EP0662635B1 - Verfahren zur Herstellung von Farbfiltern - Google Patents

Verfahren zur Herstellung von Farbfiltern Download PDF

Info

Publication number
EP0662635B1
EP0662635B1 EP19950100144 EP95100144A EP0662635B1 EP 0662635 B1 EP0662635 B1 EP 0662635B1 EP 19950100144 EP19950100144 EP 19950100144 EP 95100144 A EP95100144 A EP 95100144A EP 0662635 B1 EP0662635 B1 EP 0662635B1
Authority
EP
European Patent Office
Prior art keywords
light
layer
gelatin
color
color filter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19950100144
Other languages
English (en)
French (fr)
Other versions
EP0662635A2 (de
EP0662635A3 (de
Inventor
Hiroyuki Hirai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0662635A2 publication Critical patent/EP0662635A2/de
Publication of EP0662635A3 publication Critical patent/EP0662635A3/de
Application granted granted Critical
Publication of EP0662635B1 publication Critical patent/EP0662635B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/04—Additive processes using colour screens; Materials therefor; Preparing or processing such materials
    • G03C7/06—Manufacture of colour screens
    • G03C7/10—Manufacture of colour screens with regular areas of colour, e.g. bands, lines, dots
    • G03C7/12—Manufacture of colour screens with regular areas of colour, e.g. bands, lines, dots by photo-exposure
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/805—Photosensitive materials characterised by the base or auxiliary layers characterised by stripping layers or stripping means
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/485—Direct positive emulsions
    • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure

