JPH0349422B2 - - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to transparent colored images, and more particularly to color liquid crystal displays, color facsimiles, three-tube or single-tube color video cameras, solid-state color video cameras, etc. This invention relates to transparent colored images used in color filters attached to windows, stained glass, etc.

Technical background of the invention and its problems 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, and for this reason extremely fine stripes of two or more different hues are provided on a transparent substrate. A single-tube color video camera is used in which a color filter is attached to the lens system. Furthermore, for the same purpose, a single-tube color video camera has been proposed in which a color filter is provided in direct contact with the light-receiving surface of the 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. As a solid-state image sensor, CCD.MOS.CID.
CPD etc. are used.

On the other hand, there is a growing interest in colorizing the displayed images in liquid crystal display devices, and one method for this purpose is to seal a liquid crystal material between a pair of parallel transparent electrodes and to make the transparent electrodes discontinuous. A method in which the transparent electrode is divided into fine areas and each of the fine areas on the transparent electrode is provided with a color selected from red, blue, or green in an alternating pattern, or a transparent electrode is formed after forming a color filter on the substrate. A method of providing electrodes has been proposed.

In this way, color filters used in color video cameras, color liquid crystal display devices, etc. are made by providing extremely fine areas colored in two or more different hues on a transparent substrate or solid-state image sensor. It is formed by twisting. 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, first, a hydrophilic resin such as polyvinyl alcohol, polyvinylpyrrolidone, gelatin, casein, or griux is added to a photosensitive material such as dichromate or chromium. A photosensitive resin to which an acid salt or a diazo compound is added is coated on a support such as a transparent substrate or a solid-state imaging device to form a transparent photosensitive 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, 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, there is a limit to the heat resistance or light resistance of the resulting color filter. , was not satisfactory in this respect.

OBJECTS OF THE INVENTION AND 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) Two or three types, such as color filters, etc.
When providing multiple transparent colored images adjacent to each other on a support, it is not necessary to form a transparent resist resin film for each color, and therefore the manufacturing process is simplified. Provide colored images.

(b) To provide transparent colored images with excellent heat resistance and light resistance.

In order to achieve the above objects, the transparent colored image according to the present invention has spectral characteristics that allow light to pass through a specific region of the visible region, and particles with a particle size of 1 μm or more account for 10 of the total particles. Weight% or less, particle size
Light is irradiated onto a polyvinyl alcohol derivative photosensitive resin having a structural unit represented by the general formula below, in which a pigment having a particle size distribution such that particles of 0.01 to 0.7 μm account for 30% by weight or more of the total particles is dispersed. It is a colored image made of a water-insoluble transparent resin, and the light transmittance of the light absorption region in the spectral characteristic curve of the visible region of the colored image is 20% or less, and the light transmittance of the light transmission region is 50% or more. It is characterized by

[In the formula, R represents a hydrogen atom, an alkyl group or a lower hydroxyalkyl group, and X ^- represents a strong acid anion. ] Furthermore, in the present invention, the pigment dispersed in the above transparent resin has a particle size of 0.01 to 0.7 μm, preferably
It is desirable to have a particle size distribution such that particles of 0.01 to 0.3 μm account for 50% by weight or more.

Conventionally, colored resins in which a certain type of pigment is dispersed in a transparent resin have been known, but the particle size of the pigment used therein is significantly larger than that of the present invention, resulting in insufficient transparency. However, it is not used for purposes such as masking, and even if it were used for color filters, it would not have sufficient sensitivity due to its low transmittance. Furthermore, it is not known in the past that the transparency of the colored image obtained can be improved by controlling the particle size of the pigment dispersed in the transparent resin. It was not known whether the diameter could be controlled to such an extent that the transparency of the resulting colored image was satisfactory.

In the present invention, if the particle size of the pigment dispersed in the transparent resin is equal to or smaller than the wavelength of the incident light, a decrease in light transmittance due to light scattering is suppressed, and the transparency of the resulting colored image is sufficient for practical use. This is based on the discovery that the size of the

DETAILED DESCRIPTION OF THE INVENTION The transparent colored image in the present invention is formed by dispersing pigments in a transparent resin, and the transparent resin includes a photosensitive polyvinyl alcohol derivative having a structural unit represented by the following general formula. A resin made by irradiating light to make it water-insoluble is used.

