EP0337490B1 - Lichtempfindliches photographisches Silberhalogenidmaterial - Google Patents

Lichtempfindliches photographisches Silberhalogenidmaterial Download PDF

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Publication number
EP0337490B1
EP0337490B1 EP19890106744 EP89106744A EP0337490B1 EP 0337490 B1 EP0337490 B1 EP 0337490B1 EP 19890106744 EP19890106744 EP 19890106744 EP 89106744 A EP89106744 A EP 89106744A EP 0337490 B1 EP0337490 B1 EP 0337490B1
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EP
European Patent Office
Prior art keywords
group
photographic material
silver halide
layer
color
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
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EP19890106744
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English (en)
French (fr)
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EP0337490A3 (en
EP0337490A2 (de
Inventor
Keisuke C/O Fuji Photo Film Co. Ltd. Shiba
Junichi C/O Fuji Photo Film Co. Ltd. Yamanouchi
Kazunori C/O Fuji Photo Film Co. Ltd. Hasebe
Seiichi C/O Fuji Photo Film Co. Ltd. Taguchi
Kazuo C/O Fuji Photo Film Co. Ltd. Shioda
Toshihiro C/O Fuji Foto Film Co. Ltd. Nishikawa
Shigeru C/O Fuji Foto Film Co. Ltd. Ohno
Tetsuro C/O Fuji Foto Film Co. Ltd. Fuchizawa
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication date
Priority claimed from JP63255425A external-priority patent/JPH07111558B2/ja
Priority claimed from JP1027894A external-priority patent/JP2533367B2/ja
Priority claimed from JP1030405A external-priority patent/JP2879106B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0337490A2 publication Critical patent/EP0337490A2/de
Publication of EP0337490A3 publication Critical patent/EP0337490A3/en
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Publication of EP0337490B1 publication Critical patent/EP0337490B1/de
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    • 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
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • 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
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

  • the present invention relates to a silver halide light-sensitive color photographic material having a reflective support, which exhibits excellent sharpness and edge contrast in images and excellent whiteness in non-image areas.
  • the present invention relates to a color photographic paper especially suitable for rapid development processing.
  • the present invention also relates to a method of forming a color image to form excellent line images or character images along with photographic or CG (computer graphic) images.
  • Various means may be used to attain the improved material including, for example, use of silver halide emulsions of high sensitivity comprising fine grains, formation of plural light-sensitive layers, formation of thin light-sensitive layers, economization of the amount of silver halides to be used, use of less light-scattering silver halide emulsions, incorporation of anti-halation or anti-irradiation dyes and use of mordant layers for anti-halation or anti-irradiation dyes.
  • DIR couplers or color mixing preventing agents may be used to improve the sharpness by interimage effect.
  • Picture-taking photographic materials have, in many cases, a transparent plate or film support. The support itself may be dyed for anti-halation, or an anti-halation black backing layer (AHB) or an anti-halation layer (AHU) may be provided therefor.
  • Methods of providing AHU in color photographic materials are also known. These methods are described in, for example, US-A-2,882,156, US-A-2,326,057, US-A-2,839,401 and US-A-3,706,563 and JP-A-55-33172, JP-A-59-193447 and JP-A-62-32448.
  • JP-A-61231550 discloses an image forming method wherein the gamma value of the silver halide photographic sensitive material after development is regulated to 0.8 to 1.7 by mixing silver halide emulsions having higher and lower sensitivities and applying them to a support. This method permits a higher quality image to be obtained with reduced unevenness in image density.
  • JP-B-58-43734 and JP-A-58-17433, JP-A-58-14830 and JP-A-61-259246 the term "JP-B” as used herein means an "examined Japanese patent publication"
  • a method of forming a waterproof resin layer on a raw paper by coating a composition containing an unsaturated organic compound having one or more double bonds in one molecule and polymerizable by electron rays and a white pigment on a raw paper and hardening the composition on the paper by irradiation of electron rays thereto under heat is described in, for example, JP-A-57-27257, JP-A-57-49946, JP-A-61-262738 and JP-A-62-61049.
  • Silver halide photographic materials having a mirror-reflective or secondary diffusive reflective support are also known. For example, they are described in JP-A-63-24251, JP-A-63-24253 and JP-A-63-24255.
  • JP-A-63-63036 mentions the provision of a colloidal silver-containing antihalation layer in a direct positive color photographic paper or in a high-sensitivity reflective color photographic paper having a thinner reflective support than a conventional one so as to inhibit the deterioration of the sharpness due to the transmission density of the support being less than 0.8.
  • JP-A-63-63040 mentions the provision of an auxiliary layer in a direct positive photographic material or in a negative photographic material containing a silver chloride-containing emulsion layer and a colloidal silver layer so as to prevent the occurrance of contact fog caused by the colloidal silver in rapid processing.
  • a particular technical means is required to attain improvement, which can be apparently recognized, with respect to the image sharpness and the tone reproducibility of the highlight details in the silver halide photographic material having the reflective support, especially in the color photographic paper having a primary diffusive reflective white support, without lowering the whiteness thereof.
  • a photographic original of, for example, a color negative film or color positive slide obtained by photographing using a picture-taking photographic material is printed on a color photographic paper by imagewise exposure to obtain a color print.
  • a method of printing a film block copy, which has separately been prepared by printing the necessary characters on a lith film, and printing them in combination is employed.
  • such a method is complicated and requires a long time to be completed.
  • a printed sheet formed by printing characters on a semi-transparent raw paper with a word processor may by used, but the color print obtainable therewith has a poor image quality.
  • the method of printing CG, line images or character images on a color photographic paper from a memory means previously inputted as a digital information with a printer having a CRT exposure system is also known.
  • printers having a CRT exposure system are disclosed in JP-A-62-43281, JP-A-62-184446, JP-A-62-295037, JP-A-62-295038 and JP-A-62-295039.
  • JP-A-62-89965 discloses a printer having an FOT (fiber optics tube).
  • the image quality of the photographic picture image obtained by conventional exposure printing systems is extremely high.
  • the image quality of the line image or character image to be combined with the picture image is not as good as that of the picture image.
  • prints obtained from color photographic papers are widely used for various kinds of cards including an ID card, license card, credit card, bank card, etc.
  • Methods for preparing the cards are described, for example, in JP-A-62-50755, JP-A-62-58247, JP-A-62-58248 and JP-A-62-58249.
  • Prints obtained from thin color photographic papers are also used for seal prints or post cards which are directly stuck to other supports. These are described in, for example, JP-A-60-41949 and JP-A-60-41950.
  • VIDEOFIX-85 (trade name). This method is also described in, for example, JP-A-60-176385.
  • Scanning exposure systems are advantageous in that characters, figures and photographic images (continuous tone images) are easily digitalized for direct image synthesis or image processing or they are outputted with ease.
  • such systems are disadvantageous in that the image quality of the line images or character images formed is much poorer than the image quality of the photographic images formed.
  • a silver halide emulsion having a high silver chloride content for example, 80 mol% or more of the total silver halide
  • the sensitivity is hardly elevated and the sensitivity as well as the stability of latent images formed is rather inferior to that of a material having a conventional silver chlorobromide emulsion (for example, silver halide emulsion having a silver chloride content of less than 20 mol%).
  • Scanning exposure systems use laser rays having light intensity in at least three different wavelength ranges, fluorescent emission, LED (luminescence emitting diode) emission or liquid crystal emission and, if desired, it is combined with color separation filters.
  • a scanning exposure system with fluorescent emission for example, a CRT or FOT exposure system
  • selection of proper fluorescent bodies with pertinent light emission intensity and efficiency for the spectral sensitivity of the respective light-sensitive layers of color photographic papers to be exposed therewith is necessary so as to accelerate, simplify and stabilize the exposure step.
  • stable tungsten light, halogen lamp light or xenon lamp light is used in the photographic exposure system, and the sensitivity of the respective light-sensitive layers of color photographic papers to be exposed therewith is determined in accordance with the light source.
  • the ratio of the sensitivity of the respective light-sensitive layers of conventional color photographic papers does not match with CRT or FOT exposure systems at all. In most color photographic papers, the sensitivity to light with a longer wavelength, especially red-sensitivity is relatively insufficient.
  • the object of the present invention to overcome said problems in the prior art and to provide a white reflective support-having photographic material which has improved whiteness in the non-image part and excellent image sharpness, which has excellent tone reproducibility in the highlight details, which is suited for rapid development (for a color development time of 90 s or less) and which has been improved so that the processing solution does not penetrate into the paper from the cut edge thereof to stain the finished photograph.
  • the present invention wants to provide a method of forming color images simply, rapidly and at a low production cost, for obtaining prints composed of line images and/or character images having excellent image quality, especially having high edge contrast, and CG images and/or photographic images.
  • a color photographic material comprising: at least one silver halide light-sensitive layer provided on a reflective support containing white pigment grains in a waterproof resin layer, wherein said pigment grains are present in said waterproof resin layer in a density of from 10% by weight or more, and a colored layer which can be decolored by photographic processing located between said support and said silver halide light-sensitive layer, characterized in that the degree of dispersion of the white pigment grains in the layer is from 0.20 or less as the fluctuation coefficient (s/ R ) of the possessory area ratio (%) per unit area of 6 »m x 6 »m, where R means the mean possessory area ratio per unit area and s means the standard deviation of the possessory area ratio per the unit area.
  • the present invention there is also provided a method of forming a color image characterized in that the color photographic material of the present invention is printed by a scanning exposure system and then subjected to color development processing.
  • the color photographic material is a reflection color photographic material
  • the at least one silver halide light-sensitive layer contains a colour coupler
  • the waterproof resin layer is located on the side of the support coated with said silver halide light-sensitive layer
  • said silver halide light-sensitive layer contains an emulsion of silver chlorobromide having a mean silver chloride content of 90 mol% or more and having a silver bromide-localized phase in the inside and/or surface of the emulsion grain.
