JPS60129707A - Color filter - Google Patents

Abstract

PURPOSE:To obtain a titled color filter with a simple manufacturing process by dispersing a pigment having a specified particle diameter distribution in a photosensitive resin, coating on a supporting body, exposing and developing, and repeating said operations to form a patterned transparent colored image in plural colors. CONSTITUTION:An organic or an inorganic pigment is dispersed in a photosensitive resin (e.g., polyvinyl alcohol stilbazolium resin) so that the particle diameter distribution of the pigment particles may consist of <=10wt% particles having >=1mum particle diameter basing on the whole particles and >=20wt% particles having 0.01-0.7mum. Then the material is coated on a supporting body such as glass, pattern-exposed and developed, and a patterned transparent colored image in plural colors is formed by repeating said operations plural times to obtain the desired color filter. The formation of a resist printing resin film on each color can be dispensed with in this way, and hence the manufacturing process can be simplified.

Description

DETAILED DESCRIPTION OF THE INVENTION The technical field of the invention relates to color filters, and more particularly, to color filters used in color liquid crystal displays, color facsimiles, three-tube and single-tube color video cameras, solid-state color video cameras, etc. This invention relates to color filters.

Technical background of the invention and its problems In recent years, interest in color video cameras for 'gM' has been rapidly increasing. Home color video cameras are required to be compact, lightweight, and inexpensive, and for this reason extremely fine stripes of two or more different hues are printed on a transparent substrate. A tube-type color video camera is used in which a color filter is attached to an image pickup tube system. Furthermore, for the purpose of Ichikawa, a solid-state color video camera has been proposed in which a color quilter is provided in close contact with the light-receiving surface of the N1-body image sensor of the color video camera. A method has also been proposed in which a color filter for color separation is formed directly or indirectly on the light-receiving surface of a solid-state scanning element such as a line sensor or an area sensor, which is a photoelectric conversion element. A CCD is a solid-state image sensor.

MOS, BBD, CID, CPD, etc. are used.

On the other hand, in the case of liquid crystal display devices, there is also interest in colorizing the displayed image 13, and one method for this purpose is to create a liquid crystal phase difference between a pair of parallel transparent electrodes. At the same time, the transparent electrode is divided into discontinuous micro areas, and each of the micro areas on this transparent electrode is
A method has been proposed in which colors selected from red, iku, and green are alternately provided in a pattern, or a method in which transparent electrodes are provided after forming a color filter on a substrate. Alternatively, color filters used in color liquid crystal display devices are formed by providing extremely detailed colored areas of 2 square meters or 3 square meters or more with different hues on a transparent substrate or solid-state image sensor. .

Generally, in order to color a minute area to three or more colors, a photosensitive resin that can form a transparent colored image (pixel) is used.

Conventionally, the trap of forming transparent colored images of 2 types or 31F or more using photosensitive resins is to first use polyvinyl alcohol,
A photosensitive resin containing a hydrophilic resin K such as polyvinylpyrrolidone, gelatin, casein, or green, dichromate, chromate, or diazo compound as a photosensitive material is used as a transparent substrate or a solid imaging element. A transparent photosensitive resin layer is formed by coating on a support. Then,
A mask having an open pattern of a predetermined shape is placed on this photosensitive resin ++'rI layer, and exposure and development are performed to form the ml resin layer into a shape of 1Jla L, and this first resin layer is dyed with a desired dye. to form a lA1 transparent layer color image. next,
In order to prevent the transfer of dye onto this first transparent colored image, after forming a transparent resist dyeing resin film made of a hydrophobic resin, a second transparent colored image is formed using the same method as that for forming the first transparent colored image. Forming a two-transparent layer color image. By repeating the above operations, a transparent colored image colored in two or more colors is formed on the support.

However, the above method has the disadvantage that the manufacturing process is extremely complicated, since transparent colored images of multiple colors cannot be provided unless a transparent resist dyeing resin film is formed for each color. be. Furthermore, some color filters may be heated during use, but in the above method, the transparent image is tinted using dye, so the heat resistance or light resistance of the resulting color filter may be affected. It had its limitations and was not satisfactory in this respect.

