JPS60129738A - Transparent colored image - Google Patents

Abstract

PURPOSE:To obtain a transparent colored image superior in light resistance, etc., and suitable for manufacture of color filters, etc., by dispersing a pigment having a specified particle diameter distribution in a PVA deriv. photosensitive resin having photosensitive structural units, and exposing and insolubilizing it. CONSTITUTION:A pigment is dispersed into a PVA deriv. photosensitive resin having each structural unit represented by formula I (R is H, alkyl, or lower hydroxyalkyl, and X<-> is a strong acid anion) so as to give a particle diameter distribution contg. particles having >=1mum diameter amounting to <=10wt% of the total particles. Then, it is applied to a supprt, patternwise exposed to be insolubilized, and developed to obtain an objective colored image. Said photosensitive resin is obtained by reacting styrylpyridinium salt, such as alpha-(p-formylstyryl) pyridinium, having a formyl group represented by formula II with polyvinyl alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to transparent colored images, and more particularly to color liquid crystal display devices, color facsimiles, three-tube or single-tube color video cameras, solid state color video cameras, etc. It relates to transparent colored images used in color filters attached to windows, stained glass, etc.

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 that has a color filter 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, which uses 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 images displayed in liquid crystal display devices, and one method for achieving this goal is to insert a liquid crystal material between a pair of parallel transparent electrodes, making the transparent electrodes discontinuous. In addition to dividing into small areas,
Red in each of the microscopic areas on this transparent electrode! Color filters used in color video cameras or color liquid crystal display devices use extremely fine areas colored in two or more colors of different hues on a transparent substrate. Alternatively, it is formed by providing it on a solid-state image sensor. Generally, in order to color a minute area with two or more colors of different hues, a photosensitive resin that can form a transparent colored image (pixel) is used.

Conventionally, 24 Jl! using photosensitive resin! Alternatively, in order to form a transparent layer color image of three or more types, first, a hydrophilic resin such as polyvinyl alcohol, polyvinylpyrrolidone, gelatin, casein, or grille is coated with a photosensitive material such as a salt chromate, a chromate, or a diazo compound. The added photosensitive resin is applied onto a support such as a transparent substrate or a solid-state image sensor to form a transparent photosensitive resin layer. Then,
A mask having an open pattern of a predetermined shape is placed on the photosensitive resin layer, exposed to light 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.
Forms 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 carried out. 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, the method described above has the disadvantage that the manufacturing process is extremely complicated, since it is not possible to create a single transparent colored image of multiple colors unless a transparent resist dyeing resin film is formed for each color. . Furthermore, the color filters in some buildings may be heated during their use, whereas the above method uses dyes.

Since the transparent image is colored, there is a limit to the heat resistance or light resistance of the resulting color filter, and in this respect it was not satisfactory.

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.

(,) Transparent colored images with two or more types of colors, such as color filters, etc. - When providing adjacently on a support, it is necessary to form a transparent resist dyeing resin film for each color. To provide a transparent colored image in which the manufacturing process is simplified.

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

In order to achieve the above object, the transparent colored image according to the present invention has particles with a particle size of 1 μm or more that are 1o3I of all particles.
@% or less, preferably 5 weight t% or less, more preferably 2%
A pigment having a particle size distribution of 11 cm or less in weight is dispersed in a transparent resin made by irradiating light onto a polyvinyl alcohol derivative photosensitive resin having a structural unit represented by the following general formula to make it insoluble in water. It is characterized by

[In the formula, R represents a hydrogen atom, an alkyl group, or a lower and P-hydroxyalkyl group, and X- represents a strong acid anion. Furthermore, in the present invention, the pigment dispersed in the transparent resin has a particle size of 0.01 to 0.7/1 m, preferably 0.0 m.
It is desirable that particles of 1 to 0.3 μm have a particle size distribution such that 2 ol Li 1% or more of the total particles, preferably (2) 1 mol Li, more preferably 1 501 mol 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 only 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 has not been known to what extent the particle size of pigments dispersed in transparent resin can be controlled to increase the transparency of colored images. It was not known whether the particle size could be controlled to such an extent that the resulting colored image would have satisfactory transparency.