  • Fig. 1 shows a flow sheet of one embodiment of a process of forming prints by a CRT exposure system.
  • Fig. 2 shows the scanning exposure direction for a Japanese character and the position for determination of the density of the parts of the character.
  • Fig. 3 is a spectral graph showing the relationship between the visual density and the position of the scanning direction in determination of the density of the Japanese character by means of a scanning exposure system with a microdensitometer.
  • the axis of the ordinate indicates the visual density of fine lines constituting the character and that of the abscissa indicates the position of the scanning direction.
  • Fig. 4-a and Fig. 4-b show spectral sensitivity curves of samples (F) and (E) of Examples B-5 and B-6, respectively, where B (... ... ...), G (------) and R (_____) mean the relative spectral sensitivity of blue-sensitive layer, green-sensitive layer and red-sensitive layer, respectively.
  • the value for R is a 12-magnified one.
  • the axis of the ordinate indicates the relative spectral sensitivity, and that of the abscissa indicates the wavelength (nm).
  • Fig. 5 shows relative emission strength distribution of the mixture of fluorescent substances of P-22R and P-45.
  • the axis of the ordinate indicates the relative emission strength, and that of the abscissa indicates the wavelength (nm).
  • Fig. 6 shows spectral transmittance curves of B, G, R and Y filters.
  • the axis of the ordinate indicates the transmittance, and that of the abscissa indicates the wavelength (nm).
  • Fig. 7 is a graph to explain the evaluation method of edge sharpness, where the axis of the ordinate indicates the density and that of the abscissa indicates the distance.
  • Ds means the density difference, and L means the transition width of the stepwise image with Ds.
  • the white support for use in the silver halide photographic material of the present invention can be prepared by coating a waterproof resin layer on the substrate.
  • Suitable substrates include raw papers made from natural pulp or synthetic pulp or a mixture thereof as well as plastic films such as polyester films of polyethylene terephthalate or polybutylene terephthalate or cellulose triacetate film, polystyrene film, polypropylene film or other polyolefin films.
  • the raw paper for use in the present invention is made from materials which are generally used for photographic papers. Specifically, natural pulp derived from soft wood or hard wood is used as a main raw material for the paper, which may optionally contain filler such as fine grains of clay, talc, calcium carbonate or urea resin, a sizing agent such as resin, alkylketene dimer, higher fatty acid, paraffin wax or alkenylsuccinic acid, a paper reinforcing agent such as polyacrylamide and a fixing agent such as papermaker's alum earth or cationic polymer.
  • filler such as fine grains of clay, talc, calcium carbonate or urea resin
  • a sizing agent such as resin, alkylketene dimer, higher fatty acid, paraffin wax or alkenylsuccinic acid
  • a paper reinforcing agent such as polyacrylamide
  • a fixing agent such as papermaker's alum earth or cationic polymer.
  • a natural paper containing a reactive sizing agent such as alkylketene dimer or alkenylsuccinic acid and having a pH of from 5 to 7 (determined by conventional manner, that is, water is dropped on the paper, placing a plane electrode, for example, a pH-meter having a plane-electrode type GST-5313F manufactured by Toa Electrowave Industries (Japan), and the pH at the portion where water is dropped is measured after pH becomes constant) is preferred.
  • the natural pulp may be substituted by synthetic pulp, or a mixture comprising natural pulp and synthetic pulp in a proper ratio can also be used.
  • the surface of the pulp may be sized with a film-forming polymer such as gelatin, starch, carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol or modified polyvinyl alcohol.
  • the modified polyvinyl alcohol includes carboxyl-modified or a silanol-modified one or a copolymer with acrylamide.
  • the amount of the polymer to be coated may be from 0.1 to 5.0 g/m2, preferably from 0.5 to 2.0 g/m2.
  • the film-forming polymer may contain, if desired, an antistatic agent, a fluorescent brightening agent, pigment and a defoaming agent.
  • the raw paper for use in the present invention can be prepared by processing a pulp slurry comprising the pulp mentioned above and, if desired, other additives such as a filler, a sizing agent, a paper reinforcing agent and a fixing agent, with a papermaking machine such as Fourdrinier machine, followed by drying and rolling the paper strip thus formed.
  • a papermaking machine such as Fourdrinier machine
  • the paper strip is sized on the surface thereof, and it is subjected to calender treatment between the drying step and the rolling step.
  • the calender treatment may be effected either before or after the surface-sizing treatment.
  • the determination of whether the raw paper to be used as the substrate of the support for the photographic materials of the present invention is a neutral paper or not can be performed by measuring the pH value thereof using a plane-electrode type GST-5313F (manufactured by Toa Electrowave Industries, Japan) as an electrode.
  • a neutral paper preferably has a pH of 5 or more, and preferably up to 9, and more preferably up to 7.
  • the waterproof resin layer may also be provided in the preferred reflection color photographic material according to the invention.
  • the waterproof resin layer such as a vinyl chloride resin, may constitute the support by itself.
  • the waterproof resin for use in the present invention is one preferably having a water absorption (% by weight) of 0.5 or less, more preferably 0.1 or less, including, for example, polyalkylenes (e.g., a polymer of ethylene, or propylene or copolymer thereof), vinyl polymers or copolymers of vinyl compounds (e.g., a polymer of styrene and acrylate or copolymer thereof) and polyesters and copolyesters.
  • polyalkylene resins e.g., a polymer of ethylene, or propylene or copolymer thereof
  • vinyl polymers or copolymers of vinyl compounds e.g., a polymer of styrene and acrylate or copolymer thereof
  • polyesters and copolyesters e.g., polyesters and copolyesters.
  • Preferred are polyalkylene resins, and low density polyethylene, high density polyethylene, polypropylene and blends thereof are especially used among
  • the thickness of the resin layer may be from 5 to 200 »m, especially from 10 to 40 »m.
  • the formation of the resin layer in general, is carried out by kneading a white pigment together with the resin by a melt blending method and extruding through a melt extruder to laminate the blend on a support substrate.
  • Unsaturated organic compounds having one or more polymerizable carbon-carbon double bonds on one molecule e.g., methacrylate compounds
  • the polymer may be coated on a support substrate and then hardened by irradiation with electron rays to form a waterproof resin layer thereon.
  • a white pigment and other additives may be dispersed in the unsaturated organic compound. Any other resins may also be dispersed into the compound.
  • the waterproof resin layer on the support substrate for use in the present invention, various lamination methods as described in, for example, New Handbook for Lamination Coating (edited by Kako Kijutsu Kenkyu-kai, Japan) may be used.
  • the dry lamination method, and the non-solvent dry lamination method can be used.
  • any means selected from the gravure roll coating method, the wire bar coating method, the doctor blade coating method, the reverse roll coating method, the dip coating method, the air knife coating method, the callendar coating method, the kiss coating method, the squeeze coating method and the Fountain type coating method can be employed.
  • the waterproof resin contains a white pigment.
  • suitable white pigments include rutile-type titanium oxide, anatase-type titanium oxide, barium sulfate, calcium sulfate, silicon oxide, zinc oxide, titanium phosphate and aluminium oxide.
  • the surface of the fine grains of the titanium oxide pigment is preferably surface-treated with an inorganic oxide such as silica or aluminium oxide and a dihydric or tetrahydric alcohol such as 2,4-dihydroxy-2-methylpentane or trimethylolethane as described in JP-A-58-17151, separately or in combination.
  • the fine grains have a mean grain size of from 0.05 to 0.4 »m, and preferably from 0.1 to 0.3 »m.
  • the surface of the support is preferably treated by corona discharge, glow discharge or flame treatment and a protective layer group for silver halide photographic materials is provided on the thus surface-treated support.
  • the total thickness of the support is preferably from 30 to 350 g/m2 (from about 30 to 400 »m), more preferably from 50 to 200 g/m2.
  • the waterproof resin layer is preferably from 5 to 200 »m, more preferably from 10 to 40 »m.
  • the support for use in the present invention contains fine grains of a white pigment (especially preferably titanium oxide) in a density of 10% by weight or more, preferably 12% by weight or more, more preferably from 15% by weight to 60% by weight, as dispersed in the waterproof resin layer.
  • the fine grains of white pigment are preferably dispersed densely and uniformly (that is, in order that there is no part sparsely containing the fine grains) in the surface of the waterproof resin layer or in a thickness of e.g 10 »m from the surface of the layer.
  • the surface of the resin layer or the thickness of the layer from the surface to about 0.1 »m, preferably about 50 nm (500 ⁇ ) is subjected to glow discharge for ion-sputtering so as to sputter the surface resin, and the fine grains thus exposed are observed with an electronic microscope.
  • the photographed possessory area of the fine grains on the surface of the thus treated resin layer is obtained from the electromicroscopic photograph and the fluctuation coefficient of the possessory area ratio (%) is calculated for evaluation of the intended dispersibility.
  • the ion-sputtering method employable for this purpose is described in detail in Y. Murayama and K. Kashiwagi, Technique for Surface Treatment with Plasma (Kikai-no Kenkyu), Vol. 33, No. 6 (1981).
  • the white pigment is fully kneaded with the resin component in the presence of a surfactant. It is also preferred that the surface of the pigment grains be pre-treated with the above-mentioned di- to tetra-hydric alcohol.
  • the possessory area ratio (%) of the fine white pigment grains per a determined unit area is obtained by dividing the observed area into the adjacent unit areas having a size of 6 »m x 6 »m and determining the possessory area ratio (%) (Ri) of the fine grains as projected in the unit area.
  • the fluctuation coefficient of the possessory area ratio (%) is obtained as the ratio of (s/ R ) of the standard deviation (s) of (Ri) to the mean value ( R ) of (Ri).
  • the number (n) of the unit areas as intended for the purpose is preferably 6 or more. Accordingly, the fluctuation coefficient (s/ R ) can be obtained from the following formula:
  • the fluctuation coefficient of the possessory area ratio(%) of the fine pigment grains is 0.20 or less, preferably 0.15 or less, and more preferably 0.08 or less.
