JPH0439041B2 - - Google Patents

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a color filter, and more particularly, to a color liquid crystal display device, a color facsimile, a three-tube type and a single-tube type color video camera, and a solid-state color video camera. The present invention relates to a color filter installed in a device such as a color filter, a liquid crystal display device using this color filter, and a manufacturing method thereof.

[Background of the invention]

In recent years, with the development of liquid crystal technology, interest in displaying images in color in liquid crystal display devices has increased. One method for this purpose is to fill a liquid crystal material between a pair of parallel transparent electrodes, divide the transparent electrode into discontinuous micro-areas, and in each of the micro-areas on the transparent electrode,
A method has been proposed in which colors selected from red, blue, and green are alternately provided in a pattern, or a method in which a color filter is formed on a substrate and then a transparent electrode is provided.

Color filters used in color liquid crystal display devices are formed by providing extremely fine regions colored in two or more different hues on a transparent substrate. Generally, in order to color a minute area in two or more colors with different hues, transparent colored images (pixels) are used.
A photosensitive resin that can form the following is used.

Conventionally, in order to form two or more types of transparent colored images using transparent resins, first, a hydrophilic resin such as polyvinyl alcohol, polyvinylpyrrolidone, gelatin, casein, or griux is added to a photosensitive material such as dichromate or chromic acid. A transparent photosensitive resin layer is formed by applying a transparent resin to which a salt or a diazo compound is added onto a support such as a transparent substrate. Next, a mask having an opening pattern of a predetermined shape is placed on this transparent resin layer, and exposed and developed to form a first resin layer, and this first resin layer is dyed with a desired dye to form a first resin layer. 1. Forming a 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, a transparent colored image colored in two or more colors is formed on the support.

However, according to the above method, transparent colored images 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. moreover,
Some types of color filters may be heated during use, but since the transparent image is colored using dye in the above method, the durability of the resulting color filter, including its heat resistance and light resistance, is limited. Therefore, conventional full-color liquid crystal display devices equipped with such color filters have not been fully satisfactory in this respect.

[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 color filter that has excellent spectral characteristics that transmit light in a specific visible region and has excellent durability, and a color liquid crystal display device equipped with the same.

(b) Unlike conventional color filters, when two or more types of transparent colored images are provided adjacently on a support, there is no need to form a transparent resist dyeing resin for each color; Therefore, to provide a color filter and a color liquid crystal display device whose manufacturing process is simplified.

(c) To provide a color filter with excellent durability including heat resistance and light resistance, and a color liquid crystal display device equipped with the same.

(d) By reducing light scattering by pigments,
To provide a color liquid crystal display device which suppresses disturbance of polarized light and has good image display characteristics such as contrast ratio.

In order to achieve the above objects, the color filter according to the present invention has spectral characteristics that transmit light in a specific region of the visible region, and particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles. , and 0.01~
It is made of a transparent resin in which a pigment is dispersed and has a particle size distribution in which particles in the range of 0.3 μm account for 60% by weight or more of the total particles, and the light transmission in the light absorption region of the light absorption region in the spectral characteristic curve in the visible region. A transparent colored image having a light transmittance of 20% or less and a light transmittance of a light transmitting region of 50% or more is provided on a support in a pattern of multiple colors. Further, in the present invention, the pigment dispersed in the transparent resin preferably has a particle size distribution such that particles having a particle size of 1 μm or more account for 5% by weight or less of the total particles.

Further, the method for producing a color filter according to the present invention is a method for producing a color filter in which transparent colored images of a plurality of colors are formed on a support, and the method includes producing a color filter in which transparent colored images of a plurality of colors are formed on a support. It has a spectral characteristic that transmits 1 μm or more of particles, and the particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles, and the particle size is 0.01 to 0.3 μm.
It is made of a transparent resin in which a pigment is dispersed and has a particle size distribution such that particles in the range of 60% by weight or more of the total particles, and the light transmittance in the light absorption region of the spectral characteristic curve in the visible region is 20% or less,
Includes a step of forming a transparent resin coating film in a pattern with a light transmittance of 50% or more in the light-transmitting region, and does not include a step of forming an anti-dye coating at least immediately before the above step. It is characterized by:

Furthermore, the color liquid crystal display device according to the present invention is a color liquid crystal display device in which a liquid crystal is sealed between at least a pair of electrode substrates, wherein at least one of the electrode substrates is arranged on a transparent substrate of two or more types. a color filter on which transparent colored images of different hues are formed, at least one of the transparent colored images has spectral characteristics that transmit light in a specific region of the visible region, and particles with a particle size of 1 μm or more are formed. From a coating formed from a transparent resin in which a pigment is dispersed, with a particle size distribution such that the total particle size is 10% by weight or less, and particles in the range of 0.01 to 0.3 μm account for 60% by weight or more of the total particles. The light transmittance of the light absorption region in the visible region spectral characteristic curve of the transparent colored image is 20.
% or less, and the light transmittance of the light transmitting region is 50% or more.

Furthermore, the method for manufacturing a color liquid crystal display device according to the present invention is a color liquid crystal display device in which a liquid crystal is sealed between at least a pair of electrode substrates, wherein at least one of the electrode substrates is arranged on a transparent substrate. When manufacturing a color liquid crystal display device having a color filter on which transparent colored images of different hues or three or more kinds are formed, a first hue selected from red, green, and blue is provided on the transparent substrate. Dispersing a pigment having a particle size distribution in which particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles, and particles in the range of 0.01 to 0.3 μm account for 60% by weight or more of the total particles. A transparent resin composition consisting of
After forming this transparent resin coating film, the transparent resin coating film has a light transmittance of 20% or less in the light absorption region and a light transmittance of 50% or more in the light transmission region in the spectral characteristic curve in the visible region. is formed into a first pattern, and then, without forming a resin resist film, the particles have a second hue different from the first hue, and have a particle size.
Particles larger than 1 μm account for 10% by weight or less of the total particles,
and a transparent resin composition in which a pigment having a particle size distribution in which particles in the range of 0.01 to 0.3 μm account for 60% by weight or more of the total particles is dispersed; A transparent resin coating film is formed in a second pattern so that the light transmittance in the light absorption region is 20% or less and the light transmittance in the light transmission region is 50% or more in the spectral characteristic curve in the visible region. , without forming a resin film for resist dyeing, having a third hue different from the first and second hues, and having a particle size of
Particles larger than 1 μm account for 10% by weight or less of the total particles,
A transparent resin composition in which a pigment having a particle size distribution in which particles in the range of 0.01 to 0.3 μm account for 60% by weight or more of the total particles is dispersed, After forming a transparent resin coating film in the shape of a third pattern, the light transmittance of the light absorbing region is 20% or less and the light transmittance of the light transmitting region is 50% or more in the spectral characteristic curve of the region. ,
This method is characterized in that a transparent electrode film is formed on the first to third patterned coating films.

[Specific description of the invention]

Hereinafter, first, a transparent resin composition for forming a transparent colored image of a color filter mounted on a liquid crystal display device of the present invention will be explained.

Hitherto, transparent resin compositions in which certain pigments are dispersed have been known, but the particle size of the pigments is significantly larger than that of the pigment of the present invention, resulting in insufficient transparency, making it difficult to use for applications such as masking. Even if it were used in color filters, etc., it would not be possible to obtain one with sufficient sensitivity due to its low transmittance. When such a color filter is used in a color liquid crystal display device, the brightness of the image cannot be obtained sufficiently, and furthermore, the pigment particles scatter a lot of light, causing disturbance of polarization, which makes it difficult to use polarized light. In liquid crystal display devices that perform display, there has been a problem that image display characteristics such as contrast ratio deteriorate. Furthermore, it has not been known to what extent the transparency of the resulting colored image can be improved by controlling the particle size or distribution state of the pigment dispersed in the transparent resin. It has not been known whether the particle size of the pigment dispersed in the transparent resin can be controlled to such an extent that the transparency of the resulting colored image is satisfactory.

According to the present inventors, by setting the particle size of the pigment dispersed in the transparent resin to be less than the wavelength of the incident light and setting the distribution of the pigment within a specific range,
It has been discovered that the reduction in light transmittance due to light scattering is suppressed, and the transparency of the resulting colored image is sufficiently high for practical use.

