JPH04348142A - Resin composition for color filter formation - Google Patents

Abstract

PURPOSE:To obtain a composition consisting of a specific transparent resin, being prescribed value or above in light transmittance in light transmitting area in spectral property curve of visible region after coating film formation, having excellent spectal properties, durability, light resistance and heat resis tance and useful for color liquid crystal display device, etc. CONSTITUTION:The objective composition consisting of a transparent resin such as PVA into which a pigment (e.g. azo lake based or Milori blue) having spectral properties capable of transmitting light in specific visible light area, having particle size distribution being <=10wt.% based on total particles in particles having >=1mum particle diameter and being >=60wt.% based on total particles in particles having 0.01-0.3mum particle diameter is dispersed and being <=20wt.% in light transmittance of light absorption area in spectral property curve in visible area of transparent resin after coating film formation and being >=50wt.% in light transmittance of light transmitting area. Furthermore, the pigment is blended with the transparent resin at a ratio of 1/5 to 1/2 (expressed in terms of solid content).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a resin composition for forming a color filter using a transparent resin, and more specifically to color liquid crystal display devices, color facsimiles, three-tube and single-tube color video cameras, solid color The present invention relates to a resin composition used to form transparent colored images used in the production of color filters installed in video cameras and the like.

0002

SUMMARY OF THE INVENTION In recent years, interest in home color video cameras has been rapidly increasing. Color video cameras for home use are required to be small, lightweight, and inexpensive;
A single-tube color video camera is used in which an image pickup tube is equipped with a color filter in which extremely fine stripes of one or more different hues are provided on a transparent substrate. For the same purpose, a solid-state color video camera has also been proposed in which a color filter is provided in direct contact with the light-receiving surface of a solid-state image sensor of the color video camera. Furthermore, a method has also been proposed in which a color separation filter is formed directly or indirectly on the light receiving surface of a solid-state image sensor such as a line sensor or an area sensor that is a photoelectric conversion element. Solid-state imaging devices include CCD, MOS, CID, and CPD.
etc. are used.

On the other hand, in liquid crystal display devices as well, interest in coloring displayed images is increasing, and one method for this purpose is to seal a liquid crystal material between a pair of parallel transparent electrodes and make the transparent electrodes transparent. In addition to dividing the transparent electrode into continuous microscopic areas, each microscopic area on the transparent electrode is provided with a color selected from red, blue, or green in an alternating pattern, or a color filter is provided on the substrate. A method has been proposed in which a transparent electrode is provided after the formation.

[0004] As described above, color filters used in color video cameras, color liquid crystal display devices, etc. are made by forming extremely fine areas colored in two or more colors of different hues on a transparent substrate or a solid-state image sensor. It is formed by providing. Generally, in order to color a minute area with two or more colors having different hues, a photosensitive resin that can form a transparent colored image (pixel) is used.

Conventionally, in order to form two or more types of transparent colored images using photosensitive resins, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, casein,
A photosensitive resin made by adding dichromate, chromate, or diazo compound as a photosensitive material to a hydrophilic resin such as glue is coated onto a transparent substrate or a support such as a solid-state image sensor to make it transparent. form a synthetic resin layer. Next, a mask having an opening pattern of a predetermined shape is placed on this photosensitive resin layer, and exposure and development are performed to form the first layer.
A resin layer is formed, and this first resin layer is dyed with a desired dye to form a first transparent colored image. Next, in order to prevent dye migration, a transparent resist dyeing resin film made of a hydrophobic resin is formed on this first transparent colored image, and then the same method as that for forming the first transparent colored image is performed. A second transparent colored image is formed. By repeating the above operations, you can
A transparent colored image colored in more than one color is formed on the support.

However, according to the above method, a transparent colored image of multiple colors cannot be provided unless a transparent resist dyeing resin film is formed for each color, so the manufacturing process is extremely complicated. be. Additionally, some color filters may heat up during their use;
In the above method, since the transparent image is colored using a dye, the heat resistance or light resistance of the resulting color filter is limited and is not satisfactory in this respect.

[0007]

SUMMARY OF THE INVENTION The present invention aims to solve all of the drawbacks associated with the prior art, and has the following objects. (a) To provide a resin composition for forming a color filter that has excellent spectral properties that transmit light in a specific visible region and is also excellent in durability. (b) Two or three types, such as color filters.
When providing transparent colored images of different colors or more on a support, there is no need to form a transparent resist dyeing resin film for each color, and therefore the manufacturing process can be simplified. To provide a resin composition for forming a color filter. (c) To provide a resin composition for forming a color filter that enables the formation of transparent colored images with excellent heat resistance and light resistance.

