JPH1082906A - Production of color filter using silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color filter having little defects, high mass-productivity and high reliability under high humidity conditions without requiring a complicated process by forming a color filter layer to have a specified or lower swelling coeff. to water and covering the filter layer with a water-impermeable protective film having a specified film thickness. SOLUTION: When the color filter formed on a supporting body by using a silver halide photosensitive material containing a photosensitive silver halide, color coupler and hydrophilic binder is coated with a water-impermeable protective film, wrinkles or cracks are produced due to difference in swelling coefft. between the color filter layer and the protective film caused by contact with the external air of high humidity for a long time. In order to prevent these, after the color filter layer is exposed for patterning, color developed and desilverized, the layer is post-hardened so as to control the swelling coeff. of the color filter layer with water at 40 deg.C to <=200%, preferably <=180%. Then, the color filter layer is coated with a protective layer. Thus, no wrinkles are produced even when the filter is exposed to high humidity external air for a long time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a color filter using a color light-sensitive material suitable for easily producing a color filter having excellent molecular transmission characteristics, a small thickness, and excellent flatness. The present invention further relates to a method for producing a color filter having high reliability under high humidity.

[0002]

2. Description of the Related Art A color filter is a color face plate for CRT display, a photoelectric conversion element plate for copying,
It is used in filters for single-tube color television cameras, flat panel displays using liquid crystals, color solid-state imaging devices, and the like. The commonly used color filters are
The three primary colors of red, green and blue are arranged regularly, but some may be composed of four or more hues as required. For example, in a color filter for an image pickup tube or a color filter for a liquid crystal display device, a black pattern (black matrix) is required for various purposes. Specific arrangement methods of red, green, and blue include mosaic, stripe, and delta arrangement, and can be selected as needed.

Conventionally known methods for producing a color filter include a vapor deposition method, a dyeing method, a printing method, a pigment dispersion method, an electrodeposition method, and a resist electrodeposition transfer method. However, the color filters obtained by these methods have drawbacks such as requiring a complicated manufacturing process, easily producing pinballs and scratches, low yield, and poor accuracy.

In order to overcome these disadvantages, an external developing method using a silver halide photosensitive material (for example, Japanese Patent Application Laid-Open No.
No. 6342) and an inner mold development method (for example,
Nos. 8952 and 62-71950). In order to use the color filters created by these methods in liquid crystal displays and other precision electronic devices, a thin film made of indium oxide, tin oxide (ITO), etc. is deposited on the color filters and then used in photolithography. A transparent electrode is formed by patterning using a technique. In this step, it is necessary to cover the color filter layer with a protective film in advance so that the color filter layer does not deteriorate. The properties required for this protective film include chemical resistance, adhesion to a color filter layer, coating properties, transparency, scratch resistance, and the like. Resins (for example, JP-A-58-196506 and JP-A-62-119501), polyglycidyl methacrylate-based resins (JP-A-60-216307), epoxy resins (JP-A-63-131103) and the like. Proposed. However, when such a protective film is applied to a color filter manufactured using a silver halide photosensitive material, the swelling ratio between the color filter layer and the protective film may be affected by prolonged exposure to high humidity outside air. It was found that wrinkles occurred and the transmittance was significantly reduced.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color filter which does not impair the reliability under high humidity conditions.

[0006]

The objects of the present invention are as follows: (1) A color filter is formed on a support by using a silver halide photosensitive material containing at least a photosensitive silver halide, a color coupler and a hydrophilic binder. In the manufacturing method, the swelling ratio of the color filter layer in water at 40 ° C. is 200% or less,
A method for producing a color filter, comprising coating with a water-impermeable protective film having a thickness of 10 to 10 μm. (2) In the method for producing a color filter as described in (1) above, after the silver halide photosensitive material is subjected to pattern exposure, color development treatment and desilvering treatment, one compound containing at least one aldehyde group in the molecule is added. A method for producing a color filter, comprising: immersing in an aqueous solution containing 〜50% at room temperature to 50 ° C. for 10 seconds to 10 minutes, and then covering with a water-impermeable protective film having a film thickness of 0.1 to 10 μm. . (3) The method for producing a color filter according to the above (1), wherein the protective film is a film obtained by curing a prepolymer having two or more epoxy groups in a molecule. Achieved by using

Hereinafter, the present invention will be described in detail. The present invention relates to a case where a color filter produced using a silver halide photosensitive material containing at least a photosensitive silver halide, a color coupler and a hydrophilic binder is coated on a support with a water-impermeable protective film. It is based on the discovery that wrinkles and cracks occur due to a difference in swelling ratio between the color filter layer and the protective film when exposed to high humidity for a long time. At the same time, after pattern exposure, color development processing and desilvering processing, post-hardening processing is performed to suppress the swelling ratio of the color filter layer in water at 40 ° C. to 200% or less, preferably 180% or less, and then use the protective film It was found that wrinkles did not occur even when exposed to high humidity for a long time if the coating was applied.

Here, the swelling ratio of the color filter layer in the present invention means that the film thickness (dry film thickness) of the color filter layer at a temperature of 25 ° C. and a humidity of 50% is do, and the color filter is deionized water (40 ° C.). ) Is obtained from the following equation as dw, the swollen film thickness obtained by dropping Swelling ratio (%) = (dw−do) / do × 100 Specifically, the dry film thickness and the swelling film thickness can be measured using a normal film thickness meter.