  • the fluctuation coefficient is 0.08 or less, the dispersion of the grains is substantially "uniform".
  • the pigment density is 12% by weight or more and S/ R is 0.15 or less.
  • the photograph formed on the material would visually have a whitened background and have a worsened sharpness of the image formed.
  • the strength of the primary diffusive reflected light (see Hand Book of Science of Color (new edit.), edited by Japan Color Society: published by Tokyo Univ. Publication Association; Sept. 1985, Chap. 18) to the incident light may be elevated and the extension of the diffusive light can be reduced.
  • the improved effect of the present support is displayed not only for the incident light for exposure of the photographic material but also for the incident light for visually seeing the photograph, which is one characteristic advantage attainable by the present invention.
  • the colored layer used in the present invention can be decolored after photographic processing, e.g., development, bleach-fixation, rinsing or stabilization, and is provided between the support and the silver halide photographic light-sensitive layer.
  • Fixation of a light absorbent (a dye and/or colloidal silver) in the colored layer may effectively impart an anti-halation effect to the silver halide light-sensitive layer without a reduction of the spectral sensitivity nor an increase of fog.
  • Suitable light absorbents included colloidal silver (black to yellow) and/or dyes. Colloidal silver and a dye are preferably used in amounts such that the colloidal silver provides reflect density of from 0.1 to 1.5, and the dye provides transmission density of from 0.1 to 1.2. Provision of the colored layer is effective for more satisfactorily inhibiting the deterioration of the sharpness of the image which would be caused by the extension of the diffused light from the support.
  • a colloidal silver emulsion is preferably used as the light absorbent. Any and every colloidal silver emulsion which is generally used for picture-taking color photographic materials can be used for this purpose. Black or yellow colloidal silver can be used.
  • the colloidal silver can be prepared in accordance with the methods described in, for example, US-A-2,688,601 and US-A-3,459,563 and BE-B-622,695.
  • the colloidal silver for use in the present invention is preferably fully desalted to have an electroconductivity of not higher than 1800 »scm ⁇ 1, after preparation.
  • the content of the colloidal silver in the colloidal silver-containing layer is from 0.01 to 0.5 g/m2, and preferably from 0.05 to 0.2 g/m2, as silver.
  • Dyes may also be incorporated into the colored layer, together with the colloidal silver, to inhibit irradiation, stabilize the sensitivity, improve the safelight stability and improve the spectral sensitivity distribution.
  • the colored layer may contain a dye and a cationic polymer for mordanting the same, in combination.
  • the polymer preferably has a molecular weight of at least 5,000.
  • the cationic polymer which is preferably used in the present invention is a non-coloring polymer having at least one hydrogen-containing ammonium base in the cation site which functions as an anion exchange polymer.
  • cationic polymers represented by the following general formula (I) are preferred for use in the present invention.
  • A represents a monomer unit derived from a copolymerizable monomer having at least two copolymerizable ethylenic unsaturated groups, one of which is in the side chain of the monomer.
  • B represents a monomer unit derived from a copolymerizable ethylenic unsaturated monomer.
  • R1 represents a hydrogen atom, a lower alkyl group or an aralkyl group.
  • Q represents a single bond or an alkylene group, an arylene group, an aralkylene group, or L represents an alkylene group, an arylene group or an aralkylene group.
  • R represents an alkyl group.
  • G represents R2, R3, R4, R5, R6, R7, R8 and R9 each represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. These may be same as or different from each other. The above-mentioned groups may optionally be substituted.
  • X ⁇ represents an anion.
  • any two or more of Q, R2, R3, and R4 or Q, R5, R6, R7, R8 and R9 may be bonded to each other to form a ring structure together with the adjacent nitrogen atom.
  • R2, R3, and R4 must be a hydrogen atom.
  • x, y and z each represent a molar percentage, and x is from 0 to 60, y is from 0 to 60 and z is from 30 to 100.
  • Examples of the monomers A include divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol dimethacrylate and tetramethylene dimethacrylate.
  • divinylbenzene and ethylene glycol dimethacrylate are especially preferred.
  • Examples of the ethylenic unsaturated monomers represented by B include ethylene, propylene, 1-butene, isobutene, styrene, ⁇ -methylstyrene, vinylketone, monoethylenic unsaturated esters of aliphatic acids (e.g., vinyl acetate, allyl acetate), ethylenic unsaturated monocarboxylic acid or dicarboxylic acid esters (e.g., methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate), monoethylenic unsaturated compounds (e.g., acrylonitrile) and dienes (e.g., butadiene, is
  • R1 is preferably a hydrogen atom or a lower alkyl group having from 1 to 6 carbon atoms (e.g., methyl, ethyl, n-propyl, n-butyl, n-amyl, n-hexyl) or an aralkyl group (e.g., benzyl).
  • R1 is especially preferably a hydrogen atom or a methyl group.
  • Q is preferably an optionally substituted divalent alkylene group having from 1 to 12 carbon atoms (e.g., methylene or -(CH2)6-), an optionally substituted phenylene or an optionally substituted aralkylene having from 7 to 12 carbon atoms (e.g., or In addition, the following groups are also preferred for Q.
  • 1 to 12 carbon atoms e.g., methylene or -(CH2)6-
  • phenylene or an optionally substituted aralkylene having from 7 to 12 carbon atoms e.g., or
  • the following groups are also preferred for Q.
  • L represents an optionally substituted alkylene group having from 1 to 6 carbon atoms, or an optionally substituted arylene group, or an optionally substituted aralkylene group having from 7 to 12 carbon atoms. Especially preferably, it is an optionally substituted alkylene group having from 1 to 6 carbon atoms.
  • R represents an alkyl group having from 1 to 6 carbon atoms.
  • G represents or
  • R2, R3, R4, R5, R6, R7, R8 and R9 are the same or different and each is preferably a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, an aryl group having from 6 to 20 carbon atoms, or an aralkyl group having from 7 to 20 carbon atoms.
  • the alkyl group, aryl group and aralkyl group include a substituted alkyl group, a substituted aryl group and a substituted aralkyl group, respectively.
  • the unsubstituted alkyl group preferably has from 1 to 12 carbon atoms, more preferably from 4 to 10 carbon atoms, and it includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, isoamyl, n-hexyl cyclohexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and n-dodecyl groups.
  • Example of the substituted alkyl group include an alkoxyalkyl group (e.g., methoxymethyl, methoxyethyl, methoxybutyl, ethoxyethyl, ethoxypropyl, methoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl, vinyloxyethyl), a cyanoalkyl group (e.g., 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl), a halogenated alkyl group (e.g., 2-fluoroethyl, 2-chloroethyl, 3-fluoropropyl), an alkoxycarbonylalkyl group (e.g., ethoxycarbonylmethyl), and an allyl group, a 2-butenyl group and a propargyl group.
  • an alkoxyalkyl group e.g., methoxymethyl, methoxyethyl, meth
  • the aryl group includes an unsubstituted aryl group (e.g., phenyl, naphthyl) and a substituted aryl group, for example, an alkylaryl group (e.g., 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl), an alkoxyaryl group (e.g., 4-methoxyphenyl, 3-methoxyphenyl, 4-ethoxyphenyl), and an aryloxyaryl group (e.g., 4-phenoxyphenyl).
  • the aryl group preferably has from 6 to 14 carbon atoms, more preferably from 6 to 10 carbon atoms. It is especially preferably a phenyl group.
  • the aralkyl group includes an unsubstituted aralkyl group (e.g., benzyl, phenethyl, diphenylmethyl, naphthylmethyl) and a substituted aralkyl group, for example, an alkylaralkyl group (e.g., 4-methylbenzyl, 2,5-dimethylbenzyl, 4-isopropylbenzyl), an alkoxyaralkyl group (e.g., 4-methoxybenzyl, 4-ethoxybenzyl), a cyanoaralkyl group (e.g., 4-cyanobenzyl), a perfluoroalkoxyaralkyl group (e.g., 4-pentafluoropropoxybenzyl, 4-undecafluorohexyloxybenzyl) and a halogenated aralkyl group (e.g., 4-chlorobenzyl, 4-bromobenzyl, 3-chlorobenzyl).
  • X ⁇ represents an anion, for example, a halide ion (e.g., chloride or bromide ion), an alkyl- or arylsulfonate ion (e.g., methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate), an acetate ion, a sulfate ion or a nitrate ion.
  • chloride ion, acetate ion and sulfate ion are preferred.
  • any two or more of Q, R2, R3, and R4, may be bonded together to form a cyclic structure together with the adjacent nitrogen atom.
  • the cyclic structure include pyrrolidine ring, piperidine ring, morpholine ring, pyridine ring, imidazole ring and quinuclidine ring.
  • pyrrolidine ring, morpholine ring, piperidine ring, imidazole ring and pyridine ring are especially preferred.
  • any two or more of Q, R5, R6, R7, R8 and R9 may be bonded together to form a cyclic structure together with the adjacent nitrogen atom, and the cyclic structure is especially preferably a 6 membered or 5-membered ring.
  • x indicates from 0 to 60 mol%, preferably from 0 to 40 mol%, more preferably from 0 to 30 mol%.
  • y indicates from 0 to 60 mol%, preferably 0 to 40 mol%, more preferably from 0 to 30 mol%.
  • z indicates from 30 to 100 mol%, preferably from 40 to 95 mol%, more preferably from 50 to 85 mol%.
  • G is preferably a basic residue having a pKa value of 4.5 or more, especially 7 or more, in an aqueous solution.
  • a polymer latex is especially preferred from the view point of the film-forming quality thereof.
  • a crosslinking monomer such as divinylbenzene is generally used as a monomer component.
  • a crosslinking monomer is not indispensable, depending upon the kind of the monomer to be used.