Definitions

  • This invention relates to a process for producing a color filter and more particularly to a process for easily preparing a color filter having excellent spectral transmission characteristics.
  • a color filter is used in a color face plate for, for example, CRT display, a photoelectric element plate for copying, a filter for single tube type TV cameras, a flat panel display using liquid crystals, and a color solid-state image sensor.
  • color filters comprise regularly arranged three primary colors, i.e., blue, green and red. Color filters comprising four or more hues are also available for some uses. For example, color filers for camera tubes or for liquid crystal displays are required to have a black pattern for various purposes.
  • color filters obtained by these processes have their several disadvantages, such as involvement of a complicated step, liability to pinholes or scratches, poor yield, and insufficient precision.
  • JP-A-1-255858 discloses a color diffusion transfer photographic film unit comprising a photosensitive layer covered with a release layer containing hydroxyalkyl cellulose. Moreover, a layer containing cellulose ester between the release layer and the photosensitive layer is provided.
  • JP-A-2-156203 discloses the use of coupler-in emulsion type or coupler-in developer type color development by executing color development in the presence of a specific cyan coupler.
  • the emulsion layers of the photosensitive material provided with at least one layer of silver halide emulsion layers on light transparent bases are subjected to pattern exposing and then to color development and are thereby formed with the dye images corresponding to the pattems.
  • JP-A-63-141053 discloses a color photographic material comprising a releasing sheet on the back side, i.e. the photographic material comprises, in the following order, a light-sensitive layer, a support and a releasing sheet.
  • US-A-5,254,447 is directed to photographic glass plates comprising a silver halide emulsion layer, said plates being prepared by a process in which the silver halide emulsion layer and other required functional layers are applied to the glass plate support by lamination.
  • a process for producing a color filter comprising the steps of adhering an emulsion side of a light-sensitive material to a light-transmitting substrate by heating, wherein the light-sensitive material comprises a support having provided thereon a peeling layer and further provided thereon at least three silver halide emulsion layers which are different in color sensitivity, and the light-transmitting substrate is a glass substrate on which (a) gelatin or a derivative thereof and (b) colloidal silica are previously coated on the adhered side thereof, peeling the support off the light-sensitive material, pattern-exposing the emulsion side, subjecting the material to hardening processing prior to development processing, and subjecting the material to development processing and desilvering processing.
  • FIG. 1 illustrates an example of a color liquid crystal filter using a color filter produced in accordance with the present invention.
  • Binders or protective colloids which can be used in silver halide emulsion layers, intermediate layers or protective layers of the light-sensitive material used in the present invention include gelatin and other hydrophilic polymers, with gelatin being advantageous.
  • the hydrophilic polymers other than gelatin include homo- or copolymers, such as polyvinyl alcohol, polyvinyl alcohol partial acetal, polyvinyl butyral, poly-N-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, carrageenan, gum arabic, and cellulose derivatives, such as hydroxyalkyl cellulose, carboxymethyl cellulose, cellulose sulfate, cellulose acetate hydrogen phthalate, and sodium alginate.
  • Graft polymers of gelatin and other high polymers are also effective.
  • gelatin to which a homo- or copolymer of a vinyl monomer, such as acrylic acid, (meth)acrylic acid or a derivative thereof (e.g., an ester or an amide), acrylonitrile or styrene, is grafted can be used.
  • graft polymers of gelatin and a polymer which is compatible with gelatin to some extent, such as (meth)acrylic acid, (meth)acrylamide or a hydroxyalkyl methacrylate, are preferred. Examples of these graft copolymers are described in U.S. Patents 2,763,625, 2,831,767, and 2,956,884, and JP-A-56-65133.
  • Typical synthetic hydrophilic high polymers which can be used in the present invention are described in, e.g., West German Patent Publication (OLS) 2,312,708, U.S. Patents 3,620,751 and 3,879,205, and JP-B-43-7561 (the term "JP-B” as used herein means an "examined Japanese patent publication").
  • hydrophilic polymers may be used either individually or in combination of two or more thereof.
  • Gelatin species which can be used in the present invention include alkali-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, and a mixture thereof.
  • Gelatin derivatives obtained by reacting gelatin with various compounds, such as an acid halide, an acid anhydride, an isocyanate compound, bromoacetic acid, an alkanesultonic acid, a vinylsulfonamide compound, a maleinimide compound, a polyalkylene oxide, and an epoxy compound are also useful. Specific examples of the gelatin derivatives are given in U.S.
  • all layers constituting the light-sensitive material of the present invention other than a peeling layer each contains a binder mainly comprising gelatin or a derivative thereof while the peeling layer mainly comprises a polymer other than gelatin or a gelatin derivative.
  • binder mainly comprising gelatin or a derivative thereof means that gelatin or a gelatin derivative forms a proportion of at least 80% of the total binder.
  • the proportion of hydrophilic polymers other than gelatin (or gelatin derivatives) is preferably 80% or more based on the total binder.
  • the binder of the peeling layer may comprise a single hydrophilic polymer or a combination of two or more hydrophilic polymers.
  • Gelatin or a gelatin derivative or a dispersion of a hydrophobic compound may be contained in the binder as long as the proportion of hydrophilic polymers are 80% or more.
  • the peeling layer in the present invention is a layer mainly comprising a cellulose derivative. That is, the hydrophilic polymer to be used in the peeling layer is preferably a cellulose derivative, more preferably a hydroxyalkyl cellulose. Examples thereof include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and a mixture thereof.
  • the peeling layer is coated in an amount of from 0.02 to 2.0 g/m 2 , more preferably from 0.05 to 1.0 g/m 2 .
  • a layer mainly comprising gelatin or a gelatin derivative is preferably provided on at least one of layers directly contacting with the peeling layer.
  • gelatin or a gelatin derivative is preferably contained in a proportion of 80% or more. The remainder, i.e., about 20% or less, may contain the aforesaid hydrophilic polymers or a hydrophobic compound dispersion.
  • This layer mainly comprising gelatin or a gelatin derivative is preferably coated in an amount of from 0.01 to 2.0 g/m 2 , more preferably from 0.05 to 1.0 g/m 2 .
  • the binders (hydrophilic polymers) excluding those used in the peeling layer of the present invention are used in a total amount of 20 g/m 2 or less, preferably 10 g/m 2 or less, and more preferably from 2 to 8 g/m 2 .
  • the emulsion side of the silver halide light-sensitive material is pattern exposed and color development is carried out to obtain a color image after the emulsion side thereof is adhered to a light-transmitting glass substrate.
  • This is of great importance for assuring high precision.
  • the pattern image may be often distorted at the time of adhesion because the emulsion side is thin and soft.