Examples of the hardening agent used for the post-hardening treatment include, for example, Research Disclosure (RD), Vol. 176, No. 17643, page 26, and No. 1871.
6, page 651, left column, No. 307105, 874-87.
Usual photographic hardeners described on page 5 and the like are used. Of these hardeners, compounds containing at least one aldehyde group in the molecule are preferred. After setting the concentration of these hardeners to 1 to 50%, preferably 5 to 30%, with a hardening treatment solution, the treatment solution temperature is changed from room temperature to 50 ° C.
It is desirable to soak for 10 seconds to 10 minutes.

The protective film of the present invention is formed by curing a prepolymer having two or more epoxy groups in a molecule. The prepolymer having two or more epoxy groups is an epoxy resin that undergoes polymerization or cross-linking reaction, and is, for example, a conventionally known bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin. , Alicyclic epoxy resin, glycidyl ester epoxy resin,
Glycidylamine-based epoxy resins, heterocyclic epoxy resins and the like can be mentioned, and these can be used alone or in combination. Representative structures of these resins are shown below.

[0011]

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[0012]

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[0013]

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[0014]

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[0015]

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In addition to these epoxy resins,
Compounds having a polymer structure containing at least two epoxy groups capable of reacting in a molecule, such as a polyglycidyl methacrylate resin described in JP-A-216307, are also included in the prepolymer having two or more epoxy groups in a molecule.

As a method of curing the prepolymer having two or more epoxy groups in the molecule, a method of adding a curing agent and curing by heating, and a method of adding a polymerization initiator activated by an active energy ray to add an active energy ray And a method of curing by using both in combination.

As a curing agent for a prepolymer having two or more epoxy groups in a molecule to be added when cured by heating, commercially available amine-based curing agents, polycarboxylic anhydride-based curing agents, polycarboxylic acids, and the like. Can be used.

Examples of the amine-based curing agent include trimethylamine, triethylamine, tributylamine, dimethylbutylamine, dimethylpropylamine, methylethylpropylamine, benzyldimethylamine, benzyldiethylamine, pyridine, triethanolamine and the like.

The polycarboxylic anhydride-based curing agents include itaconic anhydride, maleic anhydride, succinic anhydride,
Aliphatic dicarboxylic anhydrides such as citraconic anhydride, dodecenyl succinic anhydride, etc., aliphatic polycarboxylic acid dianhydrides such as cyclopentanetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride And aromatic polycarboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic anhydride. As the polycarboxylic acid, itaconic acid, maleic acid, succinic acid, citraconic acid, aliphatic polycarboxylic acids such as cyclopentanetetracarboxylic dianhydride, phthalic acid, terephthalic acid,
Aromatic polycarboxylic acids such as isophthalic acid, trimellitic acid, pyromellitic acid and benzophenonetetracarboxylic acid can be mentioned. The amine-based curing agent, polycarboxylic anhydride-based curing agent, and polycarboxylic acid may be used alone or in combination of two or more.

As the polymerizing agent activated by the active energy ray, a compound capable of releasing cations by irradiation with energy rays and curing the epoxy resin by a cationic polymerization reaction can be used, and preferably, an aromatic onium salt-based polymerizing agent is used. Initiator. The aromatic onium salts include aromatic halonium salts described in JP-A-50-151996 and JP-A-50-158680, and JP-A-50-151997.
Nos. 52-30899, 56-55420, 55-125105, and the like; VIA aromatic onium salts described in JP-A-50-158698; No.56-8428, No.56-14
Oxosulfoxonium salts described in JP-A-9402 and 57-192429, aromatic diazonium salts described in JP-B-49-17040 and the like, U.S. Pat. No. 4,139,6
No. 55 and the like.

In order to improve the adhesion of the protective film in the present invention, a coupling agent can be added to the composition. As the coupling agent, a functional silane coupling agent is desirable, and a silane coupling agent having a reactive substituent such as a vinyl group, a methacryloyl group, a hydroxyl group, a carboxyl group, an amino group, an isocyanate group, or an epoxy group, specifically, Vinyl trimethoxy silane, vinyl triethoxy silane, γ-methacryloxypropyl trimethoxy silane, γ-isocyanato propyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane and the like can be mentioned. These functional silane coupling agents may be used alone or in combination of two or more.

The composition for forming a protective film in the present invention is usually dissolved in a solvent and then applied on a color filter layer, and heated or irradiated with an active energy ray.
Or it is cured by both. As the solvent, dissolve the composition for forming a protective film in the present invention,
In addition, there is no particular limitation as long as it does not react with these components and does not adversely affect the color filter prepared using the silver halide photosensitive material, such as dye extraction. Specifically, aromatic solvents such as benzene, toluene and xylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl Ether solvents such as ether, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, Diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate Over DOO, propylene glycol monoethyl ether acetate, ester solvents such as γ- butyrolactone, dimethylformamide, dimethylacetamide, an amide-based solvents such as N- methylpyrrolidone. These solvents can be used alone or in combination of two or more.

The method of preparing the composition solution by dissolving the composition for forming the protective film of the present invention in a solution is not particularly limited, and the composition solution may be prepared by simultaneously dissolving all the components. If necessary, each component may be dissolved in two or more solvents, and when used, they may be mixed to form a composition solution.
Further, stabilizers such as an antioxidant and an ultraviolet absorber may be added to the composition constituting the protective film.