  • the polymers of the formula (I) for use in the present invention are generally prepared by copolymerizing the above-mentioned copolymerizable monomer having at least two ethylenic unsaturated groups and ethylenic unsaturated monomer together with an unsaturated monomer of a formula: in which R1, R2, R3 and Q have the same meanings as defined above, for example, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N-(N,N-dimethylaminopropyl)acrylamide, N-(N,N-dihexylaminomethyl)acrylamide, 3-(4-pyridyl)propyl acrylate, N,N-dimethylaminomethylstyrene, N,N-dieth
  • the polymers of formula (I) for use in the present invention may also be prepared by copolymerizing the above-mentioned copolymerizable monomer having at least two ethylenic unsaturated groups and ethylenic unsaturated monomer together with an unsaturated monomer of a formula: in which R1, R2, R3, R4, X and Q have the same meanings as defined above, for example, N,N dimethylaminoethyl methacrylate hydrochloride, N,N-diethyl aminoethyl methacrylate sulfate, N,N-dimethylaminoethyl acrylate hydrochloride, N,N-diethylaminoethyl acrylate acetate, N,N-dimethylaminostyrene hydrochloride, N,N-diethylaminomethylstyrene sulfate, 2-vinylpyridine hydrochloride or 4-vinylpyridine hydrochloride.
  • the polymers of formula (I) for use in the present invention may further be prepared by copolymerizing the above-mentioned copolymerizable monomer having at least two ethylenic unsaturated groups and an ethylenic unsaturated monomer together with an unsaturated monomer of the formula: in which X represents a halogen atom (e.g., chlorine, bromine) or a sulfonic acid ester group (e.g., p-toluenesulfonyloxy) and R1 and Q have the same meanings as defined above, for example, ⁇ -chloroethyl methacrylate, ⁇ -p-toluenesulfonyloxyethyl methacrylate or chloromethylstyrene, followed by reacting the resulting copolymer with an amine having a structure of (where R2, R3 and R4 have the same meanings as defined above), for example, dimethylamine, diethylamine, di
  • the polymers of the formula (I) for use in the present invention can be prepared by copolymerizing the above-mentioned copolymerizable monomer having at least two ethylenic unsaturated groups and ethylenic unsaturated monomer together with an unsaturated monomer of a formula: in which R1, R5 and Q have the same meanings as defined above, for example, methyl vinyl ketone, methyl (1-methylvinyl) ketone, ethyl vinyl ketone, ethyl (1-methylvinyl) ketone, n-propyl vinyl ketone, diacetone acrylamide or diacetone acrylate, especially preferably methyl vinyl ketone, ethyl vinyl ketone, diacetone acrylamide or diacetone acrylate, followed by reacting the resulting copolymer with a compound of a formula: in which R6, R7, R8 and R9 have the same meanings as defined above, for example, aminoguanidine bi
  • the above-mentioned polymerization reaction can be carried out by any conventional method of solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization or dispersion polymerization. Solution polymerization and emulsion polymerization are preferred.
  • the emulsion polymerization can be carried out generally in the presence of at least one emulsifying agent selected from anionic surfactants (e.g., sodium dodecylsulfate, or Triton 770, a commercial product from Rhom & Haas), cationic surfactants (e.g., octadecyltrimethyl ammonium chloride), non-ionic surfactants (e.g., EMALEX NP-20, a commercial product from Nippon Emulsion), gelatin and polyvinyl alcohol, together with a radical polymerization initiator (e.g., combination of potassium persulfate and sodium hydrogen sulfite, a commercial product from Wako Pure Chemicals in the trade name of V-50), at a temperature of generally from about 30°C to about 100°C, preferably from about 40°C to about 80°C.
  • anionic surfactants e.g., sodium dodecylsulfate, or Triton 770,
  • the above-mentioned reaction of forming the corresponding ammonium salt from the copolymer is carried out at a temperature of generally from about -10°C to about 40°C, especially preferably from about 0°C to about 30°C.
  • copolymers for use in the present invention can be prepared in one reactor vessel throughout the complete manufacture process with ease.
  • Coolymer Dispersion (6) Production of ethylglycol dimethacrylate-butyl methacrylate-diethylaminomethylstytene hydrochloride Coolymer Dispersion (6) :
  • emulsifier Nasan TRAX H-54, a commercial product from Nippon Fats and Oils
  • 75 g of distilled water 5.95 g of ethylene glycol dimethacrylate, 4.98 g of butyl methacrylate and 5.34 g of chloromethylstyrene were put in a reactor vessel and stirred.
  • 0.2 g of polymerization initiator V-50 commercial product from Wako Pure Chemicals
  • the reaction mixture was cooled to 40°C, and 108 g of distilled water and 62 g of isopropyl alcohol were dropwise added thereto over a period of 15 min. The whole was then continuously stirred for 2 h at 40°C and then filtered to obtain a polymer dispersion having a solid concentration of 8.16% by weight and an amine content of 1.31 ⁇ 10 ⁇ 4 eqv/g.
  • the resulting solution was heated to 80°C under a nitrogen stream.
  • a solution of 0.5 g of potassium persulfate dissolved in 20 ml of distilled water was added to the vessel and successively continuously stirred for 5 h. After cooling, 100 g of distilled water were added and the resulting mixture was filtered to obtain an aqueous polymer solution of Compound (17) having a solid content of 17.0% by weight and an amine concentration of 8.17 ⁇ 10 ⁇ 4 eqv/g.
  • a hydrophilic protective colloid may be used as a binder for the colored layer used in the present invention.
  • Such colloid includes, for example, gelatin, modified gelatins, gelatin derivatives and graft polymers of gelatin and other polymers. These may be used in combination with proteins such as albumin or casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose or cellulose sulfates; saccharide derivatives such as dextran, sodium alginate or starch derivatives; and homopolymers or copolymers such as polyvinyl alcohol, partially acetallized polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamide, acrylic acid or methacrylic acid copolymers or polyvinyl pyrazole.
  • gelatin is used as the hydrophilic colloid, and the gelatin may be a so-called lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin.
  • the gelatin is especially preferably one having a narrow molecular weight distribution for the purpose of attaining rapid processing.
  • the molecular weight distribution of gelatin can be determined by, for example, the GPC method (gel permeation chromatography method).
  • the GPC method is described in detail in JP-A-62-87952 (main text and Example 1).
  • the colored layer used in the present invention and other hydrophilic colloid layers constituting the photographic material of the present invention are hardened with an inorganic or organic hardening agent.
  • suitable hardening agents include, for example, chromium salts, aldehydes (e.g., formaldehyde, glutaraldehyde), N-methylol compounds (e.g., dimethylolurea), active vinyl compounds (e.g., 1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methylether, N,N′-methylenebis( ⁇ -vinylsulfonyl)propionamide), active halogen compounds described in, for example, US-A-3,325,287 (e.g., 2,4-dichloro-6-hydroxy-s-triazine), mucohalogenic acids (e.g., mucochloric acid), N-carbamoylpyridinium salts (e.
  • hardening agents having two or more vinylsulfonyl groups for example, those described in JP-B-47-24259, JP-B-49-13563 and JP-B-57-240902
  • hardening agents having two or more active vinyl groups for example, those described in JP-A-53-41220, JP-A-53-57257, JP-A-59-162546 and JP-A-60-80846) as well as the compounds described in JP-A-62-222242, JP-A-62-245261 and JP-A-62-109050 and JP-A-62-295045 are especially preferably used, as these do not interfere with the cation site of the polymers to be used in the present invention.
  • the dyes to be used in accordance with the present invention are those having a selected light absorption in the spectral sensitivity range of the light-sensitive layer (to which the effect of irradiation inhibition or antihalation is intended to be provided) of the color photographic material of the present invention and especially those having a molar extinction coefficient of 102 l.mol.cm ⁇ 1 or more.
  • dyes which may be decolored by decoloration after development processings or which may be dissolved out of the photographic material during photographic processing are especially preferred as the dye.
  • the dye is preferably used in an amount of from 1 to 500 mg/m2, and more preferably from 10 to 100 mg/m2.
  • a dye which is substantially insoluble in an aqueous solution having pH of not higher than 7.0 is preferably used as a solid fine grain like dispersion thereof in a colloid together with a dispersion aid.
  • solid fine grain like means a state that the dye grains having a mean grain size (projected, circle approximate) of not more than 1 »m, and preferably from 0.01 »m to 0.5 »m are dispersed in a colloid layer, said dye grains being substantially non-diffusible to other adjacent layer(s) and not aggregating coarser than about 3 »m.
  • nonionic surface active agents such as the compounds described in patent publications cited in JP-A-62-215272, pages 649-668, and the compounds shown as practical compounds W-1 to W-99 in JP-A-62-215272, the surface active agents described in JP-B-56-36415 and 59-31688, and the surface active agents shown by formulae [VII], [VIII], and [IX] described in Japanese Patent Application No. 62-118519 can be used.
  • dispersion aid water-soluble organic solvents such as e.g. dimethylformamide, methanol, ethanol and dimethylsulfonylamide can be used.
  • dispersion aid hydrophilic colloids such as e.g. gelatin, casein, hydroxyethyl cellulose, poly-N-vinylpyrrolidone, polyacrylic acid and gelatin derivatives and also alkaline water can be used.
  • the solid fine grain dispersion of dye can be prepared by a method of dissolving dye solids in a water-soluble organic solvent and dispersing the solution in a neutral or acidic aqueous colloid solution, particularly preferably a method of wetting dye solids with water or an insoluble liquid, kneading the wet dye solids together with a dispersion aid, finely granulating the dye solids in a mill and dispersing them in an aqueous colloid solution, a method of fine-powdering dye solids using ultrasonic waves and dispersing the powdered dye in a colloid solution using a surface active agent as a dispersion aid, or a method of dissolving dye solids in alkaline water and dispersing the solution in an acidic aqueous colloid solution.