In the present invention, if the particle size of the pigment dispersed in the transparent material is equal to or less than the wavelength of the incident light, the decrease in light transmittance due to light scattering can be suppressed, and the transparency of the resulting colored image can be improved in practical use. It is based on the discovery that it grows large enough to

Specific explanation of the clear color image The transparent colored image in the present invention is formed by dispersing pigments in transparent samurai resin, but this transparent TJ4 resin is made of polyvinyl alcohol having a structural unit represented by the following general formula. A derivative photosensitive resin made water-insoluble by irradiation with light 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. ]

The polyvinyl alcohol derivative photosensitive resin of the present invention comprises i
The ratio of the structural unit represented by the general formula II to other structural units, such as vinyl alcohol structural units or vinyl acetate structural units, is preferably in the range of 0.5:99.5 to 10:90. The structural unit represented by the above general formula is hydrophilic but not completely water-bathable;
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 resulting polyvinyl alcohol derivative photosensitive resin will become dissolvable or insoluble in water, which is not preferable. However, if a polar solvent such as hydrous alcohol, dimethylformamide P1 formamide, dimethyl sulfoxide, 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. Doing so becomes ag ability and improves sensitivity.

The polyvinyl alcohol derivative photosensitive attenuator used in the present invention is easily bathable in water before irradiation with light, and is
An absorption peak in the ultraviolet absorption spectrum is observed around 40 nm, and it becomes water-insoluble when exposed to light up to around 460 nm.

This polyvinyl alcohol conductor annotation is applied, for example, to 41J vinyl alcohol or partially cured polyvinyl acetate, with a formyl group t- It can be produced by reacting a styrylpyridinium salt.

The following compounds are used as the styrylpyridinium salt.

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? ) N-methyl-α-(O-formylstyryl)pyrinidiram 8) N-ethyl-α-(P-formylstyryl)pyridinium 9) N-(2-hydroxyethyl)-α-(p-formylstyryl)pyridinium 10 ) N-(2-hyroxyethyl)-γ-(p-formylstyryl)pyridinium 11) N-71J-α-(p-formylstyryl)pyridinium 12) N-methyl-r-(p-formylstyryl)pyridinium 13) N-,7'thyl-γ-(m-formylstyryl)
Pyridinium 14) N-benzyl-α-(p-pormylstyryl)
Pyridinium 15) N-benzyl-γ-(p-formylstyryl)
Pyridinium 16) N-carbamoylmethyl-r-(p-formylsteryl)pyridinium, etc.

These quaternary salts are salt c! *Haki, hydrobromide, hydroiodide, perchlorate, fluoroborate, methosulfate, phosphate, sulfate, methanesulfonate,
It may also exist in the form of P-F luenesulfonate or the like. These compounds contain the corresponding choline or N-
Salt of alkyl picolinimylstyryl pyridine or 4
It is graded and used as a specific salt.

On the other hand, the polyvinyl alcohol to be used may partially contain unsaponified acetyl groups, and it is desirable that the content of acetyl groups is less than 10%. In addition, the degree of polymerization is preferably about 400 to 3000. If the degree of polymerization is less than 400, the irradiation time required for water insolubilization will be significantly longer, which is undesirable. If the degree of polymerization exceeds 3000, the viscosity will increase, so handling is difficult. This is not desirable as it may cause problems.

The reaction between the styrylpyridium salt having a formyl group and polyvinyl alcohol or partially saponified polyvinyl acetate, that is, the acetalization reaction, can be carried out in water by an acid-catalyzed reaction.

In this case, the amount of styrylpyridinium salt used is preferably 0.5 to 1 mole 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, hydrofluoroboric acid, methanesulfonic acid, 1)-1' toluene Examples include sulfonic acid. If the amount added is large, the reaction time will be shortened, but the amount usually ranges from 0.01 to 5 normality. 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 the stilbazolium group around 340 nm of a 4+1 molar aqueous solution reprecipitated in alcohol.

This polyvinyl alcohol derivative photosensitive resin is described in detail in Japanese Patent Publication No. 56-5761, written by one of the inventors.

In the present invention, the transparent glaze obtained as described above is
Pigments are dispersed in the fat to form a transparent colored image.