OBJECTIVES AND SUMMARY OF THE INVENTION The present invention attempts to solve all of the drawbacks associated with the prior art, and has the following objects: (a) Coloring of 2m or 3fi or more When manufacturing a color filter by placing transparent colored images adjacent to each other on a support, there is no need to form a transparent resist resin film for each color, which simplifies the manufacturing process. To provide color filters with different colors.

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

In order to achieve the above object, the color filter according to the present invention has a structure in which particles having a particle size of 1 μm or more are present on a bone support at 10% by weight or less, preferably 5% by weight or less, and more preferably 5% by weight or less of the total particles. It is characterized in that a transparent colored image of multiple colors is provided in a patterned manner, which is made by dispersing pigments having a particle size distribution of 2% by weight or less in a transparent resin.

Furthermore, in the present invention, the pigment dispersed in the transparent resin is
Branch sail 01~0.7μmtJf-preferably 0.01~0
．． 3μm particles or 2DNk% or more of all particles, preferably 3
It is desirable to have a t-diameter distribution that is 0% or more, more preferably 50% or more.

In the past, a transparent resin was known in which a certain pigment was dispersed in a transparent resin, but since the particle size of the pigment used there was significantly larger than that of the present invention, Since it is non-light sensitive, it is used only for purposes such as masking, and even if it were used in color filters, it would not be able to provide high sensitivity due to its low transmittance. It is also known that the transparency of the colored image obtained can be improved by controlling the particle size of pigments dispersed in transparent resins. rL is the particle size of the pigment,
It was not known whether the transparency of the resulting colored 1ItIi image could be controlled to a satisfactory degree.

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, the decrease in light transmittance due to light scattering can be suppressed, and the transparency of the resulting colored image can be improved. This is based on the discovery of J# fruit that is thick enough to withstand practical use.

3. Detailed Description of the Invention In the present invention, the pigment is dispersed in a transparent resin.
A photosensitive resin is used as the transparent resin. In particular, water-soluble or alcohol-based photosensitive 494 fats are preferred.
Specifically, the following compounds can be used.

a) Water-soluble photosensitive resin having a photosensitive group Polyvinyl alcohol/stilbazolium, etc.

b) Oil-soluble photosensitive resin having a photosensitive group; photocrosslinking type photosensitive resin such as cinnamic acid type; photolytic crosslinking type photosensitive resin such as bisazide type; photolytic polarity changing type photosensitive resin such as O-quinonediazide type; and the like.

C) The following combinations of (a) binder resin and (b) photocrosslinking agent, (b) Polymer 4I (1) Animal protein-based gelatin, casein, green, etc. (iiJ carboxymethyl hydroxyethyl cellulose, Cellulose threads (III) such as hydroxyethylcellulose, hydroxy7"lopylcellulose, methylcellulose; Vinyl gold-based threads (IVL) such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl methyl ether, polyacrylic acid, polyacrylamide, polydimethylacrylamide; Open condensation systems such as polyethylene glycol and polyethyleneimine, condensation systems such as water-soluble nylon, etc.

(vG 7-tyral resin, styrene-maleic acid co-monomer, chlorinated polyethylene or chlorinated polypropylene, polyvinyl chloride, hinyl chloride-vinyl chloride copolymer,
Oil-soluble resins such as polyvinyl acetate, acrylic resin, polyamide, polyester, phenolic resin, polyurethane resin, etc.゛(0) Photocrosslinking agent dichromate, chromate, diazo compound.

Bisazide compounds, etc.

d) (a) The above binder resin and the following,
(b) Monomer or oligomer and (/1 initiator (monomer or oligomer) acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, 2-human tetraxyglobyl acrylate, 2-
Hydroxyethyl acrylate, vinyl acetate, N-vinylpyrrolidone, acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-(1
, 1-dimethyl-3-oxobutyl)acrylamide,
Polyethylene glycol diacrylate, polyethylene glycodimethacrylate, methylene bisacrylamide, 1,3.5-)lyacryloyl-1,3,5)
Riazacyclohexane, pentaerythritol triacrylate, styrene, vinyl acetate, acrylic esters of 60%, various methacrylic esters, acrylonitrile, etc. Inbutyronitrile, benzoin alkyl ether, thioacridone, benzyl, N-[alkylsulfonyloxy)-1
, 8-naphthalene dicarboximide, 2,4,6-tri(trichloromethyl"triazine, etc.) i) Hydrogen transfer type initiators such as benzophenone, anthraquinone,
9-phenylacridine etc. 1ii) as a child transfer type complex initiator such as benzanthrone/triethanolamine, methylene blue/benzenesulfinate, triallylimidazolyl dimer/
Michler's ketone, carbon tetrachloride/manganese carbonyl, etc. In the present invention, a pigment is dispersed in the above-mentioned transparent resin, and a transparent colored UhJ image is formed on the central support. '' means a colored powder that is soluble in water or an organic bath agent, and includes amorphous pigments and inorganic pigments. Note that some dyes are soluble in water or organic solvents, and this woodcutter dye can be used as the "pigment" in the present invention.