  • the dye or the aqueous colloid solution is used together with an organic acid such as e.g. citric acid, oxalic acid, acetic acid or tartaric acid.
  • an organic acid such as e.g. citric acid, oxalic acid, acetic acid or tartaric acid.
  • the solid fine grains of dye for use in this invention may be fine crystals of the dye, micell-structural fine grains of the dye, or finely aggregated particles of the dye.
  • the grains' size of the solid fine grains can be measured by observing the section of a colloid layer containing them using a transmission type electron microscope.
  • substantially insoluble in an aqueous solution means that the dispersed fine grains are insoluble to an extent capable of keeping the dispersed state in a hydrophilic colloid such as an aqueous gelatin solution having pH of not higher than 7.
  • a dye having a solubility in an aqueous solution of pH 7 or less at room temperature (24°C) of not more than 10% by weight, and preferably not more than 5% by weight is preferred.
  • the dyes can be selected from conventional known dyes, for example, arylidene dyes, styryl dyes, butadiene dyes, oxonole dyes, cyanine dyes, merocyanine dyes, hemicyanine dyes, diarylmethane dyes, triaryl dyes, azomethine dyes, azo dyes, metal-chelated dyes, anthraquinone dyes, stilbene dyes, chalcone dyes and indophenol dyes.
  • conventional known dyes for example, arylidene dyes, styryl dyes, butadiene dyes, oxonole dyes, cyanine dyes, merocyanine dyes, hemicyanine dyes, diarylmethane dyes, triaryl dyes, azomethine dyes, azo dyes, metal-chelated dyes, anthraquinone dyes, stilbene dyes, chalcone dyes and indo
  • they may also be selected from the dyes described in US-A-3,880,658, US-A-3,931,144, US-A-3,932,380, US-A-3,932,381 and US-A-3,942,987 and in J. Fabian & H. Hartmann, Light Absorption of Organic Colorants (published by Springer Verlag) as well as from non-diffusive analogues thereof.
  • the dyes for use in the present invention which have the coincidence with the light absorption characteristic and which can be decolored after development processings, can be selected from the functional dyes described in JP-A-63-271351, the dyes of formula (I) described in JP-A-62-21527, JP-A-62-293243 (pages 109 to 117), JP-A-63-208846 and JP-A-63-316853 and the dyes of the formula (II) described in Japanese Patent Application No. 62-226131.
  • dyes having a light absorption in the spectral sensitivity wavelength range of the light-sensitive layer or layers, preferably the layer adjacent to the colored layer, to be provided on the colored layer are used; and for correction of the light-sensitivity range, dyes having a light absorption in the sensitivity wavelength range to be corrected are used.
  • 80% or more of the dye to be used in the photographic emulsion layer or in other constitutional layers is preferably contained in the cationic polymer-containing layer.
  • the amount of dye to be added is advantageously from 0.01 to 10, preferably from 0.2 to 1, as the number of the anion groups in the dye, per cation site of the cationic polymer.
  • Preferred dyes for use in the present invention include the dyes described in JP-A-63-139947, JP-A-63-244034, JP-A-63-264745, Japanese Patent Application Nos. 61-314428, 62-226121, 62-277669 and 62-284448 for antihalation; and the dyes described in JP-A-63-200146, Japanese Patent Application Nos. 62-239032, 62-264396, 62-261052 and 62-247477 for correction of the spectral sensitivity.
  • Especially preferred dyes for use in the present invention include the dyes described in JP-A-63-139949, JP-A-63-244034, JP-A-63-316853, Japanese Patent Application Nos. 62-226131, and 62-284448 and JP-A-62-123454.
  • Dye-18, Dye-37 and Dye-43 described above are suitable for the solid fine grain dispersion and furthermore, Dye-45 can be also used for the solid fine grain dispersion.
  • the dyes for use in this invention shown by formulae (II), (III), (IV), (V) and (VI) described below are particularly preferred for the solid fine grain dispersion.
  • a colored layer e.g., a colored layer utilizing colloidal silver and a layer colored by utilizing a cation polymer capable of providing cation site as a mordant
  • the following features can be obtained.
  • the filter layer is properly formed while changing the layer construction of light-sensitive layers constituting the color photographic material, such as a blue-sensitive layer (BL), a green-sensitive layer (GL), and a red-sensitive layer (RL).
  • BL blue-sensitive layer
  • GL green-sensitive layer
  • RL red-sensitive layer
  • a filter layer can be formed by incorporating the solid fine grains of the dye in an interlayer.
  • B2 represents a basic nucleus having at least one substituent selected from a carboxy group, a sulfamoyl group, and a sulfonamido group (said basic nuclei may further have a substituent in addition to the aforesaid group), said basic nuclei being selected from pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole, and pyrrole;
  • R40 represents a hydrogen atom or an alkyl group;
  • R41 and R42 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group, or a sulfonyl group, said R41 and R42 may combine with each other to form a 5- or 6-membered ring;
  • R43 and R46 each represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group
  • the carboxyphenyl group of the acidic nucleus shown by A2 and the carboxyphenyl group of the electron attractive group shown by X3 or Y3 include not only a phenyl group having only one carboxy group but also a phenyl group having 2 or 3 carboxy groups.
  • the sulfamoylphenyl group, the sulfonamidophenyl group, and the hydroxyphenyl group of the acid nucleus shown by A2 and of the electron attractive group shown by X3 or Y3 each includes not only a phenyl group having only one sulfamoyl group, sulfonamido group or hydroxy group but also a phenyl group having 2 or 3 sulfamoyl groups, sulfonamido groups, or hydroxy groups.
  • the aforesaid carboxyphenyl group or the sulfamoylphenyl group, sulfonamidophenyl group and hydroxyphenyl group each may further have another substituent than the aforesaid groups [as to the substituent, there is no particular restriction if the substituent is a dissociative substituent having pKa (acid dissociation constant) in a solution of water and ethanol (1 : 1 by volume ratio) of at least 4 or a non-dissociative substituent].
  • pKa acid dissociation constant
  • the carboxyalkyl group of the acidic nucleus shown by A2 or of the electron attractive group shown by X3 or Y3 has preferably from 1 to 10 carbon atoms and specific examples thereof are carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 2-carboxypropyl, 4-carboxybutyl, and 8-carboxyoctyl.
  • the alkyl group shown by R40, R43, or R46 has preferably from 1 to 10 carbon atoms and specific examples thereof are methyl, ethyl, n-propyl, isoamyl, and n-octyl.
  • the alkyl group shown by R41 or R42 has preferably from 1 to 20 carbon atoms and specific examples thereof are methyl, ethyl, n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl, and isopropyl.
  • the alkyl group may have a substituent [such as a halogen atom (e.g., chlorine or bromine), a nitro group, a cyano group, a hydroxy group, a carboxy group, an alkoxy group (e.g., methoxy and ethoxy), an alkoxycarbonyl group (e.g., methoxycarbonyl and i-propoxycarbonyl), an aryloxy group (e.g., phenoxy), a phenyl group, and amido group (e.g., acetylamino and methanesulfonamido), a carbamoyl group (e.g., methylcarbamoyl and ethylcarbamoyl), and a sulfamoyl group (e.g., methylsulfamoyl and phenylsulfamoyl)].
  • a substituent such as a halogen atom (e.
  • the aryl group shown by R41 or R42 is preferably a phenyl group or a naphthyl group and may have a substituent such as the group illustrated above as the substituent for the alkyl group shown by R41 or R42 and an alkyl group (e.g., methyl and ethyl).
  • the acyl group shown by R41 or R42 has preferably from 2 to 10 carbon atoms and specific examples thereof are acetyl, propionyl, n-octanoyl, n-decanoyl, isobutanoyl, and benzoyl.
  • alkylsulfonyl group and the arylsulfonyl group shown by R41 and R42 are methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl and o-carboxybenzenesulfonyl.
  • the alkoxy group shown by R43 or R46 has preferably from 1 to 10 carbon atoms and specific examples thereof are methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, and isopropoxy.
  • halogen atom shown by R43 or R46 there are chlorine, bromine, and fluorine.
  • ring formed by R41 and R44 or by R42 and R45 there is, for example, a durolysine ring.
  • examples of the 5- or 6-membered ring formed by R41 and R42 are, for example, a piperidine ring, a morpholine ring, and a pyrrolidine ring.
  • the methine group shown by L1, L2, and L3 may have a substituent such as, e.g., methyl, ethyl, cyano, phenyl, hydroxypropyl and a chlorine atom.
  • the aforesaid dyes for use in this invention can be easily synthesized by the methods described in WO 88/04794, EP-A-274,723, JP-A-52-92716, 55-155350, 55-155351, 61-205934, and 48-68623, US-A-2,527,583, US-A-3,486,897, US-A-3,746,539, US-A-3,933,798, US-A-4,130,429, and US-A-4,040,841 and by similar manners to the aforesaid methods.
  • the cationic polymer is dispersed in the hydrophilic colloid in the form of an aqueous solution or a latex.
  • a dye may further be added to give a coating liquid for the colored layer.
  • a master coating liquid to which previously a dye is added may be diluted and dispersed in the hydrophilic colloid to form a coating liquid.
  • the dispersion containing a water-soluble cationic polymer would coagulate relatively easily, thus, a small amount of dye is used relative to the cationic polymer.
  • the amount of the cationic polymer to be used is, although this can vary in accordance with the condition in the use thereof, preferably from about 1 g to about 100 g, more preferably from about 1 to about 50 g, especially preferably from about 1 to about 20 g, per 100 g of the hydrophilic protective colloid.
  • the cationic polymer is used in an amount of 0.1 or more, preferably from 0.1 to 100, especially preferably from 1 to 5, as the number of the cation sites of the polymer, per one anionic group of the anionic compound of the dye to be used.
  • the amount of the water-soluble cationic polymer to be used is preferably from 1 to 20 g per 100 g of the hydrophilic protective colloid, and it corresponds to from 5 to 30 cation sites of the polymer to one anionic group of an acidic dye.