  • the emulsion side of a silver halide light-sensitive material can be adhered to a light-transmitting glass substrate via a commercially available adhesive with which the substrate and the emulsion layer, particularly a protective layer, of the light-sensitive material may be bonded together.
  • the adhesive to be used can be selected from among various adhesives, such as thermosetting resin adhesives, thermoplastic resin adhesives, elastomer adhesives, and polymer alloy adhesives, according to the material of the adherents.
  • adhesives such as thermosetting resin adhesives, thermoplastic resin adhesives, elastomer adhesives, and polymer alloy adhesives, according to the material of the adherents.
  • epoxy polymer alloy adhesives are preferred.
  • adhesion of the emulsion side (or protective layer) to a glass substrate is carried out as follows.
  • a solution containing (a) gelatin or a gelatin derivative and (b) colloidal silica is previously applied to the adhered surface of the glass substrate (for example, by means of a spin coater), and the emulsion side, particularly the protective layer, of the light-sensitive material is laminated thereon, followed by heat adhering by means of, for example, a laminator, an iron, and a hot press.
  • the mixing ratio of gelatin or a gelatin derivative and colloidal silica is from 10:1 to 1:10 by weight.
  • the colloidal silica preferably has an average particle size of 0.5 ⁇ m or less, more preferably 0.1 ⁇ m or less.
  • the heat adhering is conducted at a temperature of from 60 to 180°C for an arbitrarily set time, preferably from 0.1 to 60 seconds. The heat adhering may be effected in the presence of a trace amount of water.
  • the support of the light-sensitive material after heat adhering is peeled off and removed (in this processing, it is preferred that a relative humidity is adjusted to 50% or more in order to inhibit generation of static electricity), the pattern exposure is carried out, and then hardening processing is carried out prior to the development processing.
  • Hardening agents known in the art such as aldehyde compounds, ethylene-imine derivatives, isoxazole derivatives, epoxy compounds, vinylsulfone compounds, acryloyl compounds, carbodiimide compounds, cyanuric chloride derivatives, maleimide derivatives, acetylene compounds, methanesulfonic ester compounds, chromium alum, and potassium alum, can be used.
  • materials which are transparent and have optical isotropy and sufficient heat resistance are preferred as the material constituting the light-transmitting glass substrate, and examples thereof include those made of soda-lime glass, borosilicate glass, and quartz.
  • the surface of the substrate may be subjected to undercoating processing, if necessary. Further, surface processing, such as glow discharge, corona discharge, and ultraviolet irradiation, may be conducted.
  • the light-transmitting glass substrate may be used in the form of, for example, a plate, a sheet, a film.
  • the thickness of the glass substrate can be selected appropriately according to the purpose and the material and is usually from 0.01 to 10 mm, preferably from 0.3 to 3 mm.
  • the light-sensitive materials which can preferably be used in the present invention include coupler-in-developer type color reversal films, coupler-in-emulsion type color reversal films, color negative films by color negative processing, color films for displays, and auto positive color films.
  • coupler-in-developer type color reversal films include coupler-in-developer type color reversal films, coupler-in-emulsion type color reversal films, color negative films by color negative processing, color films for displays, and auto positive color films.
  • T.H. James ed.
  • the Theory of the Photographic Process 4th Ed., MacMillan (1977) or Kagaku Shashin Binran I, pp. 559-564 & 569, Maruzen Co., Ltd.
  • coupler-in-emulsion type color films containing two or more couplers capable of developing different hues on color development in the same light-sensitive silver halide emulsion layer as described in JP-A-63-261361 and coupler-in-developer type color films which are developed with a developer containing one developing agent and two or more couplers capable of developing different colors for the same light-sensitive silver halide as described in JP-A-64-79701 are also employable.
  • the light-sensitive material and the method for processing the same which can preferably be used in the present invention will be explained below.
  • Silver halides in the light-sensitive silver halide emulsion layers used in the present invention preferably include silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide.
  • the average iodide content is preferably 3 mol% or less, more preferably 0 mol%. Substantially pure silver bromide or chloride is more preferred.
  • the silver halide grains in emulsions may have a regular crystal form, such as a cubic form, an octahedral form or a tetradecahedral form, an irregular crystal form, such as a spherical form or a plate form, a crystal form having a crystal defect, such as a twinning plane, or a composite crystal form thereof.
  • Cubic grains or octahedral grains are particularly preferred.
  • the silver halide grains may have a wide range of grain size, including from fine grains of 0.2 ⁇ m or smaller to giant grains having a projected area diameter reaching about 10 ⁇ m. While either a mono-dispersed emulsion or a poly-dispersed emulsion is used, a mono-dispersed emulsion having a grain size ranging from 0.1 to 1.5 ⁇ m with a coefficient of variation of 15% or less is preferred.
  • the silver halide emulsions can be prepared by the processes described in, e.g., Research Disclosure (hereinafter abbreviated as RD ), Vol. 176, No. 17643 (Dec., 1978), pp. 22-23, "I. Emulsion Preparation and Types", ibid, No. 18716 (Nov., 1979), p. 648, P. Glafkides, Chemic et Phisique Photographique , Paul Montel (1967), G.F. Duffin, Photographic Emulsion Chemistry , Focal Press (1966), and V.L. Zelikman et al., Making and Coating Photographic Emulsion, Focal Press (1964).
  • Research Disclosure hereinafter abbreviated as RD ), Vol. 176, No. 17643 (Dec., 1978), pp. 22-23, "I. Emulsion Preparation and Types", ibid, No. 18716 (Nov., 1979), p. 648, P. Glaf
  • Mono-dispersed emulsions described in U.S. Patents 3,574,628 and 3,655,394 and British Patent 1,413,748 are preferably used as well.
  • Tabular grains having an aspect ratio of about 5 or more are also useful. Such tabular grains can easily be prepared by the processes described, e.g., in Gutoff, Photographic Science and Engineering , Vol. 14, pp. 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048, and 4,439,520, and British Patent 2,112,157.
  • the silver halide grains may have a uniform crystal structure throughout the individual grains or may be heterogeneous grains including those composed of a core and an outer shell or layers different in halogen compositions, and those having fused thereto silver halide of different halogen composition through epitaxy.
  • Silver halide grains fused with compounds other than silver halides, e.g., silver rhodanide or lead oxide may also be used.
  • a mixture comprising grains of various crystal forms is employable.
  • Additives which can be used in these steps are described in RD , Nos. 17643, 18716 and 307105 as hereinafter listed.
  • Known photographic additives which can be used in the present invention are also described in the same publications as tabulated below.
  • Additive RD 17643 RD 18716 RD 307105 1. Chemical Sensitizer p. 23 p. 648, right column (RC) p. 866 2. Sensitivity Increasing Agent ditto 3. Spectral Sensitizer, Supersensitizer pp. 23-24 p. 648, RC to p.
  • the three silver halide emulsion layers are preferably a layer containing at least cyan coupler, a layer containing at least magenta coupler, and a layer containing at least yellow coupler.