The method for applying the composition solution for forming the protective film in the present invention is not particularly limited, and various methods such as a spray method, a roll coating method, a spin coating method and the like can be used.

The silver halide grains usable in the light-sensitive material of the present invention are silver chloride, silver bromide, silver iodochloride, silver iodobromide, silver chlorobromide, and silver iodochlorobromide. Preferably, the silver chloride content is 50 mol% or more. More preferably, the silver chloride content is 70 mol% or more. The silver iodide content is preferably 2 mol% or less, more preferably 1 mol% or less.
More preferably, it is 0.5 mol% or less. The silver halide emulsion used in the present invention may be a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, the crystal structure may be uniform or a multi-structure particle having a different halogen composition between the inside of the grain and the grain surface. Further, silver halides having different compositions may be bonded by epitaxial bonding, and further, a compound other than silver halide, such as, for example, silver rhodan or lead oxide may be bonded. In particular, in the high silver chloride emulsion used in the present invention, the silver bromide localized phase,
As described above, those having a layered or non-layered structure inside and / or on the surface of silver halide can also be used. The halogen composition of the localized phase preferably has a silver bromide content of at least 20 mol%, and more preferably exceeds 30 mol%. The silver bromide content of the silver bromide localized phase is X
It is analyzed by a line diffraction method or the like. See, for example, C. A. Berry, S. J. Marino (CR Berry, S.M.
J. Marino) Photographic Science
And Technology (Photographic S
science and Technology) Volume 2 1
Pages 49 (1955) and 4, 22 (1957) describe methods of applying X-ray diffraction to silver halide grains. The silver bromide localized phase is formed inside the grain, at the edge of the grain surface,
It can be on a corner or on a plane, but a preferred example is one that is epitaxially bonded to a corner of a particle.

The average grain size of the silver halide grains used in the present invention is preferably from 0.05 to 0.9 μm, and more preferably from 0.1 to 0.9 μm, in order to obtain a high developing activity with a silver content as low as possible. ０．５0.5 μm is preferred. In the case of tabular grains, the thickness is preferably 0.05 to 0.9 μm, and particularly preferably 0.1 to 0.9 μm.
1 to 0.5 μm is preferred. Monodisperse emulsions having a narrow grain size distribution may be used. Monodisperse emulsions, for example,
It is a silver halide emulsion having a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size in terms of the number or weight of grains. Further, a monodispersed silver halide emulsion having a variation coefficient of 20% or less, particularly 15% or less may be used. Polydisperse emulsions having a wide grain size distribution may be used.

The silver halide emulsion usable in the present invention is
The above-mentioned RD Magazine, Vol. 176, No. 17643 (Jan.
February, pp. 22-23, "I. Emulsion Production (Emulsion Pre
paration and types) "and No. 18716 (1
Nov. 979), p. 648, Grafkid, "Physics and Chemistry of Photography", published by Paul Montel (P. Glafkides, Chemi).
c et Phisique Photographique, (Paul Montel, 196
7)), by Duffin, "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemistr)
y, (Focal Press, 1966)), "Production and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZeli).
kman et al, Making and Coating Photographic Emulsi
on, (Focal Press, 1964)) and the like.

US Pat. Nos. 3,574,628;
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gaft, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970): U.S. Patent No. 4,43
4,226, 4,414,310, 4,43
It can be easily prepared by the methods described in 3,048, 4,439,520 and British Patent 2,112,157. Also, a mixture of particles of various crystal forms may be used.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitized layer known in emulsions for conventional photosensitive materials, selenium sensitization, chalcogen sensitization such as tellurium sensitization, gold, platinum, A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-110,55).
No. 5, Japanese Patent Application No. 4-75,794). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, U.S. Pat.
Sensitizing dyes described in JP-A-617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The addition amount is generally from 10 ^-8 to 10 per mol of silver halide.
^-2 moles.

The additives used in such a process are described in the above-mentioned RD Nos. 17,643, 18, 716 and 307, 105. Put together. Type of additive RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 right column 866 page 2 Sensitivity enhancer 648 page right column 3 Spectral sensitizer, 23-24 page 648 right column-866-868 Super color enhancement Sensitizer 649 right column 4 Optical brightener 24 page 648 right column 868 page 5 Antifoggant, 24-25 page 649 right column 868-870 Stabilizer 6 light absorber, 25-26 649 Right column to page 873 Filter dye, page 650 Left column Ultraviolet absorber 7 Dye image stabilizer 25 page 650 page Left column 872 8 Hardener 26 page 651 left column 874-875 page 9 Binder 26 page 651 left column 873-874 page 10 Plasticizer, lubricant page 27 page 650 right column 876 page 11 Coating aid, surface 26-27 page 650 right column 875-876 Activator 12 stat P. 27 p. 650 p. Right column 876-877 p.

The color developer which can be used in the present invention may be any one as long as an oxidized form of the developer formed by developing silver halide forms a dye by coupling reaction with a coupler. It is known. An example of a color developer is THJames `` The Theory of the Photog
raphic Process ", 4th edition, pages 291 to 334 and 353
To 361 pages. Particularly preferred color developers are p-phenylenediamine derivatives.

