 200 ° C. for 60 minutes, its spectral transmittance characteristics are almost unchanged and good.
The result of the 000-hour light resistance test was also good.

Operation 3 Chromophtal red A2B (a red pigment manufactured by Ciba-Geigy) was used as an organic pigment, and an emulsion of a red pigment-dispersed oligomer which was a red photosensitive resin composition was obtained in the same manner as in Operation 1. The emulsion particles were also stable for a long period of time as in the case of the operation 1.

Further, a red transparent colored image formed by using the red photosensitive resin composition prepared in the same manner as in the operation 1,
The developability, adhesiveness and uniformity were all good, and the transmittance was 85% at 630 nm and 5% at 540 nm. Further, even if the red transparent colored image is heated at 200 ° C. for 60 minutes, its spectral transmittance characteristics are almost unchanged and good.
The result of the 000-hour light resistance test 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 mosaic of three colors of blue, green and red on a 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 Procedure 1 As an organic pigment, 20 parts by weight of chromophthal blue 4GNP (blue pigment manufactured by Ciba-Geigy), 50 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, they were sufficiently dispersed so that the pigment particle size was 0.2 μm or less, to obtain a blue pigment-dispersed oligomer.

Next, the blue pigment-dispersed oligomer 10
0.5 parts by weight of 2,4-diethylthioxanthone as a photopolymerization initiator was added to 0 parts by weight, and 10 parts by weight of partially saponified polyvinyl acetate having an average polymerization degree of 1700 and a saponification degree of 88 mol% were used as a protective colloid agent. % Aqueous solution and emulsified in a conventional manner. The particle size of the synthesized emulsion of blue pigment-dispersed oligomer was 0.5 μm or less, the blue pigment particles were included in the emulsion particles, and the dispersion state of the emulsion particles was not changed over a long period of 3 months or more.

Then, the solid content concentration of the emulsion of the blue pigment-dispersed oligomer was adjusted to 20% by weight, and then 0.2 part by weight of ammonium dichromate was added to 100 parts by weight of the emulsion after the solid content concentration was adjusted. A blue photosensitive resin composition was obtained. A blue transparent colored image was formed in the same manner as in operation 1 of Example 1 using the above blue photosensitive resin composition. Since the dry film of the blue photosensitive resin composition has poor water solubility, it is difficult to completely remove the unexposed portion by water development, and a thin film-like blue residue tends to remain on the entire surface of the glass substrate. In this case, the residual film in the unexposed portion can be removed by increasing the spray pressure of the developing machine or by polishing with a brush and sponge after development. However, the above-mentioned development process often causes peeling of the image, falling off, and the like, resulting in a poor yield. The properties of the image thus obtained were as good as those of operation 2 of example 1.

Operation 2 Chromophtal green GFN (green pigment manufactured by Ciba Geigy) was used as an organic pigment, and an emulsion of a green pigment-dispersed oligomer was obtained in the same manner as in Operation 1 of Example 2. The emulsion particles were also stable for a long period of time as in the case of the operation 1 of Example 2.

Next, 0.2 part by weight of ammonium dichromate was added to 100 parts by weight of the emulsion of the green pigment-dispersed oligomer adjusted to a solid content concentration of 20% by weight to obtain a green photosensitive resin composition. Using the above green photosensitive resin composition, a green transparent colored image was formed in the same manner as in the operation 2 of Example 1. The properties of the image obtained were as good as those of operation 2 of example 1 except that the yield was reduced.

Operation 3 Using Chromophtal red A2B (a red pigment manufactured by Ciba Geigy) as an organic pigment, a red pigment-dispersed oligomer emulsion was obtained in the same manner as in Operation 1 of Example 2.
The emulsion particles were also stable for a long period of time as in the case of the operation 1 of Example 2.

Next, 0.2 part by weight of ammonium dichromate was added to 100 parts by weight of the emulsion of the red pigment-dispersed oligomer adjusted to a solid content concentration of 20% by weight to obtain a red photosensitive resin composition. Using the above red photosensitive resin composition, a red transparent colored image was formed in the same manner as in the operation 3 of Example 1. The properties of the image obtained were as good as those of operation 3 of Example 1, except that the yield was reduced.