[In the formula, R represents a hydrogen atom, an alkyl group or a lower hydroxyalkyl group, and X ^- represents a strong acid anion. ] In the polyvinyl alcohol derivative photosensitive resin of the present invention, the ratio of the structural units represented by the above general formula to other structural units, such as vinyl alcohol structural units or vinyl acetate structural units, is in the range of 0.5:99.5 to 10:90. It is preferable that Although the structural unit represented by the above general formula is hydrophilic, it is not completely water-soluble. Therefore, if the structural unit represented by the above general formula is introduced into the polyvinyl alcohol derivative photosensitive resin in an amount exceeding the above range, the resultant The polyvinyl alcohol derivative photosensitive resin obtained is poorly soluble or insoluble in water, which is not preferable. However, if a polar solvent such as hydrous alcohol, dimethylformamide, formamide, dimethyl sulfoxide, etc. or a mixed solvent of these solvents and water is used as a solvent, the structural unit represented by the above general formula can be introduced at a higher level than the above range. This makes it possible to improve sensitivity.

The polyvinyl alcohol derivative photosensitive resin used in the present invention is easily soluble in water before irradiation with light, exhibits an absorption peak in the ultraviolet absorption spectrum around 340 nm in an aqueous solution, and is sensitive to light up to around 460 nm. Becomes insoluble.

This polyvinyl alcohol derivative photosensitive resin is produced by adding polyvinyl alcohol or partially saponified polyvinyl acetate with the general formula (In the formula, R and X ^- have the same meanings as above)
It can be produced by reacting a styrylpyridinium salt having a polmyl group represented by:

As this styrylpyridinium salt, the following compounds can be used.

(1) α-(p-formylstyryl)pyridinium (2) γ-(p-formylstyryl)pyridinium (3) α-(m-formylstyryl)pyridinium (4) N-methyl-α-(p-formylstyryl) )
Pyridinium(5) N-methyl-β-(p-formylstyryl)
Pyridinium(6) N-methyl-α-(m-formylstyryl)
Pyridinium(7) N-methyl-α-(o-formylstyryl)
Pyridinium(8) N-ethyl-α-(p-formylstyryl)
Pyridinium (9) N-(2-hydroxyethyl)-α-(p-formylstyryl)pyridinium(10) N-(2-hydroxyethyl)-γ-(p-formylstyryl)pyridinium(11) N-allyl- α-(p-formylstyryl)
Pyridinium(12) N-methyl-γ-(p-formylstyryl)
Pyridinium(13) N-methyl-γ-(m-formylstyryl)
Pyridinium (14) N-benzyl-α-(p-formylstyryl)pyridinium (15) N-benzyl-γ-(p-formylstyryl)pyridinium (16) N-carbamoylmethyl-γ-(p-formylstyryl)pyridinium Such.

These quaternary salts include hydrochloride, hydrobromide,
It may be present in the form of hydroiodide, perchlorate, hydroborate, methosulfate, phosphate, sulfate, methanesulfonate, p-toluenesulfonate, and the like. These compounds are
It is obtained by a condensation reaction between the corresponding picoline or N-alkylpicolinium salt and an aromatic dialdehyde, that is, formylbenzaldehyde, and is used as a formylstyrylpyridine salt or a quaternized salt.

On the other hand, the base polyvinyl alcohol is
It may contain a partially saponified acetyl group,
The content of acetyl groups is preferably less than 30%. The degree of polymerization is preferably about 400 to 3000, and if the degree of polymerization is less than 400, the irradiation time required for water insolubilization will be significantly longer, which is preferable.
Further, if the degree of polymerization exceeds 3000, the viscosity increases, which may cause handling problems, which is not preferable.

a styrylpyridium salt having a formyl group,
The reaction with polyvinyl alcohol or partially saponified polyvinyl acetate, that is, the acetalization reaction, is
It can be carried out in water by an acid-catalyzed reaction.
At this time, the amount of styrylpyridinium salt used is preferably 0.5 to 30 mol % per vinyl alcohol unit. As the acid catalyst, either an inorganic acid or an organic acid can be used, and specifically, for example, hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, hydroborofluoric acid, methanesulfonic acid, p-
Examples include toluenesulfonic acid. The larger the amount added, the shorter the reaction time, but usually 0.01
~5 normality is sufficient. The reaction is carried out at a temperature ranging from room temperature to 100°C, and a reaction time of about 1 to 24 hours is sufficient.