As the organic pigment, azo lake type, insoluble azo type, condensed azo type, phthalocyanine type, quinacridone type, dioxazine type, isoindolinone type, anthraquinone type, perinone type, theoindico type, perylene type or a mixture of these pigments can be used. nUru.

Examples of inorganic pigments include Mirolipur-1 yellow to 11 tons-vermilion, cobalt purple, manganese purple, ultramarine, navy blue, cobalt blue, cerulean blue, and
-→ to Viridian, emerald green, cobalt green and mixtures thereof can also be used.

The pigment dispersed in the transparent resin contains particles with a particle size of lpm or more of 10% or less, preferably 5% of the total pigment particles.
It is desirable to have a particle size distribution such that the amount is more preferably 2% by weight or less.

If particles with a particle diameter of 1 μm or more exceed 104 itt% of the total pigment particles and are dispersed in transparent (1! The pigment used in the invention has a particle size U of 01~
0.7μmn preferably U, 01-0.3μm particles or more than Katokei νb of all pigment particles, preferably λ%
Hereinafter, it is desirable to have a particle size distribution of preferably 50% by weight or more.

A transparent colored image can be obtained by blending a pigment having such a particle size distribution and a transparent resin at a solid content ratio of 40 to 1, preferably h to 1. 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 which has been ground quite finely and the solution of the photosensitive tree layer described above are mixed, The resulting mixture is milled using a pigment dispersion machine such as a three-roll mill, a ball mill, or a sand mill to sufficiently disperse the pigment, and then granulated by centrifugation or filtration using a glass filter, membrane filter, etc. Pigment particles with a diameter of 1 pm or more are removed by T-ray to prepare a pigmented photosensitive resin composition, or the pigment is used as described above for photosensitivity 41! ! Binder 11 that is compatible with fats is mixed with the fat liquid, sufficiently dispersed in the same manner as above, and then centrifuged or filtered through a glass filter, membrane filter, etc. to remove large pigments with a particle size of 1 μm or more. A pigment-containing photosensitive resin composition can be prepared by preparing the removed colorant and mixing this colorant with the above-mentioned photosensitive resin.

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 in which pigments are dispersed or from a yII coloring agent, it is preferable that the viscosity of the composition or coloring agent is adjusted to less than 1500 cps. The pigment-containing photosensitive resin composition prepared in this way is then coated onto the autopsy carrier using a coating device such as a spinner, roll coater, tip coater, foil coater, or bar coater, until the dry film thickness is 0. .1 to 10 µIll, preferably 0.5 to 3 µm, applied to a thickness of 8 degrees, and after drying, patterned using a light source such as a gysenon lamp, metal halogen lamp, or ultra-high pressure mercury lamp through a mask having a pattern with a desired opening. Expose. Next, the non-exposed areas are selectively removed by spray development with a developer such as water or water/organic solvent or by dipping 1A, and the same operation is repeated multiple times.
Transparent colored images of multiple colors can be provided on the 8 supports without forming a resist resin film.

The transparency of the finally obtained colored image is determined by the amount of the transparent resin used as the base, the liI type of the pigment dispersed in the transparent resin, and the amount of the pigment dispersed in the transparent resin, as well as the gray color image layer provided on the faded support. Determined by the film thickness, etc. First, the transparent resin used as the base should have 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. desirable. After the pigment is dispersed in this base transparent resin and then formed on the Harusaki support to a predetermined thickness, the t4M of the pigment used is
Depending on K, the absorption region and the transmission region change, or the light transmittance in the absorption region is preferably 1i, 1 at% or less.
At the same time, it is desirable that the light transmittance in the transmission region be 40° or more, preferably 50° or more, and preferably 60°1 or more.