In the present invention, various known color couplers can be used together with the coupler of the present invention. Specific examples thereof are described in Research Disclosure (RD) Nos. 17643 and VII-C to G described above. It is described in the mentioned patent. As the coupler used in the present invention, a two-equivalent color coupler in which the active site is substituted with a leaving group is more preferable than a four-equivalent color coupler having a hydrogen atom in that the amount of coated silver can be reduced.

As a typical example of the yellow coupler that can be used in the present invention, an oil-protected acylacetamide coupler can be mentioned. Specific examples thereof are described in U.S. Pat. Nos. 2,407,210, 2,875,057 and 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,44.
No. 7,928, No. 3,935,501 and No. 4,022,620, etc., and an oxygen atom-elimination type yellow coupler or JP-B-58-10739.
Nos. 4,401,752 and 4,32
No. 6,024, RD18053 (April 1979), British Patent No. 1,425,020, West German Application Publication No. 2,2
No. 19,917, No. 2,261,361, No. 2
329,587 and 2,433,812, the nitrogen atom-elimination type yellow couplers are typical examples. α-pivaloylacetanilide couplers are excellent in the fastness of coloring dyes, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

The magenta coupler usable in the present invention includes oil-protected couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof are described in US Pat.
No. 1,082, No. 2,343,703, No. 2,6
No. 00,788, No. 2,908,573, No. 3,
Nos. 062,653, 3,152,896 and 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone coupler, a nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or an arylthio group described in U.S. Pat. No. 4,351,897 is particularly preferred. European Patent 73,63
The 5-pyrazolone coupler having a ballast group described in No. 6 can provide a high color density.

As the pyrazoloazole couplers, pyrazolobenzimidazoles described in US Pat. No. 3,369,879, preferably US Pat. No. 3,725,06
No. 7, pyrazolo [5, 1-c] [1, 2,
4] Triazoles, Research Disclosure 2
4220 (June 1984) pyrazolotetrazoles and Research Disclosure 24230
(June 1984). The imidazo [1,2-b] pyrazoles described in EP 119,741 are preferred from the viewpoint of low yellow side absorption and light fastness of the coloring dye, and the pyrazolo described in EP 119,860. [1,5-b]
[1,2,4] triazole is particularly preferred.

Cyan couplers usable in the present invention include those described in US Pat. Nos. 2,474,293 and 4,052.
No. 2,212, No. 4,146,396, No. 4,2
Naphthol-based couplers described in U.S. Pat. No. 3,771 and No. 4,233,200;
No. 2,002,162, and phenolic cyan couplers having an alkyl group at the meta position of the phenol nucleus having an ethyl group or more, described in U.S. Pat.
No. 58,308, No. 4,126,396, No. 4,
Nos. 334,011, 4,327,173, West German Patent Publication No. 3,329,729 and Japanese Patent Publication No. 3-181.
No. 75, etc. and 2,5-diacylamino-substituted phenolic couplers and U.S. Pat. No. 3,446,62.
No. 2, No. 4,333,999, No. 4,451,5
And phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position as described in JP-A-59-59 and JP-A-4,427,767.
Especially as a coupler excellent in heat resistance and light resistance, Japanese Patent Application Hei 6
-84315 are preferred and can be used in the present invention. In the present invention, the following various couplers can be used in addition to the above-mentioned couplers. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
Nos. 80,211 and 4,367,282 and British Patent No. 2,102,173. Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers which release a development inhibitor are described in the aforementioned RD17643, the patents described in VII to F, JP-A-57-151944, and JP-A-57-151944.
Preferred are those described in US Pat. Nos. 7,154,234 and 60-184248, and U.S. Pat. No. 4,248,962. Examples of couplers which release a nucleating agent or a development accelerator in an image-like manner during development include British Patent 2,097,140.
No. 2,131,188, JP-A-59-1576.
Nos. 38 and 59-170840 are preferred.

Other couplers that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,42.
No. 7,283, etc .; U.S. Pat.
No. 472, No. 4,338,393, No. 4,310,
No. 618, etc .;
5950 and the like, and couplers that release a dye that recolors after release described in EP 173,302A, and the like. Further, the coupler for black color correction is not limited to couplers that emit yellow, magenta, and cyan, but may be couplers that emit, for example, brown, orange, purple, and black.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 2,027. The amount of the high boiling point solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g per 1 g of the coupler. In addition, 2 g or less, preferably 1 g or less for 1 g of the binder,
More preferably, it is 0.5 g or less. The size of the coupler dispersion (coupler emulsion) obtained by the oil-in-water dispersion method is 0.05 μm to 0.9 μm, preferably 0.1 μm to
0.5 μm.

The steps, effects, and specific examples of the latex for impregnation in the latex dispersion method are described in US Pat. No. 4,199,
No. 363, West German Patent Application (OLS) No. 2,541,27
No. 4, No. 2,541,230 and the like. In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in EP 0,277,589 A2 in a layer containing a coupler. In particular, combination use with a pyrazoloazole-based magenta coupler is preferable.

That is, the compound (F) which reacts with the aromatic amine-based developing agent remaining after the color development to form a chemically inert and substantially colorless compound, and / or the compound (F) remaining after the color development. The compound (G), which reacts with the oxidized form of the aromatic amine-based developing agent to form a chemically inert and substantially colorless compound, can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stain and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

The silver halide emulsion layer and the intermediate layer of the light-sensitive material according to the present invention contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color fogging inhibitor or a color mixing inhibitor. You may. Among these compounds, those which hardly generate stain even when heated to 160 to 200 ° C. are preferable.