  • the coating liquid for the colored layer contains a non-ionic, ampholytic or anionic surfactant, and preferably it contains a cationic surfactant.
  • a water-soluble cationic polymer it is preferably combined with a polymer latex dispersion, especially with a cationic polymer latex dispersion.
  • the water soluble cationic polymer and the cationic polymer latex dispersion may be used in an optional proportion, however, it is preferable that the weight ratio of the amount of the polymer in the latex dispersion to the amount of the water soluble cationic polymer is not more than 1/2.
  • the mean grain size of the fine grains of the cationic polymer latex for use in the present invention is 1 »m or less, preferably from 1 to 0.001 »m, especially from 0.2 to 0.01 »m, and the grain size distribution of the grains is preferably narrow.
  • Other polymer latexes as described in US-A-3,411,911 and US-A-3,411,912 and JP-B-45-5331 can also be co-used in the photographic constitutional layers.
  • an anionic compound such as an acidic dye is adsorbed on the polymer and dispersed
  • it is preferred that the anionic compound is previously adsorbed on the cation site of the polymer and then dispersed.
  • the anionic compound is prevented from being desorbed by the action of the co-existing anionic surfactant and the anionic group for the hydrophilic colloid itself.
  • the colored layer is coated on the support, and it may be directly coated on the white pigment-containing waterproof resin layer and dried thereon. It is preferred to provide an interlayer between the support and the colored layer. Any other silver halide light-sensitive layer may be inserted between the two layers. Two or more colored layers may be provided in a photographic material. The colored layer is provided between the support and the silver halide light-sensitive layer closest to the support. It is preferred that the colored layer is provided so that the spectral sensitivity distribution of the silver halide light-sensitive layer between the colored layer and the support may be corrected.
  • dyes are usually included therein and preferably differ from each other.
  • the colored layer may be provided between the support and the blue sensitive layer.
  • the colored layer acts as an antihalation layer.
  • the colored layer may also be provided between two emulsion layers, for example, between the green sensitive layer and the red sensitive layer.
  • the colored layer acts as an antihalation layer for the red sensitive layer and also acts as an irradiation inhibiting layer having light filtering effect for the green and blue sensitive layers (also acts as an antihalation layer).
  • the thickness of the colored layer is preferably from 0.1 to 10 »m, preferably from 0.2 to 5 »m.
  • the maximum spectral reflection density thereof is preferably 0.2 or more, especially preferably from 0.3 to 1.5.
  • the silver halide emulsion to be used for preparing the photographic material of the present invention is preferably a silver chlorobromide emulsion, and it may be prepared in accordance with the methods described in P. Glafkides, Chimie et Physique Photographique (published by Paul Montel, 1967), G.F. Duffin, Photographic Emulsion Chemistry (published by Focal Press, 1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion (published by Focal Press, 1964). Specifically, it may be prepared by any method including the acid method, neutral method and ammonia method, but it is preferably prepared by the acid method.
  • the reaction of the soluble silver salt and soluble halide(s), can be carried out by methods including the single jet method, double jet method or combination thereof.
  • the double jet method is especially preferred so as to obtain the monodispersed grains for use in the present invention.
  • a so-called reverse mixing method where grains are formed under conditions of excess silver ions can also be employed.
  • One type of the double jet method i.e., a so-called controlled double jet method, where the silver ion concentration in the liquid phase to form silver chlorobromide is kept constant, may also be used.
  • a mono-dispersed silver chlorobromide emulsion which comprises grains having a regular crystal form and having a narrow grain size distribution and which is suited for use in the present invention can be obtained.
  • Suitable silver halide composition include compositions having a silver chloride content of 15 mol% or more.
  • the silver chloride content is preferably 95 mol% or more, and more preferably 98 mol% or more for the photographic material which is required to have rapid processability.
  • the composition of the silver halide may contain silver iodide in an amount not exceeding 1 mol%, but the photographic material which is required to have rapid processability desirably contains no silver iodide.
  • the silver halide grains for use in the present invention are silver chlorobromide grains having a silver chloride content of 90 mol% or more, they are preferably hetero-structural grains having a "localized phase" where the silver bromide content is different from that in the adjacent phase.
  • the localized phase may be in the inside and/or on the surface of the silver halide grain.
  • the localized phase may be on the surface of the grain non-uniformly or discontinuously or isolated from others on the surface Above all, the localized phase is preferably on the surface of the silver halide grain non-uniformly or is isolated from others.
  • the silver bromide content in the localized phase is preferably at least 5 mol%, more preferably 10 mol% or more, esepcially preferably 20 mol% or more.
  • the upper limit is preferably 70 mol%. If the silver bromide content is too high, the material would be desensitized under pressure, or the sensitivity or gradation would fluctuate in continuous development processing.
  • the silver bromide content in the localized phase as well as the difference in the silver bromide content between the localized phase and the base phase (area other than the localized phase in the grain) is varied depending on the proportion of the silver bromide to the total silver halide, the molar ratio of the bromide used, the speed of feeding the water-soluble bromide to base grains and the pAg and pH of the reaction solution in forming the silver halide grains.
  • a silver nitrate solution and a halogen ion are added at a determined ratio, during the step of forming the base grain or after forming the same, while properly controlling the pAg and pH values in the reaction system.
  • the silver chloride on the surface of the grain may be substituted by silver bromide by halogen substitution.
  • the so-called CR-compounds described in, for example, EP-B-0273404, EP-B-0273429, EP-B-0274330, GB-B-2,206,974 and JP-A-63-235939 are used and a water-soluble bromide and silver nitrate are added to the base grains or fine silver bromide grains are added thereto for physical-ripening, whereby the nonuniform or isolated localized phase, which are especially advantageous for the silver halide grains for use in the present invention, is formed on the base grain.
  • the hetero-structual grains for use in the present invention advantageously contain a metal ion selected from metal ions of Group VIII in the Periodic Table, for example, an iron ion, rhodium ion, iridium ion or platinum ion.
  • the metal ion is preferred to be incorporated into the localized phase or the base phase of the silver halide grains in a different concentration.
  • iridium ion or iron ion is incorporated into the localized phase while a different metal ion selected form osmium, iridium, platinium, ruthenium, palladium, cobalt and nickel ions or a complex ion thereof is incorporated into the base phase in combination.
  • metal ions of cadmium, zinc, lead, mercury and thallium ions may also be used.
  • the amount of the metal ion to be incorporated into the silver halide grain is from 10 ⁇ 8 to 10 ⁇ 5 mol per mol of silver halide.
  • the silver bromide content in the localized phase can be analyzed by an X-ray diffraction method (for example, as described in " New Experimental Chemistry, Lecture VI, Analysis of Structure " (edited by Japan Chemical Society and published from Maruzen, Japan) or XPS method (for example, as described in “ Surface Analysis - Application of IMA, Auger Electron and Photoelectronic Spectrography” (published by Kodansha, Japan).
  • the silver bromide content in the localized phase as existing non-uniformly or being isolated on the surface of the silver halide grain, especially in the edges or corners thereof, can be determined by the EDX (energy dispersive X-ray analysis) method (for example, described in H. Soejima, Electron Ray Microanalysis , published from Nikkan Kogyo Newspaper Co., 1987), with an EXD spectrometer as installed in a transmission type electron microscope, up to an accuracy of about 5 mol% with an aperture of from about 0.1 to about 0.2 »m diameter.
  • EDX energy dispersive X-ray analysis
  • the silver halide grains for use in the present invention may be regular crystal grains, for example, cubic or 6-hedral or 14-hedral grains having (100) plane or 8-hedral grains having (111) plane, or may also be tabular grains.
  • Such silver halide grains can selectively be formed by properly adjusting the pAg or pH value in the reaction solution for forming the silver halide grains, or by selectively using CR-compounds having a function of selectively adsorbing to (100) plane or (111) plane (for example, described in the above-mentioned patent specifications) or using any other appropriate organic compounds.
  • 6-hedral or 14-hedral silver halide grains having (100) plane and having the localized phase in the corner parts of the surface thereof as well as tabular silver halide grains having the localized phase in the corner parts or edge parts of the surface thereof are preferred for use in the present invention.
  • the color photographic paper according to the present invention is processed by a "printer processor" as described in, for example, JP-A-62-184446 to form an image. It is first imagewise exposed, for example, with a CRT exposure system and then, generally, immediately subjected to color development.
  • the color photographic paper according to the present invention which contains a silver chloride-rich silver halide emulsion is especially preferred to be rapidly processed.
  • the balance of the red-sensitivity (S R ), green-sensitivity (S G ) and blue-sensitivity (S B ) in general color photographic papers is low in the order of S B , S G and S R .
  • the light emitted from red-fluorescent bodies has a wavelength falling near the range of from 600 to 630 nm and near 700 nm, and therefore the bodies could hardly match with the red-sensitive wavelength for color photographic materials.
  • elevation of the spectral sensitivity of the preferred reflection color photographic material as weel as improvement of the proper wavelength distribution of the spectral sensitivity thereof is especially important.
  • the characteristic aspects of the preferable reflection color photographic material of the present invention are as follows: First, a silver chlorobromide emulsion having a high silver chloride content is used for the purpose of attaining rapid processing of the material. Second, multi-layered silver halide grains (halogen composition distribution) are used and the grains are particularly chemically sensitized and spectrally sensitized, for the purpose of obtaining a sufficient spectral sensitivity necessary for compensating the sensitivity as lowered because of the dye added to the material so as to efficiently inhibit the diffusion of the luminous flux of the light applied to the material for exposure thereof. Third, an anti-halation layer is provided on a new support.
  • the silver chloride-rich silver chlorobromide emulsion for use in the present invention is preferably one which can form a latent image mainly on the surface of the silver chlorobromide grains.