The above-mentioned case f! In this specification, a colored image can be said to be "transparent" when c/l is also used.

Supports include transparent glass, transparent resin), metal plates, ceramic plates, and solid-state photography with photoelectric conversion elements.
#! element etc. can be used. Solid-state imaging devices include CCD, MOB, BBD, and CID.

A CPD or the like can be used, and a color filter according to the present invention can be provided directly or indirectly on this light receiving surface to form a color filter for a color separation cone.

Effects of the Invention The color filter according to the present invention has transparent colored images of several colors formed on a support by dispersing in a transparent resin a Hi material having a constant particle size distribution. It has the following effects:

(,) When a newly colored image of multiple colors is provided on a support, it is not necessary to form a transparent resist dyeing resin film for each color, and the manufacturing process of color filters is therefore significantly systematized. I can do it with Jin.

(b) A color filter 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.

Kai-轡獅1- Lionol Green 2Y-301 (green pigment made by Toyo Ink Manufacturing @) 1 heavy wind part, average degree of polymerization 1750 degree of saponification 8
8 mo1% polyvinyl alcohol was mixed with 10 parts by weight of a 10% aqueous solution of polyvinyl alcohol, the resulting mixture was milled and dispersed using three rolls, and then centrifuged at 12,000 rpm to give a 1μ
I got P treatment with a glass filter. Next, 1 wt % ammonium dichromate was added as a crosslinking agent to the obtained aqueous colored resin solution to prepare a green QJ photosensitive resin composition, and this was spun on a transparent glass substrate with a film thickness of 1.5 μm. After coating, it was dried at ω°C for 3 minutes and pattern exposed through a mask. Next, the pattern-exposed photosensitive resin composition is mixed with water/
Shun 150 was spray developed with a developer containing isopropyl alcohol (=7.<** ratio) and the non-exposed areas were selectively removed.
A green image was formed by heating at <RTIgt;°C</RTI> for minutes.

This green image is based on Fig. 1 curved paddy (as shown in the field)
Although the transmittance in the wavelength range of 1 to 600 nm was 1% or less, the transmittance in the wavelength range of 500 to 560 nm was 80% or higher. The sensitivity was four times that of conventional gelatin/Cr-based colored images. The edge shape was comparable to that of the gelatin/Cr colored image. The particle size distribution of the pigment in this green transparent #l resin was analyzed using a Coulter N4 submicron particle analyzer, and the average particle size was 0.08 and 0.0.
Particles having a particle size of 1 to 0.3 μm accounted for 97% of the total particles.

Even when the green image thus obtained was heated at 200° C. for an additional period, its spectral transmittance characteristics hardly changed. Note that general organic dyed images are significantly discolored by heating at 200°C.

Furthermore, when this green image was irradiated with a carbon lamp, the green image according to the present invention was 3 to 3 times higher than the organically stained image.
The fading phenomenon has been improved by 4 times.

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

Comparative Example 1 A mixture of Lionol Green 2 Y-301 and polyvinyl alcohol was prepared in the same manner as in Example 1, except that it was not centrifuged and was not passed through V. After forming a green IIi]I image, light transmission The particle size of the pigment dispersed in the photosensitive resin composition must be adjusted to obtain sufficient performance. Yes - "Ruhiriroki II! It turns out that the 11th mound was built by a tty.

In this case, the snake ε Ming painting 1'1! Of the particles dispersed in the instep, those with a particle size of 1μ711 or more account for as much as 1% of the total particles.