In the present invention, the above-mentioned transparent resin includes:
A photosensitive resin having a photosensitive group and a transparent resin imparted with photosensitivity by a photocrosslinking agent can be used, but water-soluble, oil-soluble or alcohol-soluble photosensitive resins are particularly preferred. 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, etc.

b Oil-soluble photosensitive resin having a photosensitive group Photocrosslinkable photosensitive resins such as cinnamic acid type, photolytic crosslinkable photosensitive resins such as bisazide type, photolytic polarity changing type photosensitive resins such as O-quinonediazide type, etc. .

c Combination of (a) binder resin and (b) photocrosslinking agent as shown below (b) Binder resin () Animal protein-based such as gelatin, casein, griux () Carboxymethyl hydroxyethyl cellulose, hydroxyethyl cellulose, hydroxy Cellulose-based products (such as propyl cellulose and methylcellulose); Vinyl polymer-based products (such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyacrylic acid, polyacrylamide, polydimethylacrylamide, and copolymers thereof); polyethylene glycol, polyethylene imine, etc. Ring-opening polymerization systems () Condensation systems such as water-soluble nylon, etc.

() Butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene or chlorinated polypropylene, polyvinyl chloride, vinyl chloride-
Oil-soluble resins such as vinyl acetate copolymers, polyvinyl acetate, acrylic resins, polyamides, polyesters, phenolic resins, polyurethane resins, etc.

(b) Photocrosslinking agents: dichromates, chromates, diazo compounds, bisazide compounds, etc.

d (a) The above binder resin and the following,
(b) Monomer or oligomer and (c) 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, styrene, vinyl acetate, various acrylic esters, various methacrylic esters, acrylonitrile, etc.

(c) Initiator Photodegradable initiator, such as azobisisobutyronitrile, benzoin alkyl ether,
Thioacridone, benzyl, N-[alkylsulfonyloxy]-1,8-naphthalene dicarboximide, 2,4,6-tri[trichloromethyl]triazine, etc.

Hydrogen transfer type initiators such as benzophenone, anthraquinone, 9-phenylacridine, etc.

Electron transfer type complex initiators such as benzanthrone/triethanolamine, methylene blue/benzenesulfinate, triallylimidazolyl dimer/Michael's ketone, carbon tetrachloride/manganese carbonyl, etc.

In the present invention, a transparent resin composition for forming a transparent colored image is constructed by dispersing a pigment in the transparent resin as described above.

The term "pigment" as used herein means a colored powder that is poorly soluble in water or an organic solvent, 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.

Examples of 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 pigments or mixtures of these pigments can be used.

Inorganic pigments include Miloli Blue, Cobalt Purple, Manganese Purple, Ultramarine Blue, Deep Blue, Cobalt Blue,
Cerulean blue, viridian, emerald green, cobalt green and mixtures thereof are also used.

The pigment dispersed in the transparent resin has a particle size distribution such that particles with a particle size of 1 μm 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. It is desirable to be present.
If particles with a particle size of 1 μm or more are dispersed in the photosensitive resin in an amount exceeding 10% by weight of the total pigment particles, it is not preferable because the light transmittance decreases due to light scattering. At the same time, it is important that the pigment used in the present invention has a particle size distribution such that particles with a particle size of 0.01 to 0.3 μm account for 60% by weight or more of the total pigment particles. By satisfying both of the above particle size distribution conditions, it is possible to effectively suppress a decrease in light transmittance due to light scattering and to exhibit excellent spectral characteristics suitable for color filters.

The pigment having such a particle size distribution and the transparent photosensitive resin are mixed in a solid content ratio of 1/10 to 2/1, preferably 1/5 to 1/5.
By blending at a ratio of 1/2, a photosensitive resin composition for forming transparent colored images can be obtained. 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.

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, and the obtained The mixture is kneaded 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 filtered through a glass filter, membrane filter, etc. to obtain particles with a particle size of 1 μm or more. removing pigment particles of particle size to create a pigmented transparent resin composition, or mixing the pigment with a solution of a binder resin that is compatible with the transparent resin described above;
After sufficient dispersion in the same manner as above, a colorant is prepared by removing large pigments with a particle size of 1 μm or more by centrifugation or filtration with a glass filter, membrane filter, etc., and this colorant and the above-mentioned A pigment-containing transparent resin composition can be prepared by mixing with a transparent resin.

When dispersing a 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. Furthermore, 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, an example of a method for manufacturing a transparent colored image constituting a color filter using the transparent resin composition prepared as described above will be described.