In this specification, [#I material] means a colored powder that is soluble in water or an organic solvent, and includes both organic pigments and inorganic pigments. Note that some types of dyes are soluble in water or organic solvents, and these types of dyes can be used as "pigments" in the present invention. Examples of organic pigments include azo lake type, insoluble azo type, Condensed azo pigments, phthalocyanine pigments, quinacridone pigments, dioxazine pigments, inindolinone pigments, anthraquinone pigments, perinone pigments, thioinzaco pigments, perylene pigments, or mixtures of these pigments can be used.

Examples of inorganic pigments that can be used include Milolipur, Cobalt Purple, Manganese Purple, #Blue, Prussian Blue, Cobalt Blue, Cerulean Blue, Cerulean Blue, Viriazin, Emerald Green, and Cobalt Green. .

The pigment dispersed in the transparent resin has a particle diameter of 1 μm or more that is dispersed in the transparent resin in an amount of less than 10 μm, preferably more than 10 μm, of the total pigment particles. This is not preferable because the light transmittance decreases due to damage.

At the same time, the pigment used in the present invention has a particle size of 0.01 to 0.
．． 7fim preferably has a particle size distribution such that particles of 0.01 to 0.3 μm account for more than 20% by weight of the total pigment particles, preferably less than 50% by weight, and more preferably more than 50% by weight. It is desirable that you do so.

A transparent colored painter can be obtained by blending a pigment having such a particle size distribution M and a transparent iR resin at a solid content ratio of 1/10 to 2/1, preferably 1A to V2.

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 painting in which pigments having the desired particle size distribution as described above are dispersed, first, the pigments that have been ground quite finely are mixed with the photosensitive resin described above. The resulting 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 the particle size is determined by centrifugation or r-filtration through a glass filter, membrane filter, etc. is 1
Pigment particles with a large particle size of μm or more are removed to create a pigment-containing photosensitive resin composition, or the pigment is mixed with a solution of a binder resin that is compatible with the photosensitive resin described above, and the pigment is 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 using a glass filter, membrane filter, etc., and this colorant is mixed with the above-mentioned photosensitive resin. , a pigmented photosensitive resin composition can be produced.

When dispersing the pigment in the photosensitive resin, it is preferable to add a nonionic surfactant as a dispersant in order to improve the dispensing of the pigment. Furthermore, when removing large particle diameter pigments from a photosensitive resin composition or colorant in which pigments are dispersed, it is preferable that the viscosity of the composition* or colorant be adjusted to 500 ap or less.

Next, the photosensitive resin composition M containing pigment produced in this way is coated on the support with 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 0. 10μm preferably 0.5~
The coating is applied to a thickness of 3 μm at 8 degrees Celsius, and after drying, pattern exposure is performed using a xenon lamp, metal halogen lamp, ultra-high pressure mercury lamp, etc. light +5@ through a mask having a lobe pattern for a predetermined period. Next, the non-exposed areas may be selectively removed by spray development or dip development with a developer such as water or water/organic static medium.

By repeating the same operation several times, transparent colored images of multiple colors can be created without forming a greasy film for resist dyeing.
! can be provided on the support.

The final transparency of 1 dil of coloring depends on the light transmittance of the transparent resin used as the paste, the type of pigment dispersed in the transparent resin, and the W! It is determined by 1Jit and the thickness of the colored image layer provided on the support. First, the above-mentioned polyvinyl alcohol derivative transparent resin used as a paste has a visible light range of 40
Its light transmittance is 9 in the entire range from 0 to 700 nm.
5- or more, which is fully satisfactory in terms of transparency.

After the pigment is dispersed in the transparent resin that serves as the paste and then formed on the support to a predetermined thickness, the absorption area and transmission area vary 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. At the same time, in the transmission region, it is desirable that the light transmittance is 40% or more, preferably 50% or more, and more preferably t50% or more.

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

Here, the relationship between the particle size of the pigment dispersed in the transparent uA bond and the light transmittance is shown in Figure @1. Curve (a) in FIG. 1 indicates the particle size of the pigment dispersed in the transparent resin from 0.01 to 0.
The weight of the particles is 97 g of the total particles having a particle size of 3 μm, and the weight of the particles having a particle size of 1 μm or more is less than 2 weight of the total particles. On the other hand, the curve (,) in Figure 1 is obtained by simply dispersing a commercially available pigment in a transparent resin without performing any particle size distribution operation, and particles with a particle size of 1 pm or more account for 1% of all particles. 15
It also extends to % by weight.