  • the silver chlorobromide emulsion for use in a preferred reflection color photographic material of the present invention is one substantially comprising silver chloride or silver chlorobromide, and it has a silver iodide content of 2 mol% or less, preferably 1 mol% or less, especially preferably 0.1 mol% or less. It has a silver chloride content of at least 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, especially preferably 95 mol% or more.
  • the balance component may be silver bromide, silver iodide or silver rhodanide.
  • the halogen components preferably form layers in the inside or surface of the silver halide grains, or are preferred to be differently and discontinuously isolated from others.
  • a silver bromide-localized phase which has a higher silver bromide content than the adjacent phases and is near the surface of the grain in layers or is discontinuously isolated from others, is used.
  • the silver content in the localized phase is 5 mol% or more, preferably 10 mol% or more, especially preferably from 20 mol% to 70 mol%.
  • the silver halide grains to be contained in the silver halide emulsion for use in the reflection color photographic material of the present invention may have any crystal habit, but they are preferably regular crystal grains such as cubic, 14-hedral or 8-hedral grains or tabular grains rather than spherical grains or polymorphic grains.
  • the silver halide grains are preferably multi-layered grains having different crystal structures in the inside of the grain or near the surface thereof. Especially preferred are grains having a layered structure composed of different halogen compositions or grains having a silver bromide-localized phase near the surface of the grain.
  • the grains are core/shell grains, it is preferred that the silver chloride content in the core part is higher than that in the shell part.
  • High silver chloride grains having a high silver chloride content for use in the photographic material of the present invention are generally formed only in the form of cubic grains composed of (100) plane, but they may be obtained also in the form of 8-hedral grains having (111) plane or tabular grains, as the case may be, by any particular means.
  • Preparation of 8-hedral grains having (111) plane is disclosed in JP-A-63-212932, JP-A-55-26589, Claes et al, Journal of Photographic Science , Vol. 21, page 39 (1973) and Wyrsh, International Congress of Photographic Science , III-13, page 122 (1978). The method described in JP-A-63-212932 is preferred.
  • X represents a divalent group, including an alkylene, arylene, alkenylene, -SO2-, -SO-, -O-, -S-, -CO- or -NR3-
  • R1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group
  • R2 represents a hydroxyl group, an alkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group or an arylthio group
  • Y represents -CO- or -SO2-
  • m represents 0 or 1
  • R3 represents a hydrogen atom, an alkyl group or an aryl group, and the groups may optionally be further substituted, as described in JP-A-63-41845, is preferably
  • the chloride concentration in the aqueous gelatin solution to be added during formation of the core grains is advantageously low, i.e., 0.15 mol/l or less.
  • the chloride concentration during the step of growing the grains is preferably 5 mol/l or less, especially from 0.07 to 3 mol/l.
  • the silver chlorobromide grains for use in the preferred reflection color photographic material can be formed by growing grains after forming core grains by adding silver ion and a chloride or bromide or a mixture thereof thereto preferably in the presence of the above-mentioned crystal habit-controlling compound.
  • fine silver halide grains for example fine silver bromide grains or fine silver chloride grains or a mixture thereof may be blended with a silver chloride, silver bromide or silver chlorobromide emulsion.
  • layer-structured grains or grains having an isolated and localized phase in the surface of the grain can be formed. Formation of the grains is preferably effected at 10 to 95°C, especially at 40 to 90°C.
  • Suitable silver halide solvents which can be used in formation of the grains include thiocyanates, thioethers and thioureas. Ammonia may also be used in an amount which does not badly interfere with the formation of the grains.
  • thiocyanates for example, those described in US-A-2,222,264, US-A-2,448,534 and US-A-3,320,069
  • thioether compounds for example, those described in US-A-3,271,157, US-A-3,574,628, US-A-3,704,130, US-A-4,297,439 and US-A-4,276,34
  • thione compounds for example, those described in JP-A-53-144319, JP-A-53-82408 and JP-A-55-77737
  • amine compounds for example, those described in JP-A-100717)
  • a cadmium salt, a zinc salt, a lead salt, a thallium salt, an indium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt or a complex salt thereof may be added.
  • use of an iridium salt, rhodium salt, iron salt or complex salt thereof is preferred.
  • a silver salt solution for example, aqueous AgNO3 solution
  • a halide solution for example, aqueous NaCl solution
  • the addition speed, the amount of the solutions to be added and the concentration of the solutions are elevated so as to accelerate the speed of grain formation.
  • the structure of the surface and near the surface of the high silver chloride grains used according to the present invention is important for the sensitivity, stability and reciprocity characteristics of the emulsions and for the stability of the latent images to be formed.
  • the method of forming grains as well as CR-compounds (inhibitor for halogen conversion or chemical sensitization) described in Japanese Patent Application No.s 62-86252, 62-329265 and 62-152330 are preferably employed.
  • the halide is preferably a halogen-donor which can control the feeding speed of chloride ion or bromide ion or control the amount of the ion to be fed.
  • a silver bromide-localized phase which has a silver bromide content different from the adjacent phase may be formed in the surface and/or near the surface of the silver halide grain.
  • the high silver chloride emulsion of the photographic material contains silver halide grains having a diameter preferably of from 0.1 to 3 »m as the diameter of a circle corresponding to the projected area of the grain, in an amount of 50% or more of the total grains as the projected area thereof.
  • the ratio of the circle-corresponding diameter to the grain thickness is preferably 2 or more, more preferably from 3 to 10, especially preferably from 5 to 8.
  • the high silver chloride emulsion according to the present invention is preferably a monodispersed emulsion, and the emulsion preferably has a dispersion coefficient of the circle-corresponding diameter (ratio of the standard deviation of the circle-corresponding diameter to the mean grain size) of 0.15 or less.
  • Another preferred characteristic feature of the present invention resides in the method of chemical sensitization of the silver halide grains.
  • the emulsion containing high silver chloride grains having a localized phase is subjected to gold sensitization, especially to a combination of sulfur sensitization and gold sensitization, in the presence of a compound for controlling the chemical sensitization.
  • This method is especially preferred to apply for production of the reflection colour photographic material.
  • the high silver chloride emulsion to be subjected to gold sensitization is especially a green-sensitive emulsion and a red-sensitive emulsion. Especially preferably, a red-sensitive emulsion is gold-sensitized.
  • the conditions for gold sensitization for the emulsions according to the present invention are not specifically limited, but the pH value is preferably from 3.0 to 8.5, especially from 5.0 to 7.5, the pAg value is preferably from 5.0 to 9.0, especially from 5.5 to 7.5, the temperature is preferably from 40 to 85°C, especially from 45 to 75°C, and the time is preferably from 10 to 200 min, especially from 30 to 120 min.
  • the pH value is preferably from 3.0 to 8.5, especially from 5.0 to 7.5
  • the pAg value is preferably from 5.0 to 9.0, especially from 5.5 to 7.5
  • the temperature is preferably from 40 to 85°C, especially from 45 to 75°C
  • the time is preferably from 10 to 200 min, especially from 30 to 120 min.
  • Preferred gold sensitizer compounds include the compounds described in US-A-2,399,083, US-A-2,540,085, US-A-2,540,086 and US-A-2,597,856.
  • suitable compounds include chloroauric acid and salts thereof, potassium gold cyanide, potassium gold thiocyanate and gold sulfide.
  • Suitable sulfur sensitizers which can be used in combination with the gold sensitizers include, for example, thiosulfates, sulfinic acid salts, thioureas, thiazoles, rhodanines and other compounds described in US-A-1,574,944, US-A-2,410,689, US-A-2,728,668 and US-A-3,656,955.
  • sulfur-containing compounds described in US-A-3,857,711, US-A-4,266,018 and US-A-4,054,457 can also be used for the purpose.
  • the amount of the gold sensitizer to be used in accordance with the present invention is from about 10 ⁇ 8 mol to about 10 ⁇ 5 mol per mol of silver halide and is selected so that it may elevate sensitivity with low fog. By combination with a chemical sensitization-inhibitor, it may be used in a relatively small amount to attain a high sensitivity with low fog. Use of the gold sensitizer in a relatively small amount in accordance with the intended sensitivity is preferred.
  • an optimum amount may be selected in accordance with the grain size, temperature of chemical sensitization, and other conditions of pAg and pH.
  • the sulfur sensitizer may be used in an amount of from 10 ⁇ 7 to 10 ⁇ 3 mol, preferably from 5 ⁇ 10 ⁇ 7 to 10 ⁇ 4 mol, more preferably from 5 ⁇ 10 ⁇ 7 to 10 ⁇ 5 mol, per mol of silver halide.
  • the chemical sensitization is preferably conducted in the presence of sulfur sensitizer and gold sensitizer in a ratio of at least 100/250 by mol%.
  • the silver halide emulsion used in the present invention can be processed with an oxidizing agent, after the formation of the grains. This method is discussed in JP-A-60-136736. Hydrogen peroxide can be used as the oxidizing agent.
  • At least one compound represented by anyone of the following formulae (S-I) to (S-III) is preferably added to the high silver chloride emulsion for use in the present invention, especially when a gold sensitizer is used, to noticeably effectively inhibit fog formation. It may be added to the emulsion at any time in the step of forming grains, the step of desalting, the step of chemical-ripening or immediately before coating. Especially preferably, it is added in the: step of forming grains, desalting or chemical-ripening, and particularly before the addition of the gold sensitizer to the emulsion. Compounds containing a thiosulfonyl group of formulae (S-I), (S-II) and (S-III) are mentioned below. (S-I) Z-SO2S-M
  • Z represents an alkyl group, an aryl group or a heterocyclic group, which are or are not further substituted.
  • Y represents an atomic group necessary for forming an aromatic ring or hetero ring, which is or is not further substituted.
  • M represents a metal atom or an organic cation.
  • n represents an integer of from 2 to 10.