To form a transparent colored image on a support, first, the pigment-containing photosensitive resin composition prepared as described above is placed on the support using a spinner, a roll coater,
Using a coating device such as a dip coater, foil coater, or bar coater, coat the film to a dry film thickness of 0.1 to 10 μm, preferably 0.5 to 3 μm. Halogen lamp,
Pattern exposure is performed using a light source such as an ultra-high pressure mercury lamp. This pattern exposure allows the photosensitive resin layer to
Corresponding to the predetermined pattern, an insolubilized portion is formed in the case of a negative photosensitive resin, and a solubilized portion is formed in the case of a positive photosensitive resin. The solubilized portion may then be selectively removed by spray development or dip development with a developer such as water or water/organic solvent.

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

For example, as described in the examples below, a transparent substrate is prepared by first dispersing a pigment of a first red color layer selected from red, green, and blue on a transparent substrate according to the above steps. A photosensitive resin composition (the light transmittance of the light absorption area after forming the coating film of this photosensitive resin is 20% or less, and the light transmittance of the light transmission area is 20% or less)
50% or more), then the coating film of this photosensitive resin composition is exposed to light through a mask pattern, and the thus exposed coating film is developed to form a first pattern. A pattern-shaped transparent colored image is formed on the transparent substrate, and then, a second pattern-shaped transparent colored image is formed by repeating the same process as the pattern-shaped transparent colored image described above for a second hue and, if necessary, a third hue. A full color liquid crystal display device comprising a color filter by forming a third patterned transparent colored image and further forming a transparent electrode film on the thus formed patterned transparent colored image to serve as an electrode substrate. can be obtained.

In this case, the transparency of the colored image of the color filter that is 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 colored image provided on the support. It is determined by the thickness of the layer, 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 Light transmittance is 20
% or less, preferably 10% or less, and at the same time, in the transmission region, it is desirable that the light transmittance is 50% or more, more preferably 60% or more.

In this specification, when the above conditions are satisfied, the colored image of the color filter can be said to be "transparent".

Note that as the transparent substrate, transparent glass, transparent resin film, etc. can be used.

〔Effect of the invention〕

Since the color filter, the color liquid crystal display device, and the manufacturing method thereof according to the present invention have the above-described configuration, they have the following effects.

(a) It is possible to obtain a color filter and a color liquid crystal display device that have excellent spectral characteristics that transmit light in a specific region of the visible region and are also excellent in durability.

(b) Unlike conventional color filters, there is no need to form a transparent resist dyeing resin film for each color when two or more transparent colored images are provided adjacently on a support. Therefore, it is possible to obtain a color filter and a color liquid crystal display device whose manufacturing process is simplified.

(c) A color filter and a color liquid crystal display device having excellent durability including heat resistance and light resistance can be obtained. In particular, when a transparent electrode is formed on a color filter by a sputtering method, the transparent colored image that makes up the color filter is exposed to high temperatures, but the one of the present invention has good heat resistance and does not cause deterioration of the color filter. do not have.

(d) By reducing light scattering by pigments,
It is possible to obtain a color liquid crystal display device that suppresses disturbance of polarized light and has excellent image display characteristics such as contrast ratio.

〔Example〕

The present invention will be described below based on Examples, but 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.
10wt% aqueous solution of 880mol% vinyl alcohol10
The resulting mixture was milled and dispersed using three rolls, centrifuged at 12,000 rpm, and filtered through a 1 μm glass filter. Next, 1wt% ammonium dichromate was added as a crosslinking agent to the obtained aqueous colored resin solution to prepare a green photosensitive resin composition, which was spin-coated onto a transparent glass substrate in a film thickness of 1.5 μm. After drying at 60°C for 3 minutes, pattern exposure was performed through a mask. Next, the pattern-exposed photosensitive resin composition was spray developed with a developer of water/isopropyl alcohol = 10/1 (weight ratio), and after selectively removing the non-exposed areas, the composition was developed at 150°C.
Heated for 30 minutes to form a green image. As shown in curve a in the figure, this green image has a transmittance of 500 to 600 nm, even though the transmittance of 700 to 600 nm is less than 1%.
The transmittance at 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. The particle size distribution of the pigment in this green transparent resin is
The average particle size was 0.08μm as analyzed by Coulter N4 Submicron Particle Analyzer.
Particles with a particle size of 0.01-0.3 μm account for 97% of the total particles.
It was %.