The progress of this acetalization reaction can be monitored by measuring the absorption maximum based on stilbazolium groups around 340 nm of an aqueous solution of the resin reprecipitated in alcohol.

Regarding this polyvinyl alcohol derivative photosensitive resin, the patent publication published in 1983 by one of the inventors of the present invention
It is explained in detail in Publication No.-5761.

In the present invention, pigments are dispersed in the transparent resin obtained as described above to form a transparent colored image.

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.

As the inorganic pigment, Miloli blue, iron oxide, cobalt violet, manganese violet, ultramarine blue, navy blue, cobalt blue, cerulean blue, biriazine, emerald green, cobalt green, etc. can be 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. Preferably. If particles with a particle size of 1 μm or more are dispersed in the transparent resin in an amount exceeding 10% by weight of the total pigment particles, the light transmittance will decrease due to light scattering, which is undesirable. At the same time, the pigment used in the present invention is
Particles with a particle size of 0.01 to 0.7 μm, preferably 0.01 to 0.3 μm, account for 30% by weight or more of the total pigment particles, more preferably
It is desirable to have a particle size distribution of 50% by weight or more.

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 transparent colored image can be obtained by blending at a ratio of ~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.

In order to form a transparent colored image in which a pigment having the desired particle size distribution as described above is dispersed, first, the pigment that has been ground quite finely is mixed with the photosensitive resin solution described above, and the resulting The mixture is kneaded using a pigment dispersion machine such as a three-roll mill, a ball mill, or a sand mill to fully disperse the pigment, and then centrifuged or filtered through a glass filter, membrane filter, etc. until the particle size is reduced to 1μ.
A pigment-containing photosensitive resin composition can be prepared by removing pigment particles with a large particle size of m or more, or the pigment can be mixed with a solution of a binder resin that is compatible with the photosensitive resin described above, and then thoroughly mixed in the same manner as above. After dispersion, 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 is mixed with the photosensitive resin described above. A pigment-containing photosensitive resin composition can then be produced.

When dispersing a pigment in a photosensitive 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 photosensitive 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, the pigment-containing photosensitive resin composition prepared in this way is applied onto a support using a coating device such as a spinner, bar coater, roll coater, dip coater, or foil coater to a dry film thickness of 0.1 to
The coating is applied to a thickness of 10 μm, preferably about 0.5 to 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. The non-exposed areas 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 resist resin film.

The transparency of the final colored image is determined by the light transmittance of the transparent resin used as the base, the type and amount of pigment dispersed in the transparent resin, and the thickness of the colored image layer provided on the support. Determined by etc. First, the above-mentioned polyvinyl alcohol derivative transparent resin used as a base has a light transmittance of 95% or more in the entire visible light region of 400 to 700 nm, and is fully satisfactory in terms of transparency. be.

Pigments are dispersed in this base transparent resin,
After the film is formed on the support to a predetermined thickness, the absorption region and transmission region vary depending on the type of pigment used, but the light transmittance in the absorption region is 20% or less, preferably 10%. The following is desirable. At the same time, it is desirable that the light transmittance in the transmission region is 40% or more, preferably 50% or more, and more preferably 60% or more.

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

Here, FIG. 1 shows the relationship between the particle size of the pigment dispersed in the transparent resin and the light transmittance. Curve a in Figure 1 indicates the particle size of the pigment dispersed in the transparent resin, where 97 of the total particles have a particle size of 0.01 to 3 μm.
% by weight, and the amount of particles having a particle size of 1 μm or more is adjusted to be 2% by weight or less of the total particles. On the other hand, the curve c in Figure 1 is
A commercially available pigment is simply dispersed in a transparent resin without any particle size distribution manipulation, and the particle diameter is 1 μm.
Particles having a particle size of m or more account for as much as 15% by weight of all particles.

Even when the transparent colored image according to the present invention is subjected to heat treatment at about 200° C. for several tens of minutes, its spectral transmittance properties hardly change, and it has excellent heat resistance. It should be noted that general organic dyed images fade significantly when heated at 200°C for several tens of minutes.