In order to achieve the above objects, the resin composition for forming a color filter according to the present invention has a spectral characteristic that transmits light in a specific region of the visible region, and has a particle size of 1 μm.
m or more particles account for 10% by weight or less of the total particles, and
Particles with a particle size of 0.01 to 0.3 μm account for 60% by weight of the total particles.
It is made of a transparent resin in which a pigment having a particle size distribution as described above is dispersed, and the light transmittance of the light absorption region in the spectral characteristic curve of the visible region of the transparent resin after coating film formation is 20% or less, It is characterized in that the light transmittance of the light transmitting region is 50% or more.

Conventionally, photosensitive resin compositions in which a certain type of pigment is dispersed have been known, but the particle size of the pigment is significantly larger than that of the pigment of the present invention, resulting in insufficient transparency and masking. For example, when used in color filters for solid-state image sensors, sufficient sensitivity cannot be obtained due to low transmittance, and it is also used in color filters for color liquid crystal display devices. In this case, there is a problem that the image cannot have sufficient brightness. Until now, it was not known how to improve the transparency of colored images by controlling the particle size or distribution of pigments dispersed in photosensitive resins, and how to do so. It was not known whether the particle size of the pigment dispersed in the transparent resin could be controlled to such an extent that the transparency of the resulting colored image would be satisfactory.

[0010] The present invention suppresses a decrease in light transmittance due to light scattering by setting the particle size of the pigment dispersed in a transparent resin to be equal to or less than the wavelength of incident light and to have a specific particle size distribution. This method is based on the discovery that the transparency of the resulting colored image is sufficiently and dramatically increased to the extent that it can be put to practical use.

In the present invention, the pigment is dispersed in a transparent resin, and the transparent resin may be a photosensitive resin having a photosensitive group or a transparent resin imparted with photosensitivity by a photocrosslinking agent. In this case, the photosensitive resin is preferably a water-soluble, oil-soluble or alcohol-soluble transparent resin. Specifically, the following compounds are used. a) Water-soluble photosensitive resin having a photosensitive group Polyvinyl alcohol derivative resin such as polyvinyl alcohol resin, polyvinyl alcohol/stilbazolium resin, etc. b) Oil-soluble photosensitive resin having a photosensitive group Photocrosslinkable photosensitive resin such as cinnamic acid type, photolytic crosslinkable photosensitive resin such as bisazide type, photolytic polarity changing type photosensitive resin such as O-quinonediazide type Such. c) The following (a) binder resin and (b)
Combination with photo-crosslinking agent (a) Binder resin (i) Animal protein-based such as gelatin, casein, mul (ii) Cellulose-based such as carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose (ii)
i) polyvinyl alcohol, polyvinylpyrrolidone,
Vinyl polymerization systems such as polyvinyl methyl ether, polyacrylic acid, polyacrylamide, polydimethylacrylamide, and copolymers thereof (iv) Ring-opening polymerization systems such as polyethylene glycol and polyethyleneimine (v) Condensation systems such as water-soluble nylon, Such.

(vi) Butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene or chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, acrylic resin, polyamide, polyester, Oil-soluble resins such as phenolic resins, polyurethane resins, etc. (b) Photocrosslinking agents dichromate, chromate, diazo compound, bisazide compound, etc. d) (a) The above binder resin, (b) a monomer or oligomer as shown below, and (c) an 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, methylene bisacrylamide, 1,3,5-triacryloyl-1,3,5-
Triazacyclohexane, pentaerythritol triacrylate, styrene, vinyl acetate, various acrylic esters, various methacrylic esters, acrylonitrile, etc. (c) Initiator i) Photodegradable initiator, such as azobisisobutyronitrile, benzoin alkyl ether, thioacridone, benzyl, N-[alkylsulfonyloxy]-
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 composite initiators such as benzanthrone/triethanolamine, methylene blue/benzenesulfinate, triallylimidazolyl dimer/Michel's ketone, carbon tetrachloride/manganese carbonyl, etc.

[0015] In the present invention, a pigment is dispersed in the transparent resin as described above to form a resin composition of the present invention for forming a transparent colored image.