The green image obtained in this way was heated at 200℃ for 30 minutes.
Even after heating for a minute, the spectral transmittance characteristics hardly changed. In addition, general organic dye images are
The color fades significantly when heated to 200℃.

Furthermore, 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 compared to the organic dye image.

Example 2 A mixture of Lionol Green 2Y-301 and polyvinyl alcohol was centrifuged at 6000 rpm and
Example 1 except that it was passed through a glass filter.
A green image was formed in the same manner as above. The light transmittance of this green image was measured in the same manner as in Example 1, and is shown in curve b in the figure.

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 filtered. This is shown in curve c.

From curve c in the figure, 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 Chromophthaled BRN (red pigment manufactured by Ciba Geigy: disazo pigment) was mixed with 10 parts by weight of a 10% aqueous solution of polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of 88 mol%. The mixture was ground and mixed using a sand mill, centrifuged at 10,000 rpm, and filtered through a 1 μm glass filter. Then, 2 parts by weight of the obtained aqueous colorant,
88mol% saponified polyvinyl alcohol (degree of polymerization
1700) with 1.4 mol% of N-methyl-γ-(p, formylstyryl)-pyridinium methosulfate.
A red photosensitive resin composition was prepared by thoroughly mixing the introduced photosensitive resin with 10 parts by weight. Next, this red photosensitive resin composition was placed on a transparent glass substrate.
After spin coating to a thickness of 1.5 μm and drying at 70°C for 30 minutes, a contact pattern was exposed 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 for 30 minutes. to form a red image. 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.
The particles with a particle size of 0.01 to 0.3 μm accounted for 75% of the total particles.

Example 4 10 parts by weight of Fastogen Blue GNPS (blue pigment manufactured by Dainippon Ink Chemical Co., Ltd.: copper phthalocyanine pigment) was mixed with a resin solution in which 12 parts by weight of casein was dissolved in 88 parts by weight of a 1% ammonia aqueous solution. After grinding and dispersing the mixture in a sand mill,
It was centrifuged at 10,000 rpm and passed through a 1 μm glass filter. Then, to the obtained colored resin solution,
A blue photosensitive resin composition was prepared by adding 1 part by weight of ammonium dichromate as a crosslinking agent, and this was spin-coated onto a transparent glass substrate in a film thickness of 1 μm, dried at 90°C for 10 minutes, and a mask was removed. Pattern exposure was carried out through 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
Although the transmittance of 560 to 700 nm was 1% or less, the transmittance of 440 to 520 nm was 85% or more. When the particle size of the pigment was measured in the same manner as in Example 1, 90% of the total particles had a particle size of 0.01 to 0.3 μm.
It was %. 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 mixed with 10 parts by weight of a 10 wt% aqueous solution of polyvinyl alcohol having an average degree of polymerization of 500 and a degree of saponification of 88 mol%, and the resulting mixture was mixed. After dispersing the dough using three rolls, it was centrifuged at 10,000 rpm for 15 minutes and filtered through a 1 μm glass filter. Next, 3 parts by weight of the obtained aqueous colorant and an average polymerization degree of 450
p- to polyvinyl alcohol with saponification degree of 88 mol%.
A red photosensitive resin composition was prepared by thoroughly mixing with 10 parts by weight of a photosensitive resin into which 6 mol % of formylstyrylpyridine was introduced. 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.
A red image was formed by heating at 150°C for 30 minutes. Although the transmittance of this red image was less than 1% 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 Astopyrazolone Red BT (red pigment: pyrazolone pigment manufactured by Dainippon Ink Chemical) was added to water-soluble nylon (substitution rate 52% manufactured by Toray Industries).
After mixing with a 20% ethanol solution and grinding the resulting mixture with a sand mill, it was centrifuged at 10,000 rpm for 20 minutes and passed through a 1 μm glass filter.
Next, 40 mol% of chloromethylstyrene was added to the obtained colored resin solution, and pentaerythritol triacrylate as a polymerizable monomer was added.
A red photosensitive resin composition was prepared by adding 5 wt% and 10 wt% of benzoin isopropyl ether as an initiator. Place this on a transparent glass substrate
It was spin-coated 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. Sensitivity is gelatin/
It was twice that of Cr-based photosensitive materials. This red image is 580nm
Even though the transmittance below is less than 1%,
The transmittance above 620nm was over 80%. Example 1
When the particle size of the pigment was measured in the same way, it was 0.01~
Particles with a particle size of 0.3 μm were 60% of the total particles.