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.

Example 3 Operation 1 In the same manner as in Operation 1 of Example 2, an emulsion of blue pigment-dispersed oligomer was synthesized. To 100 parts by weight of the emulsion of the blue pigment-dispersed oligomer adjusted to a solid content concentration of 20% by weight, 0.2 part by weight of a diazo compound composed of a condensate of p-diazophenylamine and formaldehyde was added to obtain a blue photosensitive resin. A composition was obtained.

Using the above blue photosensitive resin composition, a blue transparent colored image was obtained in the same manner as in the operation 1 of Example 1. The properties of the resulting image were as good as those of Run 1 of Example 1 except that the yield was reduced.

Operation 2 In the same manner as in Operation 2 of Example 2, an emulsion of a green pigment-dispersed oligomer was synthesized. To 100 parts by weight of the emulsion of the green pigment-dispersed oligomer adjusted to a solid content concentration of 20% by weight, 0.2 part by weight of the same diazo compound as used in the operation 1 of Example 3 was added to prepare a green photosensitive resin composition. I got a thing.

A green transparent colored image was obtained in the same manner as in the operation 2 of Example 1 using the above green photosensitive resin composition. The properties of the image obtained were as good as those of operation 2 of example 1 except that the yield was reduced.

Operation 3 In the same manner as in Operation 3 of Example 2, an emulsion of red pigment-dispersed oligomer was synthesized. To 100 parts by weight of the emulsion of the red pigment-dispersed oligomer adjusted to a solid content concentration of 20% by weight, 0.2 part by weight of the same diazo compound used in the operation 1 of Example 3 was added to give a red photosensitive resin composition. Obtained.

Using the above red photosensitive resin composition, a red transparent colored image was obtained in the same manner as in the operation 3 of Example 1. The properties of the image obtained were as good as those of operation 3 of Example 1 except that the yield was reduced.

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.

[0059]

The transparent colored image-forming photosensitive resin composition according to the present invention is an emulsion of a compound having an ethylenically unsaturated group having excellent dispersion stability. Since it is dispersed and contained in, it has the following effects.

1) When two or more colored transparent colored images such as color filters are provided adjacent to each other on a support, it is necessary to form a transparent dye-proof resin film for each color. Therefore, the manufacturing process of the transparent colored image can be significantly simplified.

2) It is possible to easily obtain a homogeneous transparent colored image without color loss. 3) A transparent colored image having excellent heat resistance and light resistance can be easily obtained. 4) The dispersion of the pigment is stable even during long-term storage, and there is no aggregation or precipitation. Therefore, according to the present invention, it is possible to fabricate a color filter having a fine pattern which is free from local color bleeding and is excellent in various characteristics of light resistance and heat resistance by a simple manufacturing process.

Therefore, the present invention can be applied to a wide variety of devices that require 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 (4)

[Claims] 1. A water-soluble compound in which a photopolymerization initiator is dissolved and a pigment is dispersed, and which is water-insoluble or sparingly soluble and has at least one ethylenically unsaturated group, contains a water-soluble photocrosslinking agent. Photosensitive resin for transparent colored image formation characterized by being emulsified in an aqueous solution of a water-soluble polymer selected from a polymer and a water-soluble polymer having a photocrosslinkable group having photocrosslinkability by itself. Composition. 2. The water-soluble polymer having a photocrosslinkable group having photocrosslinkability by itself is one or more selected from styrylpyridinium salt compounds, styrylquinolinium salt compounds and N-methylolacrylamide. The transparent colored image-forming photosensitive resin composition according to claim 1, wherein the photosensitive compound is a water-soluble polymer obtained by addition condensation. 3. The photosensitive resin composition for forming a transparent colored image according to claim 1, wherein the water-soluble photocrosslinking agent is selected from a dichromate and a diazo compound. 4. A color filter, wherein a pattern of a plurality of colors obtained by photocrosslinking the transparent colored image-forming photosensitive resin composition according to claim 1 is provided on a support.