[0016] In this specification, the term "pigment" refers to a colored powder that is sparingly soluble in water or organic solvents, and includes both organic pigments and inorganic pigments. Note that some dyes are poorly soluble in water or organic solvents, and these dyes can be used as "pigments" in the present invention.

The organic pigments include azo lake type, insoluble azo type, condensed azo type, phthalocyanine type, quinacridone type, dioxazine type, isoindolinone type, anthraquinone type, perinone type, thioindico type, perylene type, or a mixture of these pigments. can be used.

As inorganic pigments, Miloli blue, cobalt violet, manganese violet, ultramarine, navy blue, cobalt blue, cerulean blue, viridian, emerald green, cobalt green and mixtures thereof can also be used.

The pigment dispersed in the transparent resin has a particle size of 1 μm.
It is desirable that the pigment has a particle size distribution such that particles having a size of m or more account for 10% by weight or less, preferably 5% by weight or less, and more preferably 2% by weight or less of the total pigment particles. Particle size 1μm
If the above particles exceed 10% by weight of the total pigment particles and are dispersed in the transparent resin, it is not preferable because the light transmittance decreases due to light scattering. At the same time, the pigment used in the present invention desirably has a particle size distribution such that particles with a particle size of 0.01 to 0.3 account for 60% by weight or more of the total pigment particles.

[0020] The pigment having such a particle size distribution and the transparent resin are mixed in a solid content ratio of 1/10 to 2/1, preferably 1/5.
A photosensitive resin composition for forming a color filter can be obtained by blending at a ratio of 1/2 to 1/2. An appropriate combination of pigment and transparent resin is selected in consideration of the spectral characteristics of the pigment and the spectral characteristics of the transparent resin.

[0021] In order to form a transparent colored image in which a pigment having a desired particle size distribution as described above is dispersed, first, the pigment that has been ground quite finely and the solution of the transparent resin described above are mixed, The resulting mixture is milled using a pigment dispersion machine such as a three-roll mill, a ball mill, or a sand mill to sufficiently disperse the pigment, and then centrifuged or passed through a glass filter, membrane filter, etc. until the particle size is 1 μm or more. A transparent resin composition containing a pigment is prepared by removing the large pigment particles of After that, a colorant is prepared by removing large pigments with a particle size of 1 μm or more by centrifugation or filtration through a glass filter, membrane filter, etc., and this colorant and the above-mentioned transparent resin are mixed to create a pigmented transparent resin. Resin compositions can be made.

When dispersing the pigment in a transparent resin, it is preferable to add a nonionic surfactant as a dispersant in order to improve the dispersibility of the pigment. Further, when removing large particle diameter pigments from a transparent resin composition or colorant in which pigments are dispersed, the viscosity of the composition or colorant is preferably adjusted to 500 cps or less.

Next, a method for producing a transparent colored image using the transparent resin composition of the present invention prepared as described above will be explained.

To form a transparent colored image on a support,
First, the pigment-containing transparent resin composition prepared as described above is applied onto a support using a coating device such as a spinner, roll coater, dip coater, foil coater, or bar coater, so that the dry film thickness is preferably 0.1 to 10 μm. is 0.5~
The coating is applied to a thickness of about 3 μm, and after drying, pattern exposure is performed using a light source such as a xenon lamp, metal halogen lamp, or ultra-high pressure mercury lamp through a mask having a predetermined opening pattern. By this pattern exposure, an insolubilized portion is formed in the transparent resin layer corresponding to a predetermined pattern if the resin is a negative photosensitive resin, and a solubilized portion is formed if the resin is a positive photosensitive resin. Then, the solubilized portion is selectively removed by spray development or dip development with a developer such as water or water/organic solvent to obtain a patterned transparent colored image.

By repeating the same operation several times, transparent colored images in a plurality of colors can be provided on the support without forming a transparent resist dyeing resin film.

The transparency of the colored image finally obtained depends on the type of transparent resin used as the base, the type and amount of pigment dispersed in the transparent resin, and the film of the colored image layer provided on the support. Determined by thickness etc. First, it is desirable that the transparent resin used as the base has a light transmittance of 80% or more, preferably 90% or more, and more preferably 95% or more in the entire visible light region of 400 to 700 nm. After pigments are dispersed in this base transparent resin and then formed on a support to a predetermined thickness, the absorption area and transmission area change depending on the type of pigment used, but in the absorption area It is desirable that the light transmittance is 20% or less, preferably 10% or less, and at the same time, it is desirable that the light transmittance in the transmission region is 50% or more, more preferably 60% or more.