Example 7 1 part by weight of chromophthal blue A3R (blue pigment manufactured by Ciba Geigy: thren-based pigment) was added to the resin.
PSF-2803 (Novolac resin manufactured by Gunei Chemical Co., Ltd.) was mixed with 20 parts by weight of a 20% cellosolve acetate solution, and the resulting mixture was milled and dispersed using a sand mill.
It was centrifuged at 10,000 rpm and passed through a 1 μm glass filter. Add PSF- to the obtained colored resin liquid.
Naphthoquinone-1,2-diazide-(2)- in 2803
A blue photosensitive resin composition was prepared by adding 1 part by weight of a photosensitive resin in which 30 mol% of 5-sulfonic acid was esterified. Next, this was placed on a transparent glass substrate with a thickness of 1 μm.
After drying at 90°C for 10 minutes, the pattern-exposed photosensitive resin composition was spray-developed with a 5% sodium metasilicate aqueous solution to form a non-containing film. After selectively removing the exposed areas, rinse with water and heat at 150℃.
Heated for 30 minutes to form a blue image. This blue image was a positive type image with excellent transparency and edge shape. When the particle size of the pigment was measured in the same manner as in Example 1, 65% of all particles had a particle size of 0.01 to 0.3 μm.

Example 8 1 part by weight of Chromophthaled BRN (red pigment manufactured by Ciba Geigy) was mixed with an average degree of polymerization of 1750 and a degree of saponification.
10wt% aqueous solution of 88mol% polyvinyl alcohol
After mixing 10 parts by weight and dispersing the resulting mixture using three rolls, centrifugation was carried out at 12,000 rpm.
It was passed through a 1 μm 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, and then heated at 90°C for 10
After drying for a minute, a contact pattern was exposed through a mask having a predetermined shape. Next, the pattern-exposed photosensitive resin composition is mixed with water/isopropyl alcohol=
Spray development was performed using a developer of 10/1 (weight ratio) to selectively dissolve and remove non-exposed areas, and then heating was performed 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, and particles with a particle size of 0.5 μm or more accounted for less than 3% of the total particles. It was hot.

Next, 1 part by weight of Lionol Green 2Y-301 (a green pigment manufactured by Toyo Ink Mfg. Co., Ltd.) was added and mixed with 10 parts by weight of the above polyvinyl alcohol aqueous solution, and the resulting mixture was milled and dispersed using three rolls. After that, it was centrifuged at 12,000 rpm and passed through a 1 μm glass filter. Next, 1wt% ammonium dichromate was added to the obtained aqueous green resin solution to prepare a green photosensitive resin composition, and this was applied on the entire surface of the glass substrate on which the red transparent image was provided.
After spin-coating with a film thickness of 1 μm and drying at 90°C for 10 minutes, after precisely aligning the prescribed mask, a contact pattern was exposed, and the non-exposed areas were selectively exposed using the above developer. It was dissolved and dried to form a transparent green image 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, the above polyvinyl alcohol aqueous solution
To 10 parts by weight, 1 part by weight of Chromo Blue A3R (blue pigment manufactured by Ciba Geigy) was added and mixed, and the resulting mixture was kneaded and dispersed with three rolls, and then rolled at 12,000 rpm.
After centrifugation and passing through a 1 μm glass filter, 1 wt% ammonium dichromate was added. Next, the obtained blue photosensitive resin composition was spin-coated to a film thickness of 1 μm on the entire surface of the glass substrate on which the red and green transparent images were provided, and heated at 90°C for 10 minutes.
After drying for a few minutes, a predetermined mask is precisely aligned and exposed in a close contact pattern, and the non-exposed areas are selectively dissolved and removed using the developer and dried so that they are adjacent to the green transparent image. , 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.

A transparent conductive film with a film thickness of 800A was applied to 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 a rubbing treatment and combined with a thin film transistor that would serve as a counter electrode. Next, a liquid crystal cell was assembled by injecting liquid crystal between the electrodes, and a color liquid crystal display device having a color filter having the above-mentioned transparent colored image inside the liquid crystal cell was 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.