In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto. Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794) and 4-thiazolidone compounds (for example, U.S. Pat. No. 3,314,794) No. 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamate compounds (for example, U.S. Pat. No. 3,705,805 and U.S. Pat. No. 3,707,395), butadiene compounds (for example, US Pat.
045,229) or a benzoxazole compound (for example, US Pat. No. 3,406,070).
No. 4,271,307). An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted to a specific layer. Above all, a benzotriazole compound substituted with the above aryl group is preferable.

The light-sensitive material according to the present invention is provided with a fungicide, such as that described in JP-A-63-271247, in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add a fungicide.

As the binder or protective colloid which can be used in the silver halide emulsion layer, intermediate layer and protective layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic polymers are also used. be able to. As the hydrophilic polymer, for example, polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl butyral, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinyl imidazole,
Polyvinyl pyrazole, carrageenan, gum arabic,
Further, a homo- or copolymer such as hydroxyalkyl cellulose, carboxymethyl cellulose, cellulose sulfate, cellulose acetate hydrogen phthalate and cellulose derivatives such as sodium alginate may be mentioned. Also, a graft polymer of gelatin and another polymer may be used. Examples of the gelatin-graft polymer include gelatin, acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, and vinyl monomer such as acrylonitrile and styrene. Those grafted with one or a copolymer can be used. In particular, polymers that are somewhat compatible with gelatin, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide,
A graft polymer with a polymer such as hydroxyalkyl methacrylate is preferred. These examples are described in U.S. Pat.
No. 763,625, No. 2,831,767, No. 2,9
No. 56,884 and JP-A-56-65133. Representative synthetic hydrophilic polymer substances are described in, for example, West German Patent Application (OLS) 2,312,708, U.S. Pat. Nos. 3,620,751, 3,879,205, and JP-B-43-7561. Those described may also be used. The above hydrophilic polymers may be used alone or in combination of two or more.

As gelatin, alkali treatment, acid treatment,
Those subjected to any of the enzyme treatments, or a mixture thereof may be used. It is also obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane salutonic acids, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. Gelatin derivatives are also used. Specific examples of gelatin derivatives are described in U.S. Pat. Nos. 2,614,928, 3,132,945, 3,186,846, 3,312,553, British Patents 861,414 and 1,033. , 189, 1,005,784, and JP-B-42-26845.

The total amount of the binder in the light-sensitive material used in the present invention is preferably from 3 to 10 g / m ² , and more preferably from 3.5 to 7 g / m ^{2, because it} is necessary to make the thickness of the color corrector as small as possible.
g / m ² are preferred. The amount of the binder in each silver halide emulsion layer is preferably 0.3 to 3 g / m ² , particularly preferably 0.35 to 3 g / m ^2.
2.0 g / m ² is preferred. The amount of the binder in each of the intermediate layer and the protective layer is preferably from 0.1 to 1.5 g / m ² , more preferably from 0.2 to 1.5 g / m ^2.
~1.0g / m ² is preferred. When a release layer or a back layer is provided on the light-sensitive material, the binder of these layers is not directly involved in the components of the color filter, and is not included in the above “total binder amount”.

The support used in the present invention is desirably a light-transmitting substrate. As described in JP-A-7-244212, a silver halide emulsion layer coated on another support is coated with a light-transmitting substrate. The photosensitive material for a color filter may be formed by being transferred and adhered onto a substrate. In this case, the support is not necessarily required to be light-transmissive, and for example, the back surface of the support may be coated with carbon black or the like.

Examples of the material constituting the light-transmitting substrate are preferably optically isotropic and excellent in heat resistance, and include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalene polystyrene, polycarbonate, and polystyrene. Examples include ether sulfone, cellulose acetate, polyarylate, soda glass, borosilicate glass, and quartz. The surface of the substrate made of these materials may be subjected to an undercoating treatment as needed. Further, treatments such as glow discharge, corona discharge, and ultraviolet (UV) irradiation may be performed. The light transmissive substrate can be used in the form of a plate, a sheet, a film, or the like.
The thickness of the substrate can be appropriately set according to the application and the material, but is generally 0.01 to 10 mm. For example, in the case of a glass substrate, the thickness is in the range of 0.3 to 3 mm.

The silver halide light-sensitive material according to the present invention comprises:
In addition to a conventional negative or positive color photographic light-sensitive material containing a yellow coupler in a blue-sensitive emulsion layer, a magenta coupler in a green-sensitive emulsion layer, and a cyan coupler in a red-sensitive emulsion layer, JP-A-55-55 No. 6342, 62-14
Nos. 8952 and 62-71950, JP-A-8-136
No. 722, No. 7-244212 and the like.

The light-sensitive material used in the present invention is the same as the RD.
No. 17643, pp. 28-29, and No. 1871
No. 6, 651, left column to right column, etc., are subjected to color development processing to obtain a micro color filter.