[0027] In this specification, a colored image can be said to be "transparent" if the above conditions are met.

[0028] As the support, transparent glass, a transparent resin film, a metal plate, a ceramic plate, a solid-state image sensor which is a photoelectric conversion element, etc. can be used. Solid-state image sensors include CCD, MOS, BBD, CID, and CP.
A color filter for color separation can be formed by directly or indirectly providing a transparent colored image according to the present invention on the light-receiving surface.

[0029]

Effects of the Invention The resin composition for forming a color filter according to the present invention is composed of a pigment having a specific particle size range and particle size distribution dispersed in a transparent resin, so that it has the following effects. has. (a) By suppressing light scattering, it is possible to obtain a color filter that has excellent spectral characteristics that transmit light in a specific visible region with high transmittance, and is also excellent in durability. (b) When providing transparent colored images of a plurality of colors on a support, it is not necessary to form a transparent resist dyeing resin film for each color, and therefore the manufacturing process of color filters can be significantly simplified. (c) Color filters with excellent heat resistance and light resistance can be easily obtained.

[0030]

[Examples] The present invention will be explained below based on Examples.
The present invention is not limited to the following examples. Example 1 1 part by weight of Lionol Green 2Y-301 (green pigment manufactured by Toyo Ink Manufacturing Co., Ltd.: chlorine-brominated copper phthalocyanine pigment) was mixed with an average degree of polymerization of 1750 and a degree of saponification of 88 mo.
10 wt% aqueous solution of l% polyvinyl alcohol 10
The resulting mixture was milled and dispersed using three rolls, centrifuged at 12,000 rpm, and filtered through a 1 μm glass filter. Next, 1w of ammonium dichromate was added to the resulting aqueous colored resin solution as a crosslinking agent.
t% was added to prepare a green photosensitive resin composition, and this was spin-coated onto a transparent glass substrate with a film thickness of 1.5 μm, and then
It was dried at 60° C. for 3 minutes and pattern exposed through a mask. Next, the pattern-exposed photosensitive resin composition is diluted with water/
After spray developing with a developer of isopropyl alcohol = 10/1 (weight ratio) and selectively removing non-exposed areas, 15
A green image was formed by heating at 0° C. for 30 minutes. This green image is shown in curve (a) of Figure 1, from 700 nm to 60 nm.
Even though the transmittance at 0 nm is less than 1%, the
The transmittance from 0 to 560 nm was 80% or more. The sensitivity was four times that of conventional gelatin/Cr-based colored images. The edge shape was comparable to that of gelatin/Cr-based colored images. Coulter's particle size distribution of the pigment in this green transparent resin
As a result of analysis using an N4 submicron particle analyzer, the average particle size was 0.08 μm, with a range of 0.01 to
Particles with a particle size of 0.3 μm accounted for 97% of the total particles.

[0031] The green image thus obtained is
Even when heated at ℃ for 30 minutes, the spectral transmittance characteristics hardly changed. In addition, general organic dye images are 20
The color fades significantly when heated to 0°C.

Further, when this green image was irradiated with a carbon lamp, the fading phenomenon of the green image according to the present invention was improved by 3 to 4 times as compared to the organic dye image. Example 2 A mixture of Lionol Green 2Y-301 and polyvinyl alcohol was centrifuged at 6000 rpm, and 1
A green image was formed in the same manner as in Example 1, except that it was filtered through a μm glass filter. The light transmittance of this green image was measured in the same manner as in Example 1, and is shown in curve (b) of FIG. Comparative Example 1 A green image was formed and the light transmittance was measured in the same manner as in Example 1, except that the mixture of Lionol Green 2Y-301 and polyvinyl alcohol was not centrifuged at all and was not sieved. It is shown in Figure 1 curve (c).