Furthermore, when the light resistance of the transparent colored image according to the present invention is examined by carbon lamp irradiation, the fading phenomenon is improved by 3 to 4 times compared to the organic dyed image. As described above, the transparent colored image according to the present invention has excellent heat resistance and light resistance.

The edge shape sharpness of each colored image is comparable to that of conventional gelatin-based sensitive materials, and the sensitivity is about twice that of gelatin.

Note that as the support, transparent glass, a transparent resin film, a metal plate, a ceramic plate, a solid-state image sensor that is a photoelectric conversion element, etc. can be used.
As a solid-state image sensor, CCD.MOS.BBD.CID.
A color filter for color separation can be formed by using a CPD or the like and directly or indirectly providing a transparent colored image according to the present invention on the light receiving surface.

Effects of the Invention The transparent colored image according to the present invention is formed by dispersing a pigment having a specific particle size distribution in a transparent resin that is insolubilized by irradiating a polyvinyl alcohol derivative photosensitive resin into which a stilbazolium group has been introduced. As a result, it has the following effects.

(a) When providing a plurality of transparent colored images on a support, it is not necessary to form a transparent resist dyeing resin film for each color, thereby significantly simplifying the manufacturing process of transparent colored images. I can do it.

(b) Since the above-mentioned polyvinyl alcohol derivative photosensitive resin forming the transparent resin has high sensitivity, the photosensitive resin can be easily made insoluble in water.

(c) A transparent colored image with excellent heat resistance and light resistance can be obtained.

The present invention will be described below based on Examples, but the present invention is not limited to the following Examples.

Example 1 Formula The average degree of polymerization is 1700, where the structural unit shown is introduced in 1.2 mol% relative to the vinyl alcohol structural unit.
A polyvinyl alcohol derivative with a degree of saponification of approximately 88% was prepared. 10 of this polyvinyl alcohol derivative
% aqueous solution 100 parts by weight, Chromophthaled BRN
(red pigment manufactured by Ciba Geigy) was added and mixed. The resulting mixture was milled and dispersed in a ball mill, centrifuged at 10,000 rpm, and filtered through a 1 μm glass filter. The particle size distribution of the obtained red photosensitive resin composition was analyzed using a Coulter N4 submicron particle analyzer, and the average particle size was 0.17 μm.
Particles having a particle size of 0.01 to 0.3 μm accounted for 75% of all particles. Next, this red photosensitive resin composition was spin-coated to a thickness of 1.5 μm on a 1 mm thick transparent glass substrate, dried at 70° C. for 30 minutes, and exposed in a contact pattern through a mosaic mask. Next, the pattern-exposed photosensitive resin composition is
Water/isopropyl alcohol = 10/3 (weight ratio)
After spray developing with a developer solution to selectively remove non-exposed areas, the film was heated at 150° C. for 30 minutes to form a transparent red image.

Next, 10 parts by weight of Lionol Green 2Y-301 (a green pigment manufactured by Toyo Ink Mfg. Co., Ltd.) was added and mixed to 100 parts by weight of a 10% aqueous solution of the polyvinyl alcohol derivative. The resulting mixture was milled and dispersed in a sand mill, centrifuged at 12,000 rpm, and filtered through a 1 μm glass filter. When the particle size distribution of the pigment in the obtained green photosensitive resin composition was similarly analyzed, the average particle size was 0.13 μm, and particles having a particle size of 0.01 to 0.3 μm accounted for 91% of the total particles. Next, this green 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 transparent image was provided, and after drying at 70°C for 30 minutes, it was applied through a mask of a predetermined shape. Pattern exposure was carried out, and unexposed areas were selectively removed and dried to form a transparent green image adjacent to the red transparent image.

Similarly, the above polyvinyl alcohol derivative
8 parts by weight of ChromoBlue-A3R (blue pigment manufactured by Ciba Geigy) were added and mixed to 100 parts by weight of a 10% aqueous solution. The resulting mixture was milled and dispersed in a sand mill, centrifuged at 12,000 rpm, and filtered through a 1 μm glass filter. When the particle size and distribution of the pigment in the obtained blue photosensitive resin composition was similarly analyzed, the average particle size was 0.18 μm, and particles having a particle size of 0.01 to 0.3 μm accounted for 75% of the total particles. . Next, this blue photosensitive resin composition was spin-coated to a film thickness of 1 μm onto the surface of the glass substrate on which the red transparent image and green transparent image were provided, and after drying at 70°C for 30 minutes, a predetermined shape of the blue photosensitive resin composition was applied. Pattern exposure is carried out through a mask, non-exposed areas are selectively removed and dried.
A transparent blue image was formed adjacent to the green transparent image.