For example, a color developing process, a desilvering process, and a washing process are performed. In the desilvering step, instead of the bleaching step using a bleaching solution and the fixing step using a fixing solution, a bleach-fixing step using a bleach-fixing solution can be performed. The bleach-fix processing steps may be combined in any order. A stabilizing step may be performed instead of the water washing step, or a stabilizing step may be performed after the water washing step. Further, a monobath processing step using a one-bath development bleach-fix processing solution in which color development, bleaching and fixing are performed in one bath can also be performed. In combination with these processing steps, a pre-hardening processing step, a neutralization step thereof, a stop fixing processing step, a post-hardening processing step, an adjustment step, an intensification step, and the like may be performed. In these processes, a so-called activator process may be performed instead of the color development process. Also, Japanese Patent Application 5-302
As described in JP-A-804, etc., a color developing process and a desilvering process may be performed by using an internal latent image type autopositive emulsion in combination with a nucleating agent and a light fogging.

In the case of a flexible support (substrate), a development processor used for ordinary photographic processing can be used as the development processing device. In the case of a hard support such as glass, a developing machine for a glass dry plate or
A developing device as described in JP-A-7-56015 can be used.

As an exposure method applied to the present invention, there are a surface exposure method through a mask and a scanning exposure method. Scanning method is line (slit)
A point scanning method such as scanning or laser exposure can be applied. As the light source, a tungsten lamp, a halogen lamp, a fluorescent lamp, a mercury lamp (such as a three-wavelength fluorescent lamp), a laser beam, a light emitting diode, or the like is used. Particularly, a halogen lamp, a fluorescent lamp, and a laser beam are preferable. As another exposure method applicable to the present invention, as described in Japanese Patent Application No. 7-24563, a liquid crystal display panel in which a color filter prepared according to the present invention is to be incorporated is used, and exposure is sequentially performed three times in combination with a color filter. There is a way.

The color filter produced by the method of the present invention can be further provided with a transparent electrode (ITO) by vapor deposition coating, for example, vacuum vapor deposition or sputtering. Further, an alignment film such as a polyimide resin can be provided thereon. Further, a polarizing plate or a retardation film may be provided on the surface of the color filter opposite to the emulsion surface of the light transmitting substrate.

Instead of a glass substrate as the light transmitting substrate,
A plastic film substrate provided with a gas barrier layer and a hard coat layer can be used. Color LC
For details on D and its manufacturing method, see Shoichi Matsumoto and Ryo Kakuda, “Basics and Applications of Liquid Crystals” (published by the Industrial Research Council in 1991), edited by Nikkei Microdevices, “Flat Panel Display 1994” (1993 Nikkei BP) Published by the company) and JP-A-1-114820.

[0058]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples. Example 1 A method for preparing a photosensitive silver halide emulsion (I) will be described. A gelatin solution having the composition shown in Table 1 which is well stirred is added with the solution (I) shown in Table 2 for 1 minute. (I)
Twenty seconds after the start of the liquid addition, the solution (II) was added in 40 seconds, and two minutes later, the solutions (III) and (IV) were simultaneously added over 4 minutes.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

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After washing with water and desalting (performed at pH 4.0 using the sedimentation agent (a)), decalcified gelatin 22
g was added and dispersed. After the pH was adjusted to 6.0, 4 cc of a 10% aqueous solution of sodium chloride was added, and 70 mg of a preservative was further added to obtain a silver chloride emulsion having a particle size of 0.15 μm. The yield of this emulsion was 630 g.

[0063]

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[0064]

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The method for preparing the silver halide emulsion (II) will be described. The silver chloride content was 70 mol% in the same manner as in the silver halide emulsion (I) except that the compositions of the aqueous gelatin solution and the solutions (I) and (II) were changed as shown in Tables 3 and 4.
Was prepared. Particle size is 0.18 μm
Met.

[0066]

[Table 3]

[0067]

[Table 4]

One side of an optically isotropic 80 μm polyarylate substrate was subjected to a corona discharge treatment, and an SBR latex layer and a gelatin layer were coated to improve adhesion to a photographic emulsion layer. On this, the following first to ninth layers were simultaneously coated in multiple layers to produce a color photosensitive material 1A. The components and coating amounts (g / m ² units) are shown below. For silver halide and colloidal silver, the coating amount is shown in terms of silver.

First layer (antihalation layer) Gelatin: 0.70 Colloidal silver emulsion (average particle size: 0.02 μm): 0.20 Hardener (H-1): 0.06

Second layer (intermediate layer) Gelatin: 0.50

Second Layer (Infrared Sensitive Layer) Silver halide emulsion (I) spectrally sensitized with infrared sensitizing dye (ExS-6) ... 0.28 Antifoggant (Cpd-12) ... 0.005 Gelatin: 0.57 Cyan coupler (ExC-2): 0.10 Magenta coupler (ExM-1): 0.14 Yellow coupler (ExY-1): 0.35 Fading Inhibitor (Cpd-3) 0.05 Anti-fading agent (Cpd-4) 0.005 Anti-fading agent (Cpd-5) 0.02 Ultraviolet absorber (Cpd-6) 0.005 UV absorber (Cpd-7) ... 0.01 Stain inhibitor (Cpd-13) ... 0.01 High boiling solvent (Solv-1) ... 0.32 High boiling solvent (Solv-2) ... 0.07 High boiling point solvent (Solv- ) ... 0.13 polymer (Cpd-14) ··· 0.01