  • suitable color couplers are described in RD , No. 17643, VII-C to G.
  • Two or more couplers which form dyes having different hue may be added to one light-sensitive layer.
  • the color light-sensitive material according to the present invention may comprise a layer containing a cyan coupler and a magenta coupler, a layer containing a magenta coupler and a yellow coupler, and a layer containing a yellow coupler and a cyan coupler.
  • 2-equivalent color couplers having the coupling site thereof substituted with a releasable group are more preferred than 4-equivalent color couplers whose coupling site is a hydrogen atom because the former can reduce the silver amount for coating.
  • Suitable yellow couplers to be used typically includes oil-protected type acylacetamide couplers. Specific examples of these couplers are given in U.S. Patents 2,407,210, 2,875,057, and 3,265,506. Two-equivalent yellow couplers are preferred as mentioned above. Included in these couplers are yellow couplers of oxygen-release type described in U.S. Patents 3,408,194, 3,447,928, 3,935,501, and 4,022,620; and nitrogen-release type yellow couplers described in JP-B-58-10739, U.S. Patents 4,401,752 and 4,326,024, RD , 18053 (Apr., 1979), British Patent 1,425,020, and West German Patent OLS Nos.
  • ⁇ -pivaloylacetanilide couplers produce dyes having excellent stability especially against light
  • ⁇ -benzoylacetanilide couplers produce dyes having high color density.
  • Suitable magenta couplers to be used in this invention include oil-protected type 5-pyrazolone couplers and pyrazoloazole couplers such as pyrazolotriazoles.
  • the 5-pyrazolone couplers are preferably substituted with an arylamino group or an acylamino group at the 3-position thereof in view of the hue or density of a developed color.
  • Typical examples of such 5-pyrazolone couplers are described in U.S. Patents 2,311,082, 2,343,703, 2,600,788, 2,908,573, 3,062,653, 3,152,896, and 3,936,015.
  • Releasable groups of 2-equivalent 5-pyrazolone couplers preferably include nitrogen-releasable groups described in U.S. Patent 4,310,619 and arylthio groups described in U.S. Patent 4,351,897. Further, 5-pyrazolone couplers having a ballast group described in European Patent 73,636 provide high color density.
  • Suitable pyrazoloazole couplers include pyrazolobenzimidazoles described in U.S. Patent 3,369,879, and preferably pyrazolo[5,1-c][1,2,4]triazoles described in U.S. Patent 3,725,067, pyrazolotetrazoles described in RD , 24220 (Jun., 1984), and pyrazolopyrazoles described in RD , 24230 (Jun., 1984).
  • imidazo[1,2-b]pyrazoles described in European Patent 119,741 are preferred, and pyrazolo[1,5-b][1,2,4]triazole described in European Patent 119,860 is particularly preferred.
  • Cyan couplers which can be used in the present invention include oil-protected type naphthol and phenol couplers. Typical examples of these cyan couplers are naphthol couplers described in U.S. Patent 2,474,293, and oxygen-release type 2-equivalent naphthol couplers described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, and 4,296,200. Examples of phenol couplers are described in U.S. Patents 2,369,929, 2,801,171, 2,772,162, and 2,895,826. Cyan couplers stable to moisture and heat are preferably used in the present invention.
  • Typical examples of such couplers include phenol cyan couplers having an alkyl group having at least two carbon atoms at the m-position of the phenol nucleus described in U.S. Patent 3,772,002, 2,5-diacylamino-substituted phenol couplers described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011, and 4,327,173, 4,500,635, West German Patent OLS No. 3,329,729, and phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position described in U.S. Patents 3,446,622, 4,333,999, 4,451,559, and 4,427,767.
  • 2,5-diacylamino-substituted phenol couplers are preferred.
  • Dye-forming couplers may be in the form of a polymer. Typical examples of dye-forming couplers in a polymer form are described in U.S. Patents 3,451,820, 4,080,211, and 4,367,282, and British Patent 2,102,173.
  • Couplers capable of releasing a photographically useful residue on coupling are also used to advantage.
  • suitable DIR couplers which release a development inhibitor are described in RD , No. 17643, Items VII-F, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and U.S. Patent 4,248,962.
  • Couplers which can be additionally used in the light-sensitive material of the present invention include competing couplers described in U.S. Patent 4,130,427; polyequivalent couplers described in U.S. Patents 4,283,472, 4,338,393, and 4,310,618; couplers capable of releasing a DIR redox compound described in JP-A-60-185950; and couplers capable of releasing a dye which restores its color after release described in EP-A-173302.
  • the light-sensitive material used in the present invention preferably contains the compound described in EP-A2-0277589, which serves for improving dye image preservability, in a coupler-containing layer.
  • the compound disclosed is particularly effective when used in combination with pyrazoloazole magenta couplers.
  • EP-A2-0277589 discloses compound (F) which chemically reacts with an aromatic amine developing agent remaining after color development to form a chemically inert and substantially colorless compound and compound (G) which chemically reacts with an oxidation product of an aromatic amine developing agent remaining after color development to form a chemically inert and substantially colorless compound. Therefore, use of compound (F) and/or compound (G) is effective to prevent the color developing agent or an oxidation product thereof remaining in a film after processing from further reacting with couplers during preservation to cause stains or any other unfavorable side effects.
  • the light-sensitive material used in the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative or an ascorbic acid derivative as a color fog inhibitor.
  • Suitable ultraviolet absorbents include aryl-substituted benzotriazole compounds (e.g., those described in U.S. Patent 3,533,794); 4-thiazolidone compounds (e.g., those described in U.S. Patents 3,314,794 and 3,352,681); benzophenone compounds (e.g., those described in JP-A-46-2784); cinnamic ester compounds (e.g., those described in U.S.
  • Ultraviolet-absorbing couplers e.g., ⁇ -naphthol cyan couplers
  • ultraviolet-absorbing polymers are also useful. These ultraviolet absorbents may be mordanted in a specific layer. Of these ultraviolet absorbents preferred are aryl-substituted benzotriazole compounds.
  • an antimicrobial or antifungal agent such as the compound disclosed in JP-A-63-271247, so as to prevent various bacteria and mold from proliferating to cause image deterioration.
  • the couplers are introduced into light-sensitive materials by various known dispersion methods.
  • the coupler-in-developer type light-sensitive materials use no hydrophobic couplers but couplers soluble in a developer, and the developer-soluble couplers are added to a color developer but not to a light-sensitive material. Specific examples of such couplers are described in JP-A-64-79701.
  • the internal latent image type emulsion may be either a conversion type emulsion or a core/shell type emulsion, with the latter being preferred.
  • the light-sensitive material used in the present invention is a direct positive light-sensitive material having a silver halide emulsion which is a beforehand unfogged internal latent image type silver halide emulsion.
  • Suitable support which can be used in the color light-sensitive materials are described, e.g., in RD , No. 17632, p. 28, and ibid, No. 18716, pp. 647 (right column) to 648 (left column).
  • the surface of the support may be subjected to undercoating processing and/or be subjected to a surface treatment, such as a glow discharge treatment, a corona discharge treatment and ultraviolet irradiation.