Example 3 Chromophthal Red 15RN (Red Coconutaceae manufactured by Chipakaigyi Co., Ltd.) 3 negative rIi parts were added to an average degree of polymerization of 500 and a degree of saponification of 88.
mo 1% polyvinyl alcohol 10% water bath ftl
10 Bigamy: A mixture of marriage and death in the capital! The mixture was ground and mixed in a sand mill, centrifuged at 10,000 rpm, and filtered through a glass filter. Then the resulting aqueous colorant 2: 8 parts m and 88 too 1%
N in saponified polyvinyl alcohol (k synthetic leather 1700)
A red photosensitive resin composition was prepared by thoroughly mixing a photosensitive resin containing 1.4 mo of 1% -methyl-γ-(p-formylstyryl)pyridinium methosulfate in a 10-layer lid. Next, this red photosensitive resin composition was spin-coated onto a transparent glass substrate to a thickness of 1.5μ, and heated at 70°C.
After drying for 30 minutes, a dense layer pattern was exposed through a mask. Next, the photosensitive resin composition that was pattern-exposed was prepared with a water/isoglobil alcohol ratio of 5/1 (compared to nails). After spray developing with I solution and selectively removing non-exposed areas 1
A red image was formed by additional heating at 50°C. This red 1-
The material has excellent transparency, and the edge shape is similar to that of conventional gelatin/C.
It was on the same level as R-type sensitive materials. Sensitivity compared to conventional gelatin/Cr
It was twice as large as other sensitive materials. As a result of measuring the particle size distribution of this red photosensitive resin composition in the same manner as in Example 1, the average particle size was O,
17p and particles having a particle size of 0.01 to 0.3 μn1 accounted for 75% of the total particles.

Example 4 Fastgen Blue-0N))8 (Dainippon Ink Chemical H)
Color M Department) 10, 'i [, M: Miyako wo -12 kuanbu casein 88! A certain amount of a 1% ammonia water bath solution was mixed with a commonly understood resin solution, and the resulting mixture was milled and dispersed in a sand mill, separated through a culture core at 10,000 rpm, and filtered through a 1-size glass filter. Next, ammonium gold romate was added as a crosslinking agent to the obtained 1t layer color side fat bath liquid.
A back-color photosensitive resin composition was prepared by adding 100% of the total amount, and this was spin-coated on a transparent glass substrate to a film thickness of 11 In, and then heated at 90°C.
After drying for 10 minutes, pattern exposure was performed through a mask. The pattern-exposed photosensitive resin Jliz composition was then spray developed with water to selectively remove the unexposed areas to form a blue image. The coloring skill for this one is 560-700 nnl
Although the transmittance of '-1' is less than 1%, 4
The transmittance from 40 to 520 nm was 85% or more.The particle size of the pigment was measured in the same manner as in Example 1 and was found to be 0.0.
Particles with a particle size of 1 to 0.3 μm0 account for (3)% of the total particles.
Met. The sensitivity was three times that of conventional gelatin/Cr-based photosensitive materials. The edge shape was the same as that of the gelatin ICr-based sensitive material.Example 5 Lake Red C (Dainichiseika Chemical's red d family)2. The ff electric part was mixed with a low't% aqueous solution of polyvinyl alcohol with an average degree of polymerization of 500 and a degree of saponification of 88 mo.
Centrifuged at 000 rpm for 15 minutes and filtered through a 11rn Noglass filter. Then, the obtained aqueous color fixing agent 3
1 with Kanbe, average polymerization degree 450 saponification degree sno 1%
A red-sensitive composition was prepared by sufficiently mixing polyvinyl alcohol with a photosensitive resin containing 6 mol % of p-formylstyrylpyridine and a blood clot. Next, this material was spin-coated onto a transparent glass substrate in a film thickness of 1#1, dried at 70.degree. C. for several minutes, and then pattern-exposed through a mask. Next, the pattern-exposed photosensitive resin composition was spray-developed with a developer of water/Inglobil alcohol to selectively remove the non-exposed areas, and then the non-exposed areas were selectively removed.
A red image was formed by heating for □□□ minutes. This red II
! iI image) Although the transmittance of the a-groove wheel of 560 nm or less was 1% or less, the transmittance of 600 nm or more was 90% or more. 2 of conventional gelatin/Cr-based sensitivity
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, particles having a particle size of 0.01 to (1,3jjfn) accounted for 81% of the total particles.