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 characteristics 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 sharpness of the edge shape 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 minerals, transparent glass, transparent resin films, metal plates, ceramic plates, solid-state imaging devices that are photoelectric conversion devices, and the like can be used as the support.

Solid-state imaging devices include CCD, MOS, BBD,
C.I.D.

CPD or the like is used to directly or indirectly provide a transparent colored image according to the present invention on the light-receiving surface of the kernel to form a layer that forms a color filter for color separation.

11F11 Town Transparent colored image L1 according to the present invention is formed by dispersing a pigment having a specific particle size distribution in a transparent resin insolubilized by irradiating a polyvinyl alcohol derivative photosensitive resin into which a stilbazolium group has been introduced. Because of this, it has the following effects.

(,) When providing a plurality of transparent colored images on a support, it is not necessary to form a transparent resist dyeing resin g for each color, thus significantly simplifying the manufacturing process of transparent colored images. be able to.

(b) Since the above-mentioned polyvinyl alcohol derivative photosensitive resin forming the transparent resin is highly sensitive, the photosensitive south side can be easily rendered water-insoluble.

(c) A transparent layer color 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.

A polyvinyl alcohol fermentation derivative was prepared in which the structural unit shown in Example 1 was introduced in an amount of 1.2 mol% based on the vinyl alcohol structural unit, an average degree of ribbing was 1700°, and a saponification degree was 88°. 10% aqueous solution of this polyvinyl alcohol derivative 1
00 parts by weight, 10 parts by weight of Chromophthal Red BRN (red pigment manufactured by Ciba Geigy) were added and mixed. After dispersing the resulting mixture in a ball mill, the mixture was heated to 10.00O
It was centrifuged at rpm and passed through a 1 μm glass filter. The particle size distribution of the obtained red photosensitive resin composition was
As a result of analysis using the ult*r N4 submicron particle analyzer, the average particle size was 0.17 μm! D 0.01
Particles with a particle size of ~0.3 μm account for 75.5% of the total particles. blood·
I failed. Next, apply this red photosensitive resin composition to a thickness of 1 mm.
The film was spin-coated to a thickness of 1.5 μm on a thick transparent glass substrate, dried at 70"C for an addition period, and then exposed to light in a dense layer pattern through a mosaic-like mask. Next, the pattern-exposed photosensitizer was Resin composition #IJ was spray developed with a developer of water/isozorobyl alcohol = 10/3 (weight ratio) to selectively remove non-exposed areas, and then heated at 150°C for an additional period to make it transparent. A red image was formed.

Next, 10% aqueous solution 1 of the above polyvinyl alcohol i conductor.
10 parts by weight of Lionol Green 2Y-301 (Toyo Ingi Manufacturing - green pigment) were added and mixed to 00 parts by weight.

The resulting mixture: After kneading and dispersing vJ with a sand mill, 1
The mixture was centrifuged at 2.00 rpm and passed through a 1 μm glass filter. When the particle size outer layer of the pigment of the obtained green photosensitive resin composition was analyzed in the same manner, the average particle size was 0.1.
3 .mu.m and 0.0 um→, particles having a particle size 't- of 3 .mu.m accounted for 91 of all particles.

Next, this green photosensitive resin composition was spin-coated on the entire surface of the glass substrate on which the above-mentioned red transparent image was provided, in a film thickness of 1 coat, dried at 70°C, and then applied through a mask of a predetermined shape. The unexposed areas were selectively removed and dried to form a transparent green image adjacent to the red transparent image.

Similarly, 10% aqueous solution of the above polyvinyl alcohol derivative was prepared. Eight layers of Chromo Blue A3R (a blue pigment manufactured by Ciba Gai Co., Ltd.) were added and mixed into the mlll portion.

After grinding and dispersing the obtained mixture with a sand mill, 12.
After centrifugation at 000 rpm, it was filtered through a 1 μm glass filter. When the particle size and distribution of the pigment in the obtained blue photosensitive resin composition were analyzed in the same manner, the average particle size was 0.
18 .mu.m, and 75 of the total particles had a particle size ratio of o, o'i to o, a .mu.m. 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, dried for a while at 70°C, and then formed into a predetermined shape. A transparent colored image was formed adjacent to the green transparent image by pattern exposure through a mask, and selectively removing and drying the non-exposed areas.