1 part by weight of Chromophthaled BRN (red pigment manufactured by Ciba Geigy) with an average degree of polymerization of 1750 and a degree of saponification.
10wt% aqueous solution of 88mol% polyvinyl alcohol
After mixing 10 parts by weight and dispersing the resulting mixture using three rolls, centrifugation was carried out at 12,000 rpm.
It was filtered through a 1 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 spin coated onto a 500 μm thick solid-state image sensor wafer to a film thickness of 1.5 μm, and
It was dried at ℃ for 10 minutes, and exposed to a contact pattern in a precisely aligned position through a mask of a prescribed shape.
Next, the pattern-exposed photosensitive resin composition was developed by spraying with a developer of water/isopropyl alcohol = 10/1 (weight ratio), and after selectively dissolving and removing the non-exposed areas, the composition was heated at 150°C. Heated for 30 minutes to form a red image. 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 0.5 μm, and particles with a particle size of 0.5 μm or more accounted for 3% of all particles. % or less.

Next, 1 part by weight of Lionol Green 2Y-301 (green pigment manufactured by Toyo Ink Mfg. Co., Ltd.) was added and mixed with 10 parts by weight of the above polyvinyl alcohol aqueous solution, and the resulting mixture was kneaded and distributed using three rolls. , centrifuged at 12,000 rpm, and filtered through a 1 μm glass filter. Next, 1wt% of 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 prescribed mask is precisely aligned, a contact pattern is exposed, and the non-exposed areas are selectively dissolved and removed using the above developer. , dried,
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, the above polyvinyl alcohol aqueous solution
To 10 parts by weight, 1 part by weight of Chromo Blue A3R (blue pigment manufactured by Ciba Geigy) was added and mixed, and the resulting mixture was mixed and dispersed using a three-roll mill.
After centrifuging at 12000 rpm and filtering with a 1 μm glass filter, 1 wt of ammonium dichromate was added.
% added. Next, the obtained blue photosensitive resin composition was spin-coated to a film thickness of 1 μm over the entire surface of the solid-state imaging device wafer on which the red and green transparent images were provided, and after drying at 90°C for 10 minutes, a prescribed mask was applied. were precisely aligned and exposed in a close contact pattern, and the non-exposed areas were selectively dissolved and removed using the developer, dried, and a transparent blue image was formed 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.

After the above steps have been completed, a transparent resin may be formed on the solid-state image sensor in areas other than the bonding butt portions for the purpose of protection, as the case may be.

In this way, the color filter is formed on the predetermined light receiving portion of the solid-state image sensor wafer on the substrate.
A color solid-state image sensor was fabricated by adding assembly processes such as dicing, die bonding, wire bonding, and packaging using the usual method. 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 Chromophthaled BRN (red pigment manufactured by Ciba Geigy) was added to an average degree of polymerization of 500 and a degree of saponification.
10% aqueous solution of 88mo1% polyvinyl alcohol10
The resulting mixture was mixed in a sand mill, centrifuged at 10,000 rpm, and 1 μm
It was filtered through a glass filter. Next, 2 parts by weight of the obtained aqueous colorant and 88 mo 1% saponified polyvinyl alcohol (degree of polymerization 1700) were mixed with N-methyl-γ-
Photosensitive resin 10 with 1.4 mo1% of (p-formylstyryl) pyridinium methosulfate introduced
parts by weight were sufficiently mixed to prepare a red photosensitive resin composition. Next, this red photosensitive resin composition was spin-coated onto the wafer substrate to a thickness of 1.5 μm,
After drying at 70° C. for 30 minutes, the wafer was precisely positioned at a predetermined position on the photosensitive portion of the wafer through a mask, and a contact pattern was exposed. Next, the pattern-exposed photosensitive resin composition was mixed with water/isopropyl alcohol=
After spray developing with a 5/1 (weight ratio) developer 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. Sensitivity is conventional gelatin/
It was twice that of Cr-based sensitive materials. The particle size distribution of this red photosensitive resin composition was 0.17 μm, and particles having a particle size of 0.01 to 0.3 μm accounted for 75% of the total particles.

The licensor substrate thus produced was subjected to assembly processes such as dicing, die bonding, wire bonding, and bagging by conventional methods to produce a licensor for color facsimile.