'Example 6 Shimura Astovirazolone Red BT (Dainippon Ink Chemical Co., Ltd.'s red color) 8μ (grave part was mixed with water bathable nylon (coat 1 whiteness ratio 52%) σ) and 9 ethanol solution death,
Obtained l' [, the mixture was mixed with a sandbar and dispersed]
I (centrifuged at 100 rpm for 9 minutes and filtered through a 1 gn glass filter. Then, the obtained colored #j
Add 1% chloromethylstyrene 4υ+no to the K/& solution, and further add 5wt% pentaerythritol triacrylate (as KjI1-combining monomer) and 10W 1% penzoin isoglobyl ether as an initiator.
・Is it possible to add more color to the composition? 1:a) #I rode. This 11 is i'fml crow A; 11Irn on the board
The film was rotated at 60° C. with an attack thickness of +) II and pattern exposed through a mask. Next, the pattern-exposed photosensitive resin composition was spray-developed with a water/inpropyl alcohol developer to selectively remove the non-exposed areas, and then heated at 150°C for minutes to form a red image. was formed.

The sensitivity was twice that of gelatin 10R type sensitive material. Although this red image had a transmittance of 80% or more at wavelengths of 620 nm or higher, even though the transmittance at wavelengths of 580 nm or lower was 1% or lower. When the particle size of the pigment was measured in the same manner as in Example 1, it was found that 00
01~Q, 3tMI) Particles with a particle size of &J of all particles
%Met.

Example 7 Chromophthalpur-A3R (w color pigment manufactured by Ciba Geigy Co., Ltd.) 1 weight 'Mk part was mixed with 20% cellosolve acetate bath solution 'AM foot part of Resitop PSF-2803 (novolak resin manufactured by Gunei Chemical Co., Ltd.), The resulting mixture was milled and dispersed in a sand mill, centrifuged at 10,000 rpm, and
I got a 1!4 with the song's glass filter.

In the obtained colored resin liquid, 30% of naphthoquinone-1,2-diazide-I2-5-sulfonic acid was added to PSF-2803.
A blue photosensitive resin composition was prepared by adding one portion of a 1% MO esterified photosensitive resin. Next, this was spin-coated onto a transparent glass substrate to a film thickness of 1 μm, and the film was heated at a low temperature of 10°C.
After drying for a minute, the pattern-exposed photosensitive resin composition was exposed to light through a mask, sprayed with a 5% aqueous sodium metasilicate solution, and the non-exposed areas were rinsed with water that had been selectively removed. A blue image was formed by heating at 150° C. for an additional period. This positive color IIIJi image was an excellent positive type image with transparent edges. As in Example 1, the particle size of m'** was determined to be 6 (0).
．． 01 to 0.3 particles having a particle size of 1 m accounted for 65% of the total particles.

Example 8 Chromophthal Red BRN (red M class manufactured by Ciba Geigy) 1 car weight part with an average weight degree of 1750 and saponification #88+n
o Mix 10 tons of 10% vt% water bath solution of 1% polyvinyl alcohol with 1 part of VC, mix the obtained mixture with three rolls, and then centrifuge at 2000 rprn and pour into lμll glass. I was treated with a filter. Then, 1 wt % of Echrome Cough Ammonium was added as a crosslinking agent to the resulting aqueous colored flank solution. The resulting red photosensitive resin composition was then spin coated onto a 1 nm thick transparent glass substrate to a film thickness of 1.5 μm, dried at 10° C. for 10 minutes, and exposed to light in a contact pattern through a mask of a predetermined shape. Next, the pattern-exposed photosensitive resin composition was spray-developed with a developer of water/isopropyl alcohol=1 □ (amount ratio of X), and after selectively dissolving and removing the non-exposed areas,
A red color was formed by heating at 0° C. for 1 minute. The particle size distribution of the pigment in this transparent red image is expressed as eulterN
As a result of analysis using a 4 submicron particle analyzer,
The average particle size was 0.3 μm, and particles having a particle size of 0.5 μm or more accounted for 3% or less of the total particles.

Next, Lionol Green 2 Y-301 (manufactured by Toyo Ink Co., Ltd.) was added to 101 parts of the polyvinyl alcohol aqueous solution.
After addition and mixing, the resulting mixture was milled and dispersed using three rolls, centrifuged at 12,000 rpm, and passed through a 1 μm glass filter.