A transparent conductive film with a thickness of 800 Å was applied 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 that would serve as a counter electrode. Next, a cell was assembled by injecting liquid crystal, and when applied to a full-color liquid crystal display device in which a colored image was formed inside the cell, excellent characteristics were obtained.

Example 2 10 parts by weight of the polyvinyl alcohol derivative shown in Example 1 was dissolved in 100 parts by weight of water, and 5 parts by weight of Lionol Green 2Y-301 (green pigment manufactured by Toyo Ink Manufacturing Co., Ltd.) was added to the resulting solution. were added and mixed.
After mixing and dispersing the obtained mixture with three rolls,
It was centrifuged at 12,000 rpm and passed through a 1 μm glass filter. Next, the obtained green photosensitive resin composition was spin coated onto a 1 mm thick 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/isopropanol = 10/3 (weight ratio), and the non-exposed areas were selectively removed.
A green image was formed by heating at 150° C. for 30 minutes.
As shown in curve a of this green image in Figure 1, 700n
Although the transmittance in the wavelength range from m to 600 nm was 1% or less, the transmittance in the wavelength range from 500 to 560 nm was 80% or more. Sensitivity is 4 compared to conventional gelatin/Cr-based colored images
It was twice as hot. 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 was analyzed using a Coulter N4 submicron particle analyzer, and the average particle size was 0.08μ.
m, and particles having a particle size of 0.01 to 0.3 μm are:
It accounted for 97% of all particles.

Example 3 A green image was formed in the same manner as in Example 1, except that a mixture of Lionol Green 2Y-301 and a polyvinyl alcohol derivative was centrifuged at 6000 rpm and passed through a 1 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 in Figure 1.

Comparative Example 1 A green image was formed in the same manner as in Example 1, except that the mixture of Lionol Green 2Y-301 and polyvinyl alcohol derivative was not centrifuged at all, and the light transmittance was measured. This is shown in curve c in Figure 1.

It can be seen from curve c in FIG. 1 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.

Example 4 Using a 4″φ silicon wafer on which a CCD solid-state imaging device of an interline transfer type was formed 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.

formula The average degree of polymerization is 1700, where the structural unit shown is introduced in 1.2 mol% relative to the vinyl alcohol structural unit.
A polyvinyl alcohol derivative with a degree of saponification of approximately 88% was prepared. 10 of this polyvinyl alcohol derivative
% aqueous solution 100 parts by weight, Chromophthaled BRN
(red pigment manufactured by Ciba Geigy) was added and mixed. The resulting mixture was milled and dispersed in a ball mill, centrifuged at 10,000 rpm, and filtered through a 1 μm glass filter. The particle size distribution of the obtained red photosensitive resin composition was analyzed using a Coulter N4 submicron particle analyzer, and the average particle size was 0.17 μm.
Particles having a particle size of 0.01 to 0.3 μm accounted for 75% of all particles. Next, this red photosensitive resin composition was spin-coated to a film thickness of 1.5 μm on a 500 μm thick solid-state image sensor substrate, dried at 70°C for 30 minutes, and then accurately aligned and formed into a contact pattern through a mosaic mask. exposed. Next, the pattern-exposed photosensitive resin composition is mixed with water/isopropyl alcohol=
After spray developing with a 10/3 (weight ratio) developer to selectively remove the non-exposed areas, the film was developed at 150°C for 30
Heated for a minute to form a clear red image.

Next, 10 parts by weight of Lionol Green 2Y-301 (a green pigment manufactured by Toyo Ink Mfg. Co., Ltd.) was added and mixed to 100 parts by weight of a 10% aqueous solution of the polyvinyl alcohol derivative. The resulting mixture was milled and dispersed in a sand mill, centrifuged at 12,000 rpm, and filtered through a 1 μm glass filter. When the particle size distribution of the pigment in the obtained green photosensitive resin composition was similarly analyzed, the average particle size was 0.13 μm, and particles having a particle size of 0.01 to 0.3 μm accounted for 91% of the total particles. Next, this green photosensitive resin composition was spin-coated to a film thickness of 1 μm over the entire surface of the solid-state image sensor substrate on which the red transparent image was provided, and after drying at 70°C for 30 minutes, it was applied through a mask of a predetermined shape. The non-exposed areas were selectively removed and dried to form a transparent green image adjacent to the red transparent image.