A transparent guiding film was provided on the colored drawing hoe thus obtained to a thickness of 500 oi by low-temperature sputtering, and then polyimide was coated thereon to a thickness of 1000 g.
A rubbing process was performed and the electrode was 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 pull-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 polyvinyl alcohol 04 shown in Example 1 was dissolved in 100 Jt of water, and 5 parts of Lionol Green 2Y-301 (green pigment manufactured by Toyo Ink Manufacturing Co., Ltd.) was added to the resulting bath liquid. part was added and mixed.

The resulting mixture was kneaded and dispersed with three rolls, and after the ratio, 120
(Centrifuged at JOrpm and filtered through a 1 μm glass filter.Then, the obtained green photosensitive resin composition was
It was spin-coated to a thickness of 1.5 μm on a transparent glass substrate of 1 mrn$, dried at 70° C. for several minutes, and then exposed to light in a contact pattern through a mask. Next, the pattern-exposed photosensitive resin composition was mixed with water/ingropanol=lO
Spray developed with a developing solution of /3 (tortoise and animal ratio),
After selectively removing the non-exposed areas, it was heated at 150° C. for several minutes to form a green image. This green image 2g1
700 nm to 600 nm, as shown in the figure curve (&)
Although the transmittance of 500-5
The transmittance at 60 nm was 801 or higher. The sensitivity was four times that of conventional gelatin/Cr-based colored images. The edge shape was similar to that of the gelatin/Cr colored image. The particle size distribution of the pigment in this green transparent resin was determined by Coulter N
As a result of analysis using a 4 submicron particle analyzer,
The average particle size is 0.01 to 0.3 μm.
Particles having a particle size of 97% of the total particles.

Example 3 A mixture of Lionol Green 2Y-301 and a polyvinyl alcohol derivative was centrifuged at 600 rpm, and 1
A green image was formed in the same manner as in Example 1 except that f4 was used with a μm glass filter. The light transmittance of this green image was measured in the same manner as in Example 1, and curve (b) in Figure 1 was obtained.
Shown below.

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 the polyvinyl alcohol derivative was not centrifuged or filtered, and the light transmittance was measured. It is shown in Figure 1 curve (c).

From the WS 1 diagram curve (c), 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.

Using a wafer with an interline transfer type COD solid-state image element formed on a 4#φ silicon wafer as a substrate, a color filter for color separation was formed on the light receiving part of the p solid-state image sensor using the following steps. .

The structural unit represented by the formula was introduced in an amount of 1.2 mol % based on the vinyl alcohol structural unit, and the average degree of polymerization was 1700.
A polyvinyl alcohol derivative with a degree of oxidation of 88ts was prepared. To 100 parts by weight of a 10% aqueous solution of this polyvinyl alcohol derivative, 10 parts by weight of Rinter Moftal Red BRN (a red pigment manufactured by Ciba Geigy) was added and mixed. After dispersing the resulting mixture in a ball mill, the
Centrifuge at 0 rpm, lpm glass filter, -
It was filtered with The particle size distribution of the obtained red photosensitive resin composition was analyzed using a Coulter N4 submicron particle analyzer (the average particle size was 0.17 μm and 0.01 μm).
Particles with a particle size of ~0.3 μm were 75% of the total particles. Next, this red photosensitive resin composition was
The film was spin-coated to a thickness of 1.5 μm on a thick solid-state imaging device substrate, dried at 70° C. for 30 minutes, and then exposed to a tightly aligned pattern through a mosaic mask. Next, the pattern-exposed photosensitive resin acid was spray-developed with a developer containing water/isoglobil alcohol=10/3 (weight ratio) to selectively remove non-exposed areas, and then
Heated for 30 minutes at 0C to form a clear red image.

Next, a 10% aqueous solution 1 of the above polyvinyl alpool derivative
10 parts by weight of Lionol Green 2Y-301 (a green pigment manufactured by Toyo Ink Manufacturing Co., Ltd.) were added and mixed to 00 parts by weight.