Next, 1 wt% of ammonium tetramate was added to the obtained aqueous green resin solution to adjust the composition of the green photosensitive resin, and this was applied onto the entire surface of the glass substrate on which the red transparent image was provided. Spin coating with a film thickness of 1μI11,
After drying for 0 minutes, after precisely aligning the I positive mask, a contact pattern is exposed, and the non-exposed areas are selectively dissolved and removed using the developer, dried, and the red transparent IItlI image is formed. A transparent green image was formed by taking pictures next to each other. 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.

8, the above polyvinyl alcohol aqueous solution 10
Kuroshichi Blue A3R (blue pigment manufactured by Chibakaiki Co., Ltd.) l Tsume Kanbu was added to and mixed with JIL-mi, and the resulting mixture was dispersed in AM with three rolls, and then rolled at 12,000 rpm.
Centrifuged at 1 μm and filtered through a 1 μm glass filter.
% added. Next, the obtained blue photosensitive 411 resin composition was spread over the entire surface of the glass substrate provided with the above-mentioned red and green transparent images in a film thickness of 1 μn1, and then heated to a temperature of 5” υ°C1.
After 0 minutes III #, rA, the required mask is precisely aligned, exposed in a canned pattern, and the non-exposed area Jt is selectively dissolved and removed using the above developer, dried, and the above green transparent Transparent blue 1 [1ii
ffl was formed. Similarly, when the particle size distribution of the pigment in this transparent W color image was analyzed, the number of particles having a particle size of 0.5 mm or more was 3 mm or less of all particles.

A transparent conductive film was formed on the colored image thus obtained to a thickness of 800 mm by low-temperature sputtering, and then a polyurethane film was applied thereon to a thickness of 1 (XKIλ).
A rubbing process was performed and the electrode was combined with a thin-film tiger woman distal electrode 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.

Using a wafer in which a CCD solid-state imaging device using an interline transfer method was formed on a 4'φ silicon wafer as a substrate, a color separation cup filter was formed in the light-receiving part of the solid-state imaging device using the following steps. .

Chromophthal Red BRN (red pigment manufactured by Ciba Geigy) 1 heavy pigment has an average degree of polymerization of 1750 and a degree of saponification of 88 mo.
10vt% water soluble i10 of 1% tosorivinyl alcohol
The resulting mixture was dispersed in a three-roll roll, centrifuged at 12 UOO rpm, and filtered through a 1 μm glass filter. Next, 500μ? n-thick solid-state imaging device Ueno-
The film was spin-coated to a thickness of 1.5 μm, dried at 90° C. for 10 minutes, and exposed to a dense pattern through a mask of a predetermined shape after precise alignment at a predetermined position. Next, the pattern-exposed photosensitive resin composition was mixed with water/isopropylene alcohol=
10/, (weight ratio) of g and fL, and after selectively dissolving and removing non-exposed areas, 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 N 4 submicron particle analyzer, and the result was that the J average particle size was skin 3.
pn, 0.5 units, and particles having a particle size of 0.5 μm or more accounted for 3% or less of the total particles.

Next, 1 part by weight of Lionol Green 2Y-301 (a green pigment manufactured by Toyo Ink Co., Ltd.) was added and mixed with 10 parts by weight of the above polyvinyl alcohol aqueous solution, and the resulting mixture was mixed and dispersed in a three-pole slurry. After that, it was centrifuged at 12,000 rpm and filtered through a 1 μm glass filter. Then, the resulting aqueous green resin melted image was spin-coated onto the entire surface of the solid-state imaging device wafer with a film thickness of 1 mm.
After drying at ℃ for 10 minutes, after precisely aligning the prescribed mask, a contact pattern is exposed, and the non-exposed areas are selectively dissolved and removed using the above developer, and dried to form the above red transparent image. A transparent green image was formed adjacently. When the particle size distribution of the pigment in this transparent green image was similarly analyzed, the number of particles having a particle size of 0.5 μm or more was 3 or less of all particles.

Similarly, 1 part of Chromo Blue A3R (true color pigment manufactured by Ciba Geigy) was added and mixed to 10 parts by weight of the polyvinyl alcohol aqueous solution, and the resulting mixture was milled and dispersed using three rolls, and then rolled at 12,000 rpm. Centrifuge and l
After filtering through a P glass filter, 1r of ammonium dichromate (1 wt %) was added.