From the curve (c) in FIG. 1, it can be seen that unless the particle size of the pigment dispersed in the photosensitive resin composition is adjusted, a colored image with sufficient performance cannot be obtained. In this case, the particles dispersed in the transparent image have a particle size of 1 μm or more and account for 20% by weight of the total particles. Example 3 3 parts by weight of chromophthal red BRN (red pigment manufactured by Ciba Geigy: disazo pigment) was added to an average polymerization degree of 500.
, 1 of polyvinyl alcohol with saponification degree of 88 mol %
The mixture was mixed with 10 parts by weight of a 0% aqueous solution, and the resulting mixture was ground in a sand mill, centrifuged at 10,000 rpm, and filtered through a 1 μm glass filter. Next, 2 parts by weight of the obtained aqueous colorant and 88 mol% saponified polyvinyl alcohol (degree of polymerization 1700) were mixed with N-methyl-
Photosensitive resin 10 into which 1.4 mol% of γ-(p-formylstyryl)-pyridinium methosulfate was introduced
Parts by weight were thoroughly mixed to prepare a red photosensitive resin composition. Next, this red photosensitive resin composition was spin-coated onto a transparent glass substrate to a thickness of 1.5 μm, dried at 70° C. for 30 minutes, and then exposed to light in a contact pattern through a mask. Next, the pattern-exposed photosensitive resin composition was spray developed with a developer containing water/isopropyl alcohol = 5/1 (weight ratio) to selectively remove specific exposed areas, and then heated at 150°C.
A red image was formed by heating for 30 minutes. This red image had excellent transparency, and the edge shape was comparable to that of conventional gelatin/Cr-based photosensitive materials. The sensitivity was twice that of conventional gelatin/Cr-based photosensitive materials. The particle size distribution of this red photosensitive resin composition was measured in the same manner as in Example 1, and the average particle size was 0.17 μm and 0.0 μm.
Particles with a particle size of 1 to 0.3 μm account for 75% of the total particles.
Met. Example 4 10 parts by weight of Fastgen Blue GNPS (blue pigment manufactured by Dainippon Ink Chemical Co., Ltd.: copper phthalocyanine pigment) was added to 1
2 parts by weight of casein was mixed with 88 parts by weight of a resin solution dissolved in 1% ammonia aqueous solution, and the resulting mixture was milled and dispersed in a sand mill, centrifuged at 10,000 rpm, and filtered through a 1 μm glass filter. . Next, 1 part by weight of ammonium dichromate as a crosslinking agent was added to the obtained colored resin solution to prepare a blue photosensitive resin composition, which was spin-coated onto a transparent glass substrate in a film thickness of 1 μm. It was dried at 90° C. for 10 minutes and pattern exposed through a mask. The pattern-exposed photosensitive resin composition was then spray-developed with water to selectively remove non-exposed areas to form a blue image. This blue image is 560-700nm
Although the transmittance of 440~5 is less than 1%,
The transmittance at 20 nm was 85% or more. The particle size of the pigment was measured in the same manner as in Example 1 and was found to be 0.01 to 0.3.
Particles with a particle size of μm accounted for 90% of the total particles. The sensitivity was three times that of conventional gelatin/Cr-based photosensitive materials. The edge shape was comparable to that of the gelatin/Cr-based sensitive material. Example 5 2 parts by weight of Lake Red C (red pigment manufactured by Dainichiseika Chemical Co., Ltd.: Azo Lake pigment) was added to an average polymerization degree of 500 and a saponification degree of 88 m.
10 wt% aqueous solution of ol% polyvinyl alcohol 1
0 parts by weight, the resulting mixture was mixed with three rolls, and then centrifuged at 10,000 rpm for 15 minutes.
It was filtered through a 1 μm glass filter. Next, 3 parts by weight of the obtained aqueous colorant and an average polymerization degree of 450 and saponification degree of 88
Photosensitive resin 10 in which 6 mol% of p-formylstyrylpyridine was introduced into mol% of polyvinyl alcohol