[Brief explanation of drawings]

The figure is a diagram showing the spectral characteristics of a colored image,
Curves a to b are spectral characteristic curves of a transparent colored image mounted on the color liquid crystal display device of the present invention, and curve c
is a spectral characteristic curve of a colored image according to a comparative example.

Claims (1)

[Claims] 1. A particle having a spectral characteristic of transmitting light in a specific region of the visible region, in which particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles, and in the range of 0.01 to 0.3 μm. It 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 transmittance in the light absorption region of the light absorption region in the visible region spectral characteristic curve is 20% or less. 1. A color filter, characterized in that a transparent colored image having a light transmittance of 50% or more in a light transmitting region is provided on a support in a pattern of multiple colors. 2. The color filter according to claim 1, wherein the pigment has a particle size distribution such that particles having a particle size of 1 μm or more account for 5% by weight or less of the total particles. 3. A method for producing a color filter in which transparent colored images of multiple colors are formed on a support, comprising:
On the support, particles having a spectral property that transmits light in a specific visible region, particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles, and particles in the range of 0.01 to 0.3 μm are present. It is made of a transparent resin in which a pigment having a particle size distribution that is 60% by weight or more of the total particles is dispersed, and the light transmittance in the light absorption region of the light absorption region in the spectral characteristic curve in the visible region is 20% or less, Includes a step of forming a transparent resin coating film in a pattern with a light transmittance of 50% or more in the light-transmitting region, and does not include a step of forming an anti-dye coating at least immediately before the above step. A method for manufacturing a color filter, characterized by: 4. A color liquid crystal display device comprising a liquid crystal sealed between at least a pair of electrode substrates, wherein at least one of the electrode substrates forms transparent colored images of two or more different hues on a transparent substrate. at least one of the transparent colored images has a spectral characteristic that transmits light in a specific region of the visible region, and particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles. , and 0.01~
It consists of a coating formed of a transparent resin in which a pigment is dispersed and has a particle size distribution in which particles in the range of 0.3 μm account for 60% by weight or more of the total particles, and in the spectral characteristic curve in the visible region of the transparent colored image. The light transmittance of the light absorption area is 20% or less, and the light transmittance of the light transmission area is
A color liquid crystal display device, characterized in that it is 50% or more. 5. A color liquid crystal display device comprising a liquid crystal sealed between at least a pair of electrode substrates, wherein at least one of the electrode substrates forms transparent colored images of two or more different hues on a transparent substrate. When manufacturing a color liquid crystal display device having a color filter, on the transparent substrate, particles having a first hue selected from red, green, and blue and having a particle size of 1 μm or more account for 10% of the total particles by weight. % or less and having a particle size distribution such that particles in the range of 0.01 to 0.3 μm account for 60% by weight or more of the total particles, the transparent resin composition comprising: The light transmittance of the light absorption region in the visible region spectral characteristic curve after coating film formation is 20% or less, and the light transmittance of the light transmission region is 50% or less.
% or more in the form of a first pattern, and then, without forming a resisting resin film, a coating film having a second hue different from the first hue and having a grain size of 1μm
A transparent resin composition obtained by dispersing a pigment having a particle size distribution such that the above particles account for 10% by weight or less of the total particles, and particles in the range of 0.01 to 0.3 μm account for 60% by weight or more of the total particles. A material that has a light transmittance of 20% or less in the light absorption region and a light transmittance of 50% or more in the light transmission region in the spectral characteristic curve in the visible region after the coating film is formed of this transparent resin. A transparent resin coating film is formed in a second pattern, and without further forming a resisting resin film, a third hue different from the first and second hues and having a particle size of 1 μm or more is formed. A transparent resin composition obtained by dispersing a pigment having a particle size distribution such that the particles account for 10% by weight or less of the total particles, and the particles in the range of 0.01 to 0.3 μm account for 60% by weight or more of the total particles. It's hot,
After forming this transparent resin coating film, the transparent resin coating film has a light transmittance of 20% or less in the light absorption region and a light transmittance of 50% or more in the light transmission region in the spectral characteristic curve in the visible region. A method for manufacturing a color liquid crystal display device, comprising: forming a third pattern, and then forming a transparent electrode film on the first to third patterned coating films.