Third layer (intermediate layer) Gelatin: 0.38 Color-mixing inhibitor (Cpd-2): 0.02 Color-mixing inhibitor (Cpd-10): 0.09 High boiling point solvent (Solv) -1) ... 0.03 High boiling point solvent (Solv-3) ... 0.01 UV absorber (Cpd-8) ... 0.02 UV absorber (Cpd-7) ... 0.0. 02 UV absorber (Cpd-6) ... 0.01 UV absorber (Cpd-9) ... 0.02 Stain inhibitor (Cpd-11) ... 0.04 Anti-irradiation dye (Dye- 1) ... 0.03 Anti-irradiation dye (Dye-2) ... 0.02

Fourth Layer (Red Sensitive Layer) Silver halide emulsion (I) spectrally sensitized with a red sensitizing dye (ExS-4, 5): 0.28 gelatin: 0.65 yellow coupler ( ExY-1) ... 0.53 Magenta coupler (ExM-1) ... 0.29 Anti-fading agent (Cpd-3) ... 0.06 Anti-fading agent (Cpd-4) ... 0.0. 005 Anti-fading agent (Cpd-5) ... 0.01 Stain inhibitor (Cpd-13) ... 0.01 Polymer (Cpd-14) ... 0.02 High boiling solvent (Solv-1) 0.32 High boiling point solvent (Solv-2) ... 0.08 High boiling point solvent (Solv-4) ... 0.20

Fifth layer (intermediate layer) Gelatin: 0.38 Color-mixing inhibitor (Cpd-2): 0.02 Color-mixing inhibitor (Cpd-10): 0.09 High boiling point solvent (Solv) -1) ... 0.03 High boiling point solvent (Solv-3) ... 0.01 UV absorber (Cpd-8) ... 0.02 UV absorber (Cpd-7) ... 0.0. 02 UV absorber (Cpd-6) ... 0.01 UV absorber (Cpd-9) ... 0.02 Stain inhibitor (Cpd-11) ... 0.04 Anti-irradiation dye (Dye- 1) ... 0.03 Anti-irradiation dye (Dye-2) ... 0.02

Sixth Layer (Green Sensitive Layer) Silver halide emulsion (I) spectrally sensitized with green sensitizing dye (ExS-3): 0.35 gelatin: 0.61 cyan coupler (ExC- 1) 0.33 Yellow coupler (ExY-1) 0.42 Anti-fading agent (Cpd-5) 0.01 Ultraviolet absorber (Cpd-6) 0.03 Ultraviolet light Absorbent (Cpd-7) ... 0.06 Stain inhibitor (Cpd-13) ... 0.02 High boiling solvent (Solv-1) ... 0.16 High boiling solvent (Solv-2) ..0.21 Polymer (Cpd-14) ... 0.02

Seventh layer (intermediate layer) Gelatin: 0.38 Color-mixing inhibitor (Cpd-2): 0.02 Color-mixing inhibitor (Cpd-10): 0.09 High-boiling solvent (Solv) -1) ... 0.03 High boiling point solvent (Solv-3) ... 0.01 UV absorber (Cpd-8) ... 0.02 UV absorber (Cpd-7) ... 0.0. 02 UV absorber (Cpd-6) ... 0.01 UV absorber (Cpd-9) ... 0.02 Stain inhibitor (Cpd-11) ... 0.04 Yellow dye (YF-1) ... 0.17

Eighth layer (blue-sensitive layer) Silver halide emulsion (II) spectrally sensitized with blue sensitizing dye (ExS-1, 2) ... 0.27 Antifoggant (Cpd-2) -0.01 gelatin ... 0.48 Cyan coupler (ExC-2) ... 0.51 Magenta coupler (ExM-1) ... 0.04 Anti-fading agent (Cpd-3) ... 0.0. 01 Anti-fading agent (Cpd-4) ... 0.001 Anti-fading agent (Cpd-5) ... 0.002 Ultraviolet absorber (Cpd-6) ... 0.03 Ultraviolet absorber (Cpd-7) ) ... 0.08 High boiling point solvent (Solv-1) ... 0.25 High boiling point solvent (Solv-2) ... 0.02

Ninth layer (protective layer) Gelatin (acid treatment) 0.31 Antistatic agent (Cpd-1) 0.03

In each layer, sodium dodecylbenzenesulfonate as an emulsification / dispersion aid, ethyl acetate as an auxiliary solvent, a surfactant (Cpd-17) as a coating aid, and potassium polysulfonate as a thickener were used.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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The color photosensitive material prepared as described above was exposed four times sequentially using tungsten light by superposing the mask filter shown in FIG. 1 and the color filter matching the spectral sensitivity of the photosensitive material. The exposed photographic material was developed according to the following steps to develop three colors of B, G, R and black, and then hardened to form a color filter 1A. (Processing process) (Temperature) (Time) Color development 38 ° C 80 seconds Bleaching and fixing 38 ° C 90 seconds Rinse-135 ° C 80 seconds Post-curing treatment 38 ° C 5 minutes Rinse-35 35 ° C 40 seconds Rinse-35 35 ° C 40 Second drying 60 ° C 2 minutes

The composition of each processing solution is as follows. (Color developing solution) Water 800 ml Ethylenediaminetetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triethanolamine 12.0 g Potassium chloride 6.5 g Bromide Potassium 0.03 g Potassium carbonate 27.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonateethyl) hydroxylamine 5.0 g Sodium triisopyrnaphthalene (β) sulfonate 0.1 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g Water was added to add 1 liter pH (25 ° C.) = 10.0

(Bleach-fixing solution) Water 600 ml Ammonium thiosulfate (750 g / liter) 93 ml Ammonium sulfite 40.0 g Ethylenediaminetetraacetic acid / ferric ammonium 55.0 g Ethylenediaminetetraacetic acid 5.0 g Nitric acid (67%) Add 30.0 g water and add 1 liter pH (25 ° C) = 5.8

(Washing water) Deionized water having a conductivity of 5 μS or less

(Post-hardening liquid) Glutaraldehyde was added to 10
% Aqueous solution

The color filter 1A obtained by the above-described process has RGB and high density black stripes without color turbidity and excellent spectral transmission characteristics.
Was 150% in water.