Parts by weight were thoroughly mixed to prepare a red photosensitive resin composition. Next, this was spin-coated onto a transparent glass substrate to a film thickness of 1 μm, dried at 70° C. for 30 minutes, and then pattern-exposed through a mask. Next, the pattern-exposed photosensitive resin composition was spray-developed with a water/isopropyl alcohol = 2/1 developer to selectively remove non-exposed areas, and then heated at 150°C for 30 minutes to form a red image. did. Although the transmittance of this red image was 1% or less at 560 nm or less, the transmittance at 600 nm or more was 90% or more. The sensitivity was twice that of conventional gelatin/Cr-based sensitive materials. The edge shape was comparable to that of the gelatin/Cr-based sensitive material. When the particle size of the pigment was measured in the same manner as in Example 1, 81% of the total particles had a particle size of 0.01 to 0.3 μm. Example 6 8 parts by weight of Shimura Fast Pyrazolone Red BT (red pigment manufactured by Dainippon Ink Chemical: pyrazolone pigment) was mixed with a 20% ethanol solution of water-soluble nylon (manufactured by Toray, substitution rate 52%), and the resulting mixture After dispersing the mixture using a sand mill, centrifugation was performed at 10,000 rpm for 20 minutes to obtain a 1μ
It was filtered through a glass filter of 1.0 m. Next, 40 mol % of chloromethylstyrene was added to the obtained colored resin solution, and 5 wt % of pentaerythritol triacrylate as a polymerizable monomer and 10 wt % of benzoin isopropyl ether as an initiator were added to prepare a red photosensitive resin composition. Prepared. This was spin-coated onto a transparent glass substrate to a film thickness of 1 μm, dried at 60° C. for 10 minutes, and pattern-exposed through a mask. Next, the pattern-exposed photosensitive resin composition was spray developed with a water/isopropyl alcohol = 1/1 developer to selectively remove non-exposed areas, and then heated at 150°C for 30 minutes to form a red image. Formed. The sensitivity was twice that of gelatin/Cr-based sensitive materials. Although the transmittance of this red image was 1% or less at 580 nm or less, the transmittance at 620 nm or more was 80% or more. When the particle size of the pigment was measured in the same manner as in Example 1, it was found that 60% of the total particles had a particle size of 0.01 to 0.3 μm. Example 7 1 part by weight of chromophthal blue A3R (blue pigment manufactured by Ciba Geigy: thren-based pigment) was mixed with Resitop PSF-
2803 (Novolac resin manufactured by Gunei Chemical Co., Ltd.) was mixed with 20 parts by weight of 20% cellosolve acetate solution, and the resulting mixture was milled and dispersed in a sand mill, and then milled at 10,000 rpm.
The mixture was centrifuged and passed through a 1 μm glass filter. In the obtained colored resin liquid, 30% of naphthoquinone-1,2-diazide-(2)-5-sulfonic acid was added to PSF-2803.
A blue photosensitive resin composition was prepared by adding 1 part by weight of a mol % esterified photosensitive resin. Next, this was spin-coated onto a transparent glass substrate to a thickness of 1 μm, and the coating was applied at 90°C for 1 μm.
After drying for 0 minutes, a contact pattern is exposed through a mask,
This pattern-exposed photosensitive resin composition was spray-developed with a 5% sodium metasilicate aqueous solution, the non-exposed areas were selectively removed, and then rinsed with water and heated at 150°C for 30 minutes.
Heated for a minute to form a blue image. This blue image was a positive image with excellent transparency and edge shape. When the particle size of the pigment was measured in the same manner as in Example 1, it was found to be 0.01~
Particles with a particle size of 0.3 μm were 65% of the total particles. Example 8 1 part by weight of Chromophthal Red BRN (red pigment manufactured by Ciba Geigy) was mixed with an average degree of polymerization of 1750 and a degree of saponification of 88m.
10 wt% aqueous solution of ol% polyvinyl alcohol 1
0 parts by weight, and the resulting mixture was dispersed into dough using three rolls, and then centrifuged at 12,000 rpm to form a powder with a diameter of 1 μm.
It was passed through a glass filter. Next, 1 wt % of ammonium dichromate was added as a crosslinking agent to the obtained aqueous colored resin solution. Next, the obtained red photosensitive resin composition was spin-coated onto a 1 mm thick transparent glass substrate to a film thickness of 1.5 μm, dried at 90° C. for 10 minutes, and exposed in a contact pattern through a mask of a predetermined shape. . Next, the pattern-exposed photosensitive resin composition was spray-developed with a developer containing water/isopropyl alcohol = 10/1 (weight ratio), and after selectively dissolving and removing the non-exposed areas,
A red image was formed by heating for a minute. As a result of analyzing the particle size distribution of the pigment in this transparent red image using a Coulter N4 submicron particle analyzer, the average particle size was 0.3 μm, and particles with a particle size of 0.5 μm or more accounted for 3% of the total particles. It was below.