After grinding and dispersing the obtained mixture with a sand mill, 12.
The mixture was centrifuged at 000 rpm and filtered through a 1 μm glass filter. The particle size distribution of the pigment in the obtained green photosensitive resin composition was analyzed in the same manner and found that the ξ filtration average particle size was 0.13/
lff$69 (particles with a particle size of 1.01 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 pickup device substrate on which the red transparent image was provided, and after drying at 70° C., a mask of a predetermined shape was formed. The non-exposed areas were selectively removed and dried, and a transparent green image was formed adjacent to the red transparent image.

Similarly, 8 parts by weight of Chromo Blue A3R (blue pigment manufactured by Ciba Geigy) was added and mixed to 100 parts by weight of a 10% aqueous solution of the polyvinyl alcohol derivative.

After grinding and dispersing the obtained mixture with a leaf mill, 12.
After centrifugation at 000 rpm, the mixture was passed through a 1 μm glass filter. When the five particle size distributions of the pigments in the obtained blue photosensitive resin composition were 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 on the surface of the solid-state image sensor substrate on which the red transparent image and green transparent image were provided, and after drying at 70° C. for 30 minutes, Pattern exposure was performed through a shaped mask, and unexposed areas were selectively removed and dried to form a transparent blue image adjacent to the green transparent image.

The substrate on which the color filter is formed on the predetermined light-receiving area of the solid-state image sensor in this way is subjected to assembly processes such as dicing, die bonding, wire bonding, and package ink using normal methods to form a solid-state image sensor. was created. Using this color solid-state image sensor, we were able to create a solid-state color camera with good color reproducibility.

Example 5 Using Ueno 1-, in which an interline transfer type COD solid-state imaging device was formed on a silicon wafer of 4'φ, 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.

A polyvinyl alcohol derivative having an average degree of polymerization of 1700 and a degree of saponification of about 88, in which the structural unit represented by the formula is introduced in an amount of 1.2 mo1% based on the vinyl alcohol structural unit, is 1Ii.
Made by II. After adding and mixing 10 parts by weight of Chromo7 Tarred BRN (red pigment manufactured by Ciba Geigy) to 100 parts by weight of a 10% aqueous solution of this polyvinyl alcohol derivative,
It was centrifuged at 10,000 rpm and passed through a 1 pm glass filter. The particle size distribution of the obtained red photosensitive resin composition was analyzed using a Coultsr N4 submicron particle analyzer and the average particle size was 0.17 pln! + Particles with a particle size of 0.01 to 0.3 μm accounted for 75% of the total particles. Next, this red photosensitive resin composition was applied to a 1.5 μm thick solid-state image sensor substrate with a thickness of 500 μm.
After drying at 70° C. for 30 minutes, the film was accurately aligned and exposed to a contact pattern through a mosaic mask. Next, the pattern-exposed photosensitive resin composition was mixed with water/isoglobil alcohol=10A (weight ratio).
The non-exposed areas were selectively removed by spray development using a developer solution, and then heated at 150 DEG C. for 30 minutes to form a transparent red image.

A red color filter is formed on a predetermined light-receiving area of a solid-state image sensor on a substrate, and then an assembly process such as dicing, die bonding, wire bonding, and packaging is added to the substrate to create a color image. The camera was stamped [7 times].

When used in a light-receiving element for color facsimile, a good quality image was obtained.

[Brief explanation of the drawing]

4. Figure 4 is a diagram showing the spectral characteristics of a colored image, where curves (1) to (b) are the spectral characteristic curves of the colored image according to the present invention, and curve (c) is the spectral characteristic curve of the colored image according to the comparative example. This is the spectral characteristic curve of Applicant's agent Kiyoshi Inomata 400 700 Ninaga (nm)

Claims (1)

[Scope of Claims] 1. A pigment having a particle size at such that particles having a particle size of 1 μm or more are less than the toots of all particles is exposed to a polyvinyl alcohol derivative photosensitive resin having a structural unit represented by the following general formula. A transparent colored image characterized by being dispersed in a transparent resin made water-insoluble by irradiation with 2. In the 1R material, particles with a particle size of 1 μm or more account for 5 times 1 of all particles.
% or less. 3. The pigment has a particle size distribution such that particles with a particle size of 1 μm or more account for 10% by weight or less of the total particles, and particles with a particle size of 0.01 to 0.7 μm weigh more than - The composition according to claim 1, characterized in that it comprises: 4. Pigments have particles with a particle size of 1 μm or more that account for 5% of the total weight of the particles.
Claim 1. Composition described in @tVc.