A solution (cured composition) having the following composition was applied on the color filter 1A produced as described above, and cured to form a protective film 1C, thereby producing a sample 1S.

The curing composition was applied and cured so that the thickness of the protective film after drying the auxiliary solvent was 2 μm, and the coating was conducted in a thermostat at 120 ° C. for 30 minutes and further at a thermostat of 150 ° C. Heat treatment was performed in a bath for 30 minutes to cure.

(Curing composition) Cresol novolak type epoxy resin (Nippon Kayaku Co., Ltd. EOCN-104S) 25 g trimellitic anhydride 5 g cellosolve acetate 70 g

For the sample 1S prepared as described above, a gobang test (JIS-K-540) using tape peeling was conducted to examine the adhesion between the protective film and the color filter.
0) was performed. As a result, no peeling of the protective film was observed.

Next, in order to examine the wet heat stability of the sample 1A, the sample 1A was placed in a thermo-hygrostat at a temperature of 60 ° C. and a humidity of 95% for 72 hours, and the surface of the sample was then subjected to an optical microscope at a temperature of 25 ° C. and a humidity of 50%. When observed, no wrinkles, cracks, etc. were seen.

Example 2 As shown in Table 5, after the same exposure as in Example 1 was performed using the color photosensitive material 1A used in Example 1,
After the treatment up to Rinse-1, the colors B, G, R and black were developed, and then post-hardening treatment was performed in place of the post-hardening treatment liquids 1B to 7B in Table 5 to give color filters 2A to 7A. Was prepared. After measuring these swelling ratios, samples 2S to 9S were prepared by applying the protective films 1C to 3C on the color filters in the same manner as in Example 1. The results of the Gobang eye test and the moist heat stability test of Samples 2S to 9S were compared with the color filter 2A.
The results are shown in Table 7 together with the swelling ratio of ~ 6A. As a comparative example, a protective film 1C was applied to the color filter prepared without performing post-hardening treatment,
And a similar test was performed.

[0098]

[Table 5]

[0099]

[Table 6]

[0100]

[Table 7]

Samples 1S to 9S that had been subjected to post-hardening treatment showed almost no wrinkles on the sample surface even after being placed in an environment at a temperature of 60 ° C. and a humidity of 95% for 72 hours. It was found that the stability under high humidity could be improved by applying the protective film after the swelling ratio of the color filter layer of the sample was 200% or less.

Example 3 An emulsion layer above the second layer of the color light-sensitive material described in Example 1 of JP-A-8-136722 was prepared by the method described in the patent example. The swelling ratio of the color filter 11A in water at 40 ° C. was 210%. A protective film 1C was applied on the color filter 11A to produce a sample 11S.

The color filter 11A was subjected to the treatment after the post-hardening treatment in Example 1 of the present invention, and the swelling ratio in water at 40 ° C. was measured to be 150%. Thereafter, a protective film 1C was applied to prepare a sample 12S.

The samples 11S, 1
As for 2S, a Gobang test was performed by tape peeling to examine the adhesion between the protective film and the color filter. As a result, no peeling of the protective film was observed in both samples 11S and 12S. Next, the samples 11S and 12S were subjected to a wet heat stability test. As a result, wrinkles were observed on the surface of the protective film in sample 11S, but no wrinkles and cracks were observed in sample 12S. From this result, as in the case of Example 1, the swelling ratio in water at 40 ° C. of the color filter layer subjected to the post-hardening treatment was reduced to 200% or less, and then the protective film was applied. It was found that the stability under the conditions could be improved.

[0105]

According to the present invention, it is possible to provide a color filter which does not require complicated steps, has few defects, is suitable for mass production, and has high reliability under high humidity conditions.

[Brief description of the drawings]

FIG. 1 is a schematic view showing one embodiment of a mask filter used when exposing a photosensitive material of the present invention.

Claims (3)

[Claims] 1. A method for producing a color filter using a silver halide photosensitive material containing at least a photosensitive silver halide, a color coupler and a hydrophilic binder on a support, comprising the steps of: A method for producing a color filter, which has a swelling ratio to water of 200% or less, and further covers this with a water-impermeable protective film having a thickness of 0.1 to 10 μm. 2. The method for producing a color filter according to claim 1, wherein the silver halide photosensitive material is subjected to pattern exposure, color development processing and desilvering processing, and then a compound containing at least one aldehyde group in the molecule. Preparation of a color filter characterized by being immersed in an aqueous solution containing 1 to 50% at room temperature to 50 ° C. for 10 seconds to 10 minutes, and then covered with a water-impermeable protective film having a thickness of 0.1 to 10 μm. Method. 3. The method for producing a color filter according to claim 1, wherein the protective film is a film obtained by curing a prepolymer having two or more epoxy groups in a molecule. .