Next, the above polyvinyl alcohol aqueous solution 1
After adding and mixing 1 part by weight of Lionol Green 2Y-301 (green pigment manufactured by Toyo Ink Manufacturing Co., Ltd.) to 0 part by weight,
The obtained mixture was mixed and dispersed using three rolls, and then 120
The mixture was centrifuged at 00 rpm and passed through a 1 μm glass filter. Next, 1 wt % of ammonium dichromate was added to the obtained aqueous green resin solution to adjust the green photosensitive resin composition, and this was applied to the entire surface of the glass substrate on which the red transparent image was provided as a film with a thickness of 1 μm. Rotate and apply at 90°C.
After drying at ℃ for 10 minutes, after precisely aligning the prescribed mask, a contact pattern is exposed, and the non-exposed areas are selectively dissolved and removed using the above developer, and dried to form the above red transparent image. A transparent green image was formed adjacently. When the particle size distribution of the pigment in this transparent green image was similarly analyzed, the particles having a particle size of 0.5 μm or more accounted for 3% or less of the total particles.

Similarly, 1 part by weight of ChromoBlue A3R (blue pigment manufactured by Ciba Geigy) was added to and mixed with 10 parts by weight of the polyvinyl alcohol aqueous solution, and the resulting mixture was milled and dispersed using three rolls, and then rolled at 12,000 rpm. After centrifuging and passing through a 1 μm glass filter,
Ammonium dichromate was added at 1 wt%. Next, the obtained blue photosensitive resin composition was spin-coated to a film thickness of 1 μm over the entire surface of the glass substrate on which the red and green transparent images were provided, and after drying at 90° C. for 10 minutes, a predetermined mask was applied. were precisely aligned and exposed in a contact pattern, and the non-exposed areas were selectively dissolved and removed using the developer and dried to form a transparent blue image adjacent to the green transparent image. Similarly, when the particle size distribution of the pigment in this transparent blue image was analyzed, particles having a particle size of 0.5 μm or more accounted for 3% or less of all particles.

A transparent conductive film with a thickness of 800A was formed on the colored image thus obtained by low-temperature sputtering.
Next, polyimide was coated on top of this to a thickness of 1000 Å, followed by rubbing treatment and combined with a thin film transistor serving as a counter electrode. Next, a cell was assembled by injecting liquid crystal, and when applied to a color liquid crystal display device in which a colored image was formed inside the cell, excellent characteristics were obtained. Example 9 Using a wafer in which an interline transfer type CCD solid-state imaging device was formed on a 4″φ silicon wafer as a substrate, a color filter for color separation was formed in the light-receiving part of the solid-state imaging device by the following steps.

[0037] 1 part by weight of Chromophthal Red BRN (red pigment manufactured by Ciba Geigy) was mixed with 10 parts by weight of a 10 wt% aqueous solution of polyvinyl alcohol having an average degree of polymerization of 1750 and a degree of saponification of 88 mol%, and the resulting mixture was rolled into three rolls. After dispersing the minced meat, centrifugation was performed at 12,000 rpm.
It was filtered through a μm glass filter. Then, 1 wt % of ammonium dichromate was added as a crosslinking agent to the obtained aqueous colored resin solution. Next, the obtained red photosensitive resin composition was applied to a 500 μm thick solid-state image sensing device wafer.
Spin coating to a film thickness of 5 μm, dry at 90°C for 10 minutes,
Through a mask of a predetermined shape, exposure was carried out in a closely aligned pattern at a predetermined position with precision. Next, the pattern-exposed photosensitive resin composition was mixed with water/isopropyl alcohol=10/1.
(weight ratio) of a developer to selectively dissolve and remove non-exposed areas, and then heated at 150° C. for 30 minutes to form a red image. The particle size distribution of the pigment in this transparent red image was analyzed using a Coulter N4 submicron particle analyzer, and the average particle size was 0.3 μm.
．． 5 μm, and particles having a particle size of 0.5 μm or more accounted for 3% or less of the total particles.

Next, the above polyvinyl alcohol aqueous solution 1
After adding and mixing 1 part by weight of Lionol Green 2Y-301 (green pigment manufactured by Toyo Ink Manufacturing Co., Ltd.) to 0 part by weight,
After the obtained mixture was kneaded and distributed with three rolls, 120
The mixture was centrifuged at 00 rpm and filtered through a 1 μm glass filter. Next, 1 wt % ammonium dichromate was added to the obtained aqueous green resin solution to prepare a green photosensitive resin composition, which was spread over the entire surface of the solid-state image sensor wafer provided with the red transparent image to a thickness of 1 μm. After drying at 90°C for 10 minutes, the mask was precisely aligned with a mask, exposed to light in a close contact pattern, and the developer was used to selectively dissolve and remove the non-exposed areas. Upon drying, a transparent green image was formed adjacent to the red transparent image. When the particle size distribution of the pigment in this transparent green image was similarly analyzed, the particles having a particle size of 0.5 μm or more accounted for 3% or less of the total particles.