Similarly, the above polyvinyl alcohol derivative
8 parts by weight of ChromoBlue-A3R (blue pigment manufactured by Ciba Geigy) were added and mixed to 100 parts by weight of a 10% aqueous solution. The resulting mixture was milled and dispersed in a sand mill, centrifuged at 12,000 rpm, and filtered through a 1 μm glass filter. When the particle size distribution of the pigment in the obtained blue photosensitive resin composition was similarly analyzed, the average particle size was 0.18 μm, and particles having a particle size of 0.01 to 0.3 μm accounted for 75% of the total particles. Next, this blue photosensitive resin composition was spin-coated to a thickness of 1 μm onto the surface of the solid-state image sensor substrate on which the red transparent image and green transparent image were provided, and the composition was heated at 70°C.
After drying for 30 minutes, pattern exposure was performed through a mask of a predetermined shape, and non-exposed areas were selectively removed and dried to form a transparent blue image adjacent to the green transparent image.

A color solid-state image sensor was fabricated by adding an assembly process such as dicing, die bonding, wire bonding, and packaging to the substrate on which a color filter was formed on a predetermined light-receiving area of the solid-state image sensor in a conventional manner. . Using this color solid-state image sensor, we were able to create a solid-state color camera with good color reproducibility.

Example 5 Using a 4″φ silicon wafer on which a CCD solid-state imaging device of an interline transfer type was formed 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.

formula The average degree of polymerization is 1700, where the structural unit shown is introduced in 1.2 mol% relative to the vinyl alcohol structural unit.
A polyvinyl alcohol derivative with a degree of saponification of approximately 88% was prepared. 10 of this polyvinyl alcohol derivative
% aqueous solution 100 parts by weight, Chromophthaled BRN
(red pigment manufactured by Ciba Geigy) was added and mixed. The resulting mixture was milled and dispersed in a ball mill, centrifuged at 10,000 rpm, and filtered through a 1 μm glass filter. The particle size distribution of the obtained red photosensitive resin composition was analyzed using a Coulter N4 submicron particle analyzer, and the average particle size was 0.17 μm.
Particles having a particle size of 0.01 to 0.3 μm accounted for 75% of all particles. Next, this red photosensitive resin composition was spin-coated to a film thickness of 1.5 μm on a 500 μm thick solid-state image sensor substrate, dried at 70°C for 30 minutes, and then accurately aligned and adhered through a mosaic mask. pattern exposed. Next, the pattern-exposed photosensitive resin composition is mixed with water/isopropyl alcohol=
Spray developed with a 10/3 (weight ratio) developer,
After selectively removing the unexposed areas, it was heated at 150° C. for 30 minutes to form a transparent red image.

A color solid-state image sensor is fabricated by adding assembly processes such as dicing, die bonding, wire bonding, and packaging using normal methods to the substrate on which a red color filter is formed on the predetermined light-receiving area of the solid-state image sensor. did.

When used in a light receiving element for color facsimile, good color images were obtained.

[Brief explanation of drawings]

FIG. 1 is a diagram showing spectral characteristics of a colored image, where curves a to b are spectral characteristic curves of a colored image according to the present invention, and curve c is a spectral characteristic curve of a colored image according to a comparative example. .

Claims (1)

[Scope of Claims] 1. Particles having a spectral characteristic of transmitting light in a specific visible region, and in which 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 0.7 μm. Transparent resin made water-insoluble by irradiating light on a polyvinyl alcohol derivative photosensitive resin having a structural unit represented by the general formula below, in which a pigment having a particle size distribution such that the particles account for 30% by weight or more of the total particles is dispersed. is a colored image in which the light transmittance of the light absorption region in the visible region spectral characteristic curve of the colored image is 20
% or less, a transparent colored image characterized by a light transmittance of 50% or more in the light transmitting area. (In the formula, R represents a hydrogen atom, ^an alkyl group, or a lower hydroxyalkyl group; The transparent colored image according to claim 1, having a particle size distribution as described above.