  • the back surface may be coated with, e.g., carbon black in order to improve heat and electric conductivities.
  • the light-sensitive materials can be development processed according to usual methods as described in RD , No. 17643, pp. 28-29 and ibid , p. 615, left to right columns.
  • the light-sensitive material used in the present invention is processed by, for example, color development, followed by desilvering, followed by washing.
  • Desilvering is effected by bleaching using a bleaching bath and fixing using a fixing bath, or bleaching and fixing may be replaced with bleach-fix using a bleach-fix bath.
  • Bleaching, fixing, and bleach-fix may be combined in an arbitrary order. Washing may be replaced with or followed by stabilization.
  • Color development, bleach, and fixing may be performed by combined color developing, bleaching and fixing using a monobath. These processing steps may be combined with prehardening, neutralization for the prehardener, stopping and fixing, post hardening, compensation and intensification. A so-called activator processing step may be conducted instead of color development.
  • nondiffusion dye-donating compounds capable of releasing a diffusing dye in correspondence or reverse correspondence to the reduction reaction of silver halide to silver can also be used as dye image-forming compounds in the light-sensitive material for color filters.
  • Specific examples of such dye-donating compounds are described in JP-A-59-185333, JP-A-63-201653, EP-B-220746, and U.S. Patents 4,500,626, 4,639,408, 4,783,396, 4,232,107, 4,619,884, 4,450,223, 4,503,137, and 4,559,290.
  • the light-sensitive material containing the above-mentioned dye-donating compound is processed in accordance with the methods described in U.S. Patent 3,923,510, West German Patent OLS No. 2,916,582, JP-A-54-143230, and Japanese Patent Application No. 205554/93 to provide a color filter having a dye image formed of the released dye.
  • the coupler-in-emulsion type light-sensitive material used in the present invention preferably has a total thickness of 20 ⁇ m or less, more preferably from 5 to 15 ⁇ m.
  • the coupler-in-developer type light-sensitive material of the present invention preferably has a total thickness of 15 ⁇ m or less, more preferably from 3 to 10 ⁇ m.
  • the pattern exposure system which can be used in the present invention includes a planar exposure system and a scanning exposure system.
  • the scanning system includes a line (slit) scanning system and a point scanning system using a leaser beam, etc.
  • Examples of a light source include tungsten lamp, halogen lamp, fluorescent lamp (e.g., three wavelengths type fluorescent lamp), laser lamp, and light emitting diode. Preferred are halogen lamp, fluorescent lamp and laser lamp.
  • band stop filter described in U.S. Patent 4,880,726 is preferably used to remarkably improve color reproducibility by removing light contamination.
  • the material after pattern exposure is subjected to color development with a surface developing solution containing an aromatic primary amine color developing agent preferably at a pH of 12 or lower, particularly between 11.0 and 10.0, either after or simultaneously with fogging by light or a nucleating agent, followed by bleaching and fixing to form a direct positive color image.
  • a surface developing solution containing an aromatic primary amine color developing agent preferably at a pH of 12 or lower, particularly between 11.0 and 10.0, either after or simultaneously with fogging by light or a nucleating agent, followed by bleaching and fixing to form a direct positive color image.
  • Fogging in this embodiment may be effected by either a method called light fogging in which the entire surface of a light-sensitive layer is subjected to second exposure or a method called chemical fogging in which a light-sensitive material is developed in the presence of a nucleating agent. Development may be conducted in the presence of both a nucleating agent and fogging light. Further, a light-sensitive material containing a nucleating agent may be subjected to fogging exposure.
  • nucleating agents are those represented by formulae (N-I) and (N-II) shown in that specification.
  • nucleation accelerators which can be used in the present invention are also described in the same specification.
  • Preferred nucleation accelerators are Compound Nos. (A-1) to (A-13) shown on pages 55 to 57.
  • the color filter produced by the process of the present invention may have a heat- and water-resistant (organic solvent-resistant) protective (overcoating) layer having a high specific resistance as an outermost layer.
  • a heat- and water-resistant (organic solvent-resistant) protective (overcoating) layer having a high specific resistance as an outermost layer.
  • the resins providing such a protective layer are described in U.S. Patents 4,698,295 and 4,668,601, EP-A-179636, EP-A-556810, and JP-A-3-163416, JP-A-3-188153, JP-A-5-78443, JP-A-1-27610, JP-A-60-216307 and JP-A-63-218771.
  • the color filter obtained has little unevenness on the surface thereof, and, for example, it is desirable that the unevenness is from -0.1 ⁇ m to 0.1 ⁇ m.
  • a transparent electrode such as an indium-tin oxide layer (ITO)
  • ITO indium-tin oxide layer
  • orientation layer such as polyimide resin, may be provided thereon.
  • a polarizer or a phase retarder may be provided on the light-transmitting substrate of the color filter on its side opposite to the emulsion layer.
  • a color liquid crystal display (hereinafter abbreviated as LCD) using the color filter according to the present invention will be described below.
  • FIG. 1 a schematic cross section of an example of LCD.
  • Color filter 2 which is formed on glass substrate 1 according to the Example, is covered with a protective film (not shown) made of the above-mentioned resin.
  • Transparent electrode e.g., an indium-tin oxide (ITO) electrode, is formed on the protective film by means of a vacuum film-forming apparatus.
  • Transparent electrode 3 is usually provided on the entire surface of the color filter in the case of active matrix-driven LCD using a three-terminal switching array like TFT or in the stripe form in the case of simple matrix-driven LCD or active matrix-driven LCD using a two-terminal switching array like MIM.
  • orientation' layer 4 comprising polyimide, etc. for alignment of liquid crystal molecules.
  • the ITO-glass substrate having color filter 3 is assembled with another glass substrate 7 having formed thereon transparent electrode (e.g., an ITO electrode) and layer 4 in this order via spacers (not shown) and sealing material 6 with both alignment layers facing to each other.
  • transparent electrode 8 forms pixels connected with TFT elements.
  • simple matrix-driven LCD such as STN mode LCD
  • transparent electrode 8 usually has the form of stripes crossing the stripes of transparent electrode 3 on the other side.
  • Black matrix 9 is usually formed among R, G, and B pixels to improve contrast or color purity. Black matrix 9 can be formed simultaneously with the formation of R, G, and B pixels, or a chromium film or a carbon film may be formed separately.
  • Polarizers 10 and 11 are placed on the back side of glass substrates 1 and 2, respectively. If desired, a phase compensator (not shown) may be provided between each glass substrate and the polarizer.
  • back light 12 is usually placed as a light source which matches the color filter in color reproduction.
  • a plastic film having a gas barrier layer or a hard coating layer may be used in place of the above-described glass substrate as a light-transmitting substrate.
  • a multi-layer color light-sensitive material designated sample A
  • the numeral for each component is the spread in terms of gram per m 2 .