Similarly, 1 part by weight of Chromo Blue A3R (blue pigment manufactured by Ciba Geigy) was added and mixed with 10 parts by weight of the polyvinyl alcohol aqueous solution, and the resulting mixture was milled and dispersed using three rolls, and then mixed at 12,000 rpm. After centrifugation and filtration with a 1 μm glass filter, 1 wt % ammonium dichromate was added. Next, the obtained blue photosensitive resin composition was applied to the entire surface of the solid-state image sensor wafer provided with the above-mentioned red and green transparent images in a layer of 1 μm.
After spin-coating with a film thickness of m and drying at 90° C. for 10 minutes, a prescribed mask was precisely aligned and a contact pattern was exposed, and the non-exposed areas were selectively dissolved and removed using the developer. Let dry and be adjacent to the green transparent image above.
A transparent blue image was formed. Similarly, when the particle size distribution of the pigment in this transparent blue image was analyzed, particles having a particle size of 0.5 μm or more accounted for 3% or less of all particles.

[0040] After the above steps are completed, a transparent resin may be formed in the area of the solid-state imaging device other than the bonding pad portion for the purpose of protection, as the case may be.

The substrate on which color filters are formed on the predetermined light-receiving areas of the solid-state imaging device wafer in this manner is subjected to assembly processes such as dicing, die bonding, wire bonding, and packaging using normal methods to produce color solid-state imaging. The device was fabricated. A color solid-state camera was fabricated by attaching optical elements, circuitry, etc. to this color solid-state image sensor. Example 10 Using a 4-inch silicon wafer on which a line sensor, which is a one-dimensional solid-state imaging device, was formed by a normal wafer process as a substrate, a color filter was directly formed by the following steps.

3 parts by weight of Chromophthal Red BRN (red pigment manufactured by Ciba Geigy) was added to 1 part of a 10% aqueous solution of polyvinyl alcohol with an average degree of polymerization of 500 and a degree of saponification of 88 mol%.
The resulting mixture was mixed in a sand mill, centrifuged at 10,000 rpm, and filtered through a 1 μm glass filter. Next, 1.4 mo of N-methyl-γ-(p-formylstyryl) pyridinium methosulfate was added to 2 parts by weight of the obtained aqueous colorant and 88 mol% saponified polyvinyl alcohol (degree of polymerization 1700).
A red photosensitive resin composition was prepared by thoroughly mixing the red photosensitive resin with 10 parts by weight of the photosensitive resin introduced in an amount of 1%. Next, this red photosensitive resin composition was spin-coated onto the wafer substrate to a thickness of 1.5 μm, dried at 70° C. for 30 minutes, and then precisely aligned at a predetermined position on the photosensitive area of the wafer through a mask. A contact pattern was exposed. Next, the pattern-exposed photosensitive resin composition was mixed with water/isopropyl alcohol=5/1.
After spray developing with a developer of (weight ratio) to selectively remove non-exposed areas, a red image was formed by heating at 150° C. for 30 minutes. This red image had excellent transparency, and the edge shape was comparable to that of conventional gelatin/Cr-based photosensitive materials. The sensitivity was twice that of conventional gelatin/Cr-based photosensitive materials. The particle size distribution of this red photosensitive resin composition is 0.17 μm, and 0.17 μm.
Particles with a particle size of 0.01 to 0.3 μm account for 75% of the total particles.
%Met.

[0043] The licensor substrate thus produced was subjected to assembly processes such as dicing, die bonding, wire bonding, and bagging by a conventional method to produce a line sensor for color facsimile.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the spectral characteristics of a colored image, showing the curve (
a) to (b) are spectral characteristic curves of a colored image obtained using the resin composition according to the present invention, and curve (c) is a spectral characteristic curve of a colored image according to a comparative example.

Claims (1)

[Claims] Claim 1: Has spectral characteristics that transmit light in a specific region of the visible region, particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles, and have a particle size of 0.01 to 0.3 μm. The transparent resin is made of a transparent resin in which a pigment is dispersed and has a particle size distribution such that the particles account for 60% by weight or more of the total particles, and the light in the light absorption region in the visible region spectral characteristic curve of the transparent resin after coating film formation. A resin composition for forming a color filter, having a transmittance of 20% or less and a light transmittance of a light transmitting region of 50% or more.