Then, the obtained evening-color photosensitive resin composition gold was used as a solid-state image carrier provided with the above-mentioned red and green transparent images.
After rotating and drying at 90°C for 10 minutes on JIj with a film thickness of 1 μm, the film was exposed to a contact pattern using a predetermined mask 'fc' with precise alignment, and the non-exposed areas were selectively coated with the above WAtdi liquid. It was dissolved and removed, dried, and a transparent green image was formed adjacent to the green transparent image.

Similarly, when we analyzed the particle size distribution of the pigment in the transparent blue image of C, we found that particle beams with a particle size of 0.5 μm or more;
In some cases, a 1-hour bright 4-4 resin was formed on the area of the mineral/solid-state photographic P4 element excluding the pounding pad part, which was less than 3% of the total particles, for the purpose of preservation. It's okay.

The substrate on which the color filter is thus formed on the predetermined light-receiving portion of the solid-state image sensor wafer is subjected to die tagging, die bonding, wire bonding, etc. using the usual methods.
A color solid-state image sensor was fabricated by adding an assembly process such as packaging.

A color solid-state camera was fabricated by adding nine optical element circuit sections and the like 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 mf&element, was formed by a normal wafer process as a substrate, a color filter was directly formed by the following steps.

3 parts by weight of chromophthal red BRN (red pigment manufactured by Ciba Geigy) with an average degree of polymerization of 500 and a degree of saponification of 88 mol.
10% aqueous solution of polyvinyl alcohol of s. ill
The resulting mixture was mixed in a sand mill, centrifuged at 10,000 rpm, and filtered through an ltltm glass filter. Next, 1.4 parts by weight of N-methyA/-1-(p-hol is rustyryl)pyridinium methosulfate was added to 2 parts by weight of the obtained aqueous colorant and 88 molS saponified polyvinyl alcohol (M degree 1700).
A red photosensitive resin composition was prepared by thoroughly mixing 10 parts by 9" parts of the photosensitive resin introduced in mol.
1., 5μm &) Spin coated to a thickness of N4, heated at 70℃30
After drying for several minutes, a close contact pattern was exposed using a mask at the M position ν (of the photosensitive area of the Ueno film).Next, the photosensitive Jugetsu Ecosil R1 material was exposed to pattern light. was spray-developed with a developer containing water/isoglobil alcohol = 1 (electric arc ratio) to selectively remove non-exposed areas, and then heated at 150°C for 30 minutes to form a red image.This red image was transparent. The sensitivity was excellent, and the edge shape t was the same as that of conventional gelatin/Cr-based sensitive materials.The sensitivity was twice that of conventional gelatin/Cr-based materials.Particle size distribution of this red photosensitive resin composition As a result of measurement in the same manner as in Example 1, the average particle size was ii, 17/fn, and 75 of the total particles had a particle diameter of 01 to 0.3 μm.

The line sensor substrate thus produced was subjected to an assembly process such as dicing, die bonding, wire bonding, and packaging using a conventional method to produce a line sensor for color facsimile.

[Brief explanation of the drawing]

The figure shows the spectral characteristics of a colored image, and shows the curve (&
) to (b)a 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. Applicant's agent Kiyoshi Inomata00 Liquid L (nm)

Claims (1)

[Claims] 1. Particles with a particle size of 1 μm or more are present on the support, out of 10 of the total particles.
1. A color filter characterized in that a transparent colored image is formed in a plurality of color patterns and is formed by dispersing a pigment having a particle size distribution as large as 1,000 mm or less in a transparent resin. 2. For pigments, particles with a particle size of 1 μm or more account for 5% by weight of the total particles.
A composition as claimed in claim 1, characterized in that it has a particle size distribution as follows: 3. The pigment has particles with a particle size of 1 μm or more that account for less than 10% by weight of the total particles, and a particle size of 0. The composition according to claim 1, characterized in that the composition has a particle size distribution such that the particles having a diameter of 0.7 μm or more are equal to or more than 5% by weight of the total particles. 4. For pigments, particles with a particle size of 1 μm or more account for 5% by weight of the total particles.
The composition of the patented whetstone described in item 1 below, and having a particle size distribution such that particles with a particle size of 0001 to 0.7 μmn account for 3ONt% or more of the total particles. thing.