  • the spreads of silver halide emulsions and colloidal silver emulsions are expressed in terms of silver amount (g) per m 2 .
  • the emulsions used were prepared by the method for preparing emulsion EM-1 hereinafter described.
  • aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous gelatin solution at 60°C with vigorous stirring over a period of 8 minutes to form octahedral silver bromide grains having an average grain size of 0.15 ⁇ m.
  • 0.3 g, per mole of silver, of 3,4-dimethyl-1,3-thiazoline-2-thione was added to the system.
  • To the resulting emulsion were added successively 6 mg of sodium thiosulfate and 7 mg of chloroauric acid tetrahydrate per mole of silver, followed by heating at 75°C for 80 minutes to carry out chemical sensitization.
  • the thus formed grains were allowed to grow under the same precipitation conditions as above to finally obtain a mono-dispersed emulsion of octahedral. core/shell silver bromide grains having an average particle size of 0.32 ⁇ m. The coefficient of variation of the grain size was about 8%.
  • To the emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid tetrahydrate per mole of silver, followed by heating at 60°C for 60 minutes to obtain an internal latent image type silver halide emulsion.
  • Each of the light-sensitive layers of sample A further contained nucleating agents ExZK-1 and ExZK-2 in an amount of 10 -3 % and 10 -2 %, respectively, and a nucleation accelerator Cpd-15 in an amount of 10 -2 %, each based on the silver halide.
  • the light-sensitive layers each furthermore contained a silver halide stabilizer Cpd-16.
  • each constituting layer contained sodium dodecylbenzenesulfonate as an emulsifying agent or a dispersant, ethyl acetate as an auxiliary solvent, Cpd-17 as a coating aid, and potassium polystyrenesulfonate as a thickener.
  • a 30 cm long, 30 cm wide and 1.1 mm thick transparent substrate made of borosilicate glass was coated with a 1:3 (by weight) mixture of gelatin and colloidal silica (average particle size: 7 to 9 m ⁇ ) to which saponin had been added as a surface active agent to a coating thickness of 0.2 ⁇ m.
  • the protective layer of sample A was adhered to the coated surface of the transparent substrate, with slight moisture being supplied to the emulsion side of sample A.
  • the laminate was passed through a laminator set to provide a temperature of about 150°C to the joint area at a linear speed of 0.45 m/minute. After allowing the laminate to cool to room temperature, the polyethylene terephthalate support of sample A was stripped off. The emulsion layers were found uniformly and intimately adhered to the glass substrate with no defect.
  • the emulsion layers thus transferred to the glass substrate were exposed to light of a tungsten lamp via a mask for a color filter composed of a blue portion, green portion, red portion, and a black portion and processed according to the following schedule to produce a color filter having three primaries (B, G and R) plus black.
  • Hardener Anhydrous sodium sulfate 160.0 g Anhydrous sodium carbonate 4.6 g Formalin (37%) 20.0 ml Water to make 1000 ml pH (25°C) 10.0
  • Color Developer D-Sorbitol 0.15 g Sodium naphthalenesulfonate-formalin 0.15 g condensate Pentasodium nitrilotris(methylenephosphonate) 1.80 g Diethylenetriaminepentaacetic acid 0.50 g 1-Hydroxyethylidene-1,1-diphosphonic acid 0.15 g Diethylene glycol 12.0 ml Benzyl alcohol 13.5 ml Potassium bromide 0.70 g Benzotriazole 0.003 g Sodium sulfite 2.40 g Disodium-N,N-bis(sulfonatoethyl)hydroxylamine 8.0 g Triethanolamine 6.00 g N-
  • Deionized water having an electrical conductivity of not more than 5 ⁇ S.
  • the resulting color filter had a pattern of B, G, R having an absorbance of 1.0 to 1.7 in each component of cyan, magenta and yellow, and black having an absorbance of 2.3 to 2.7 in each component, suffering from neither white spot nor loss of color definition.
  • a color filter having B, G, R, and black patterns was prepared in the same manner as in Example 1, except that the adhesion of the glass substrate and sample A was carried out by applying a commercially available epoxy type adhesive to the glass substrate in place of the mixture of gelatin and colloidal silica and curing the epoxy adhesive at 40°C.
  • a color light-sensitive material (designated sample B) was prepared in the same manner as for sample A, except that the 2nd gelatin layer was not provided.
  • the protective layer of sample B was adhered to a glass substrate in the same manner as in Example 1, and release of the temporary support of sample B was compared with that of sample A.
  • the support of sample A was completely peeled apart at the peeling layer, whereas stripping of the support from sample B was accompanied by peeling of about 10% area of the emulsion layer. It is thus seen that the layer adjacent to the peeling layer is preferably a layer mainly comprising gelatin.
  • a gelatin subbing layer was coated on a 100 ⁇ m thick polyethylene terephthalate support having a backing layer coated with carbon black dispersed in polyvinyl chloride as described in the example of JP-A-63-293348. Layers from 1st to 10th shown below were applied simultaneously thereon to prepare a multi-layer color light-sensitive material (designated sample C).
  • the numeral for each component is the spread in terms of gram per m 2 .
  • the spreads of silver halide emulsions and colloidal silver emulsions are expressed in terms of silver amount (g) per m 2 .
  • the compounds used were the same as used in Example 1.
  • the blue-sensitive layer, green-sensitive layer, and red-sensitive layer further contained Cpd-24 in an amount of 4.0 ⁇ 10 -6 mol, 3.0 ⁇ 10 -5 mol, and 1.0 ⁇ 10 -5 mol, respectively, per mole of the corresponding silver halide.
  • the blue-sensitive layer and green-sensitive layer furthermore contained Cpd-16 in an amount of 1.2 ⁇ 10 -2 mol and 1.1 ⁇ 10 -2 mol, respectively, per mole of the corresponding silver halide.
  • each constituting layer contained sodium dodecylbenzenesulfonate as an emulsifying agent or a dispersant, ethyl acetate as an auxiliary solvent, Cpd-17 as a coating aid, and potassium polystyrenesulfonate as a thickener.
  • the emulsion layers of sample C were transferred to the same transparent substrate as used in Example 1 in the same manner as in Example 1.
  • the emulsion layers on the glass substrate were exposed to light of a tungsten lamp via a mask for a color filter composed of a blue portion, a green portion, and a red portion, and processed according to the following schedule to produce a color filter having three primaries (B, G and R) plus black. Processing Step Temp.
  • the color developer used had the following composition. Other processing solutions each had the same composition as used in Example 1.
  • Color Developer Water 800 ml Ethylenediaminetetraacetic acid 3.0 g Disodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g Triethanolamine 12.0 g Potassium chloride 6.5 g Potassium bromide 0.03 g Potassium carbonate 27.0 g Fluorescent brightening agent WHITEX 4, produced by Sumitomo Chemical Co., Ltd.
  • a color filter having a pattern of B, G, R having an absorbance of 0.9 to 1.6 in each component of cyan, magenta and yellow, and black having an absorbance of 2.2 to 2.9 in each component with neither white spot nor peeling failure was obtained.
  • the present invention makes it possible to produce a color filter on a hard light-transmitting substrate such as a glass plate with extreme ease.
  • the color filter obtained comprises a blue portion, a green portion and a red portion each having excellent spectral transmission characteristics and a black portion of high density with good precision suffering from neither loss of color definition nor white spot.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Optical Filters (AREA)

Claims (6)

  1. Verfahren für die Herstellung eines Farbfilters, umfassend die folgenden Stufen:
    Anhaften der Emulsionsseite eines lichtempfindlichen Materials auf ein lichttransmittierendes Substrat durch Erwärmung, wobei das lichtempfindliche Material einen Träger umfasst, darauf vorgesehen eine Abpellschicht und weiter darauf vorgesehen mindestens drei Silberhalogenidemulsionsschichten, die voneinander verschieden in ihrer Farbempfindlichkeit sind, wobei das lichttransmittierende Substrat ein Glassubstrat ist, auf das (a) Gelatine oder ein Derivat davon und (b) kolloidales Silika zuvor auf die Anhaftungsseite beschichtet wurden,
    Abpellen des Trägers vom lichtempfindlichen Material;
    Musterweises Belichten der Emulsionsseite;
    Unterwerfen des Materials einer Härtungsverarbeitung vor der Entwicklungsverarbeitung; und
    Unterwerfen des Materials einer Entwicklungsverarbeitung und einer Entsilberungsverarbeitung.
  2. Verfahren für die Herstellung eines Farbfilters nach Anspruch 1, wobei die Abpellschicht hauptsächlich ein Polymer umfasst, wobei das Polymer nicht Gelatine oder ein Gelatinederivat ist, und andere Schichten als die Abpellschicht jeweils ein Bindemittel umfassen, hauptsächlich umfassend Gelatine oder ein Gelatinederivat.
  3. Verfahren für die Herstellung eines Farbfilters nach Anspruch 1, wobei eine Schicht hauptsächlich umfassend Gelatine oder ein Gelatinederivat auf mindestens einer der Schichten vorgesehen ist, die direkt die Abpellschicht berühren.
  4. Verfahren für die Herstellung eines Farbfilters nach Anspruch 1, wobei die Abpellschicht hauptsächlich ein Cellulosederivat umfasst.
  5. Verfahren für die Herstellung eines Farbfilters nach irgendeinem der Ansprüche 1 bis 4, wobei die drei Silberhalogenidemulsionsschichten eine Schicht, enthaltend mindestens einen Cyankuppler, eine Schicht, enthaltend mindestens ein Magentakuppler, und eine Schicht, enthaltend mindestens einen Gelbkuppler, sind.
  6. Verfahren für die Herstellung eines Farbfilters nach irgendeinem der Ansprüche 1 bis 5, wobei das lichtempfindliche Material ein direkt positives lichtempfindliches Material ist, mit einer Silberhalogenidemulsion, die eine zuvor unverschleierte Silberhalogenidemulsion vom internen Latentbildtyp ist.
EP19950100144 1994-01-11 1995-01-05 Verfahren zur Herstellung von Farbfiltern Expired - Lifetime EP0662635B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP1363/94 1994-01-11
JP136394 1994-01-11
JP136394 1994-01-11

Publications (3)

Publication Number Publication Date
EP0662635A2 EP0662635A2 (de) 1995-07-12
EP0662635A3 EP0662635A3 (de) 1995-10-18
EP0662635B1 true EP0662635B1 (de) 2002-07-17

Family

ID=11499422

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19950100144 Expired - Lifetime EP0662635B1 (de) 1994-01-11 1995-01-05 Verfahren zur Herstellung von Farbfiltern

Country Status (2)

Country Link
EP (1) EP0662635B1 (de)
DE (1) DE69527378T2 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69636023T2 (de) * 1995-05-22 2006-08-24 Fuji Photo Film Co., Ltd., Minami-Ashigara Lichtempfindliches Silberhalogenidmaterial für Farbfilter und Verfahren zur Herstellung eines Farbfilters zu dessen Verwendung
US5817440A (en) * 1996-02-23 1998-10-06 Hirai; Hiroyuki Silver halide photosensitive material for color filter and method for producing color filter using the same

Also Published As

Publication number Publication date
DE69527378D1 (de) 2002-08-22
EP0662635A2 (de) 1995-07-12
DE69527378T2 (de) 2002-11-07
EP0662635A3 (de) 1995-10-18

Similar Documents

Publication Publication Date Title
US5776643A (en) Light-sensitive material for color filter and process for producing color filter using the same
US5571663A (en) Silver halide light-sensitive material and color filter
EP0713137B1 (de) Lichtempfindliches Silberhalogenidmaterial für Farbfilter und Methode zur Herstellung von Farbfiltern unter Verwendung derselben
EP0662635B1 (de) Verfahren zur Herstellung von Farbfiltern
US5885736A (en) Preparation method of color filter using a silver halide light sensitive material
US5817440A (en) Silver halide photosensitive material for color filter and method for producing color filter using the same
US5576127A (en) Color filter and process for producing the color filter
JPH112713A (ja) カラー表示装置用カラーフイルター基板の製造方法
JPH08201616A (ja) カラーフィルターの製造方法及びそれにより得られるカラーフィルター
JPH08248219A (ja) カラーフィルターの製造方法
JPH09288208A (ja) カラーフイルター用ハロゲン化銀感光材料およびそれを用いるカラーフイルターの作成方法
JPH10232307A (ja) カラーフィルターの製造方法
EP0849630B1 (de) Verfahren zur Herstellung eines Farbfilters
JP3852990B2 (ja) ハロゲン化銀感光材料を用いるカラーフィルターの作成方法
JP3529492B2 (ja) カラーフィルター用ハロゲン化銀感光材料およびそれを用いるカラーフィルターの作成方法
JP2003066217A (ja) カラーフィルター及びカラーフィルターの製造方法
JPH1078505A (ja) カラーフイルター
JPH09145909A (ja) カラーフィルターおよびそれを用いたカラー液晶表示装置
JPH112714A (ja) カラー表示装置用カラーフイルター基板の製造方法
JPH08290101A (ja) 部分塗布方法及びそれを用いたカラーフィルターの製造方法
JPH0990536A (ja) カラーフイルター用ハロゲン化銀感光材料およびそれを用いるカラーフイルターの作成方法
JPH10333295A (ja) ハロゲン化銀感光材料およびこれを用いるカラーフィルターの作製方法
JPH1195023A (ja) カラーフイルター及びその製造方法
JPH10177111A (ja) 保護膜を有するカラーフイルター
JPH09204026A (ja) ハロゲン化銀カラー感光材料およびそれを用いるカラーフィルターの作成方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19951229

17Q First examination report despatched

Effective date: 19990407

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RIC1 Information provided on ipc code assigned before grant

Free format text: 7G 03C 7/06 A

RTI1 Title (correction)

Free format text: PROCESS FOR PRODUCING COLOUR FILTER

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020717

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69527378

Country of ref document: DE

Date of ref document: 20020822

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20030105

EN Fr: translation not filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20030422

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20030105

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20090102

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100803