  • Substituents for the alkyl group, aryl group, aromatic ring or heterocyclic ring include a lower alkyl group such as methyl or ethyl group, an aryl group such as phenyl group, an alkoxy group having from 1 to 8 carbon atoms, a halogen atom such as chlorine, a nitro group, an amino group and a carboxyl group.
  • the alkyl group for Z has from 1 to 18 carbon atoms; and the aryl group and aromatic ring for Z and Y independently have from 6 to 18 carbon atoms.
  • the hetero ring represented by Z and that including Y include thiazole, benzothiazole, imidazole, benzimidazole and oxazole rings.
  • M is a metal cation
  • M preferably represents alkali metal cations such as sodium or potassium ions as well as organic cations such as ammonium or guanidinium ions.
  • the compounds of the formulae (S-I), (S-II) and (S-III) can be used together with sulfites or sulfinic acid salts such as alkylsulfinic acid salts, arylsulfinic acid salts or heterocyclic sulfinic acid salts.
  • the silver halide emulsion for use in the present invention is preferably physically ripened in the presence of a known silver halide solvent (for example, ammonia, potassium thiocyanate or thioether or thione compounds described in US-A-3,271,157 and JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 and JP-A-54-155828), whereby it may be converted into a monodispersed silver halide emulsion having a regular crystal shape and a narrow grain size distribution.
  • a known silver halide solvent for example, ammonia, potassium thiocyanate or thioether or thione compounds described in US-A-3,271,157 and JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 and JP-A-54-155828
  • the emulsion may be subjected to noodle washing, flocculation precipitation or ultrafiltration.
  • the silver halide emulsion for use in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization and/or noble metal sensitization. Such chemical sensitization methods may be effected singly or in combination.
  • the emulsion may be treated by a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver ion (e.g., thiosulfates, thiourea compounds, mercapto compounds, rhodanine compounds), reduction sensitization method using a reducing substance (e.g., stannous salts, amines, hydrazine derivatives, formamidinesulfinic acids, silane compounds) and/or noble metal sensitization method using a metal compound (e.g., gold complexes or complexes of metals of VIII group of the Periodic Table such as Pt, Ir, Pd, Rh or Fe). These methods can be used singly or in combination.
  • a monodispersed silver chlorobromide emulsion is preferably sensitized by sulfur sensitization or selenium sensitization, advantageously in the presence of a hydroxyazaindene compound.
  • the monodispersed degree of the silver chlorobromide emulsion is preferably 0.15 or less, especially 0.1 or less, as the fluctuation coefficient thereof.
  • Chemical sensitization of the silver halide emulsion for use in the present invention can be effected by the conventional methods mentioned above.
  • the chemical sensitization of the emulsion is required to be properly controlled by providing the localized phase on the base grain. Control methods described in EP-A-0273404, EP-A-0273429 and EP-A-0273430 may be employed.
  • a CR-compound is used at the final step of the grain formation to restrain the halogen conversion at the grain surface or is used to restrain chemical sensitization : see EP-A-273429 or EP-A-273430).
  • the photographic materials of the present invention can contain various stabilizer compounds.
  • various known stabilizer compounds include, for example, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted derivatives); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinethione; azaindenes such as tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,7)tetra
  • conventional methine dyes can be used for spectral sensitization.
  • Particular monomethine, trimethine or pentamethine dyes or merocyanine dyes as described in Japanese Patent Application Nos. 62-86252, 62-152330 and 62-329265 are advantageously adsorbed to the high silver chloride grains during the step of grain growth or the step of chemical sensitization thereof, as a chemical sensitization controlling agent.
  • the dyes to be used for spectrally sensitizing the silver halide emulsion for use in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonole dyes. Cyanine dyes, merocyanine dyes and complex merocyanine dyes are especially useful. Any and every nuclei which are usually utilized for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes.
  • nuclei include pyrroline nuclei, oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei and pyridine nuclei; the nuclei obtained by fusing alicyclic hydrocarbon rings to these nuclei; and the nuclei obtained by fusing aromatic hydrocarbon rings to these nuclei, such as indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei and quinoline nuclei. These nuclei may be substituted on the carbon atom of the dye.
  • 5-membered or 6-membered heterocyclic nuclei can be applied to the merocyanine dyes or complex merocyanine dyes.
  • Suitable heterocyclic nuclei include pyrazolin-5-one nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanine nuclei and thiobarbituric acid nuclei, as nuclei having a ketomethylene structure.
  • Specific examples of such spectral sensitizing dyes include the compounds of the formulae (IIIa), (IIIb) and (IIIc) described in Japanese Patent Application No. 62-227338.
  • the amount of the dye to be added may be from 1 ⁇ 10 ⁇ 6 to 8 ⁇ 10 ⁇ 3 mol per mol of silver halide in the emulsion layer.
  • the amount may be more effectively from about 5 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 3 mol per mol of the silver halide.
  • the tabular silver halide emulsion is preferred to be spectrally sensitized in a blue range and used in the blue-sensitive emulsion layer.
  • Spectral sensitization in a blue range means that the emulsion contains a spectrally sensitizing dye which may give at least one absorption peak in the range of from 400 to 500 nm, preferably from 430 to 490 nm, more preferably from 445 to 490 nm, when adsorbed to the emulsion grains.
  • spectrally sensitizing dye include the compounds of the formulae (IIIa) and (IIIc) where n31 is 0 (zero) described in Japanese Patent Application No. 62-227338.
  • the compounds include the compounds (III-1) to (III-8) and (III-29) to (III-32) described in Application No. 62-227338.
  • High silver chloride-tabular grains formed in the presence of such dyes are preferably used in the present invention.
  • High silver chloride-tabular grains formed in the presence of the dye can be confirmed by the spectral sensitivity distribution of the grains.
  • the resulting emulsion may give a sharp J-band for the methine dyes of the formulae (IIIa) and (IIIb), or the resulting emulsion may give a sharp monomer band (M-band) for the merocyanine dyes of the formula (IIIc).
  • the emulsion formed in the presence of the dye may give a sharp spectral sensitivity distribution.
  • the spectral sensitizing dyes can be used singly or in combination. They are preferably used in combination with supersensitizers.
  • aminostilbene compounds e.g., those described in US-A-2,933,390, US-A-3,635,721, US-A-3,615,613, US-A-3,615,641, US-A-3,617,295 and US-A-3,635,721, and JP-A-63-239449
  • aromatic or heterocyclic mercapto compounds are preferably used as supersensitizers for the high silver chloride emulsion.
  • sensitizing dyes having a reduction potential of -1.27 (V. vs SCE) or a value more anodic than the value are preferred since they give excellent sensitivity and high stability of sensitivity and latent images.
  • V. vs SCE reduction potential of -1.27
  • a value more anodic than the value are preferred since they give excellent sensitivity and high stability of sensitivity and latent images.
  • pentamethinecyanine dyes having a ring-condensed structure via one or more methine chains as conjugated between nitrogen atoms 4-quinoline nucleus-having trimethine-cyanine dyes, as well as tetramethine-merocyanine dyes and 4-quinoline nucleus-having dimethine-merocyanine dyes are preferred.
  • Determination of reduction potential of the dyes can be effected by phase differentiation secondary higher harmonics alternate current polarography, where a dropping mercury electrode is used as the working electrode, a saturated calomel electrode as the reference electrode and a platinum as the counter electrode.
  • a dropping mercury electrode is used as the working electrode
  • a saturated calomel electrode as the reference electrode
  • a platinum as the counter electrode.
  • hydroquinone, catechol, aminophenol, silver halide-adsorbing formylhydrazine compounds or derivatives thereof are preferably used in combination. The details of the formhydrazine compounds are described in Japanese Patent Application No. 63-97905.
  • the high silver chloride emulsion used in the present invention has a lower intrinsic sensitivity in a visible ray range than any other high silver bromide emulsion.
  • the high silver chloride emulsion has a silver chloride content of 80 mol% or more, it may achieve the sensitivity substantially by spectral sensitization.
  • the spectral sensitivity in the blue wavelength of the silver halide emulsion used in the present invention is not mixed with the green-spectral sensitivity or red-spectral sensitivity, a method with ease of elevating the intrinsic sensitivity of the silver halide emulsion to substantially elevate the spectral sensitivity thereof, may be necessary.
  • a compound having a mercapto group may preferably be added to the silver halide emulsion used in the present invention, whereby fog of the photographic material may be reduced, storage stability of the raw film may be improved and the storage stability of the emulsion coating composition before preparation of photographic materials may be improved.
  • tetrazaindenes are generally used, and it has heretofore been considered that mercapto-containing compounds should be added only in an extremely small amount (only in a determined amount) for this purpose.
  • the mercapto compounds would be ineffective in an amount lower than the optimum range while they would noticeably cause desensitization when used in an amount higher than the optimum range.
  • the addition of the mercapto compounds, which have heretofore been considered to have a strong adverse effect, to the emulsion of the preferred reflection color photographic material is preferred for the above-mentioned purpose, and the mercapto compounds do not cause desensitization and inhibition of development.
  • the compounds may be used together with sensitizing dyes to attain supersensitization.
  • Mercapto-containing compounds which are preferably used in the present invention are represented by the following general formula (S): wherein M1 represents a hydrogen atom, a cation or a protective group for mercapto group which may be cleaved by the action of an alkali; and Z1 represents an atomic group necessary for forming a 5-membered or 6-membered hetero-ring.
  • the hetero-ring may have substituent(s) or may also be condensed.
  • M1 represents a hydrogen atom, a cation (for example, sodium ion, potassium ion, ammonium ion) or a protective group for mercapto group which may be cleaved by the action of an alkali (for example, -COR′, -COOR′ or -CH2CH2COR′, in which R′ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group).
  • a cation for example, sodium ion, potassium ion, ammonium ion
  • a protective group for mercapto group which may be cleaved by the action of an alkali (for example, -COR′, -COOR′ or -CH2CH2COR′, in which R′ represents a hydrogen atom, an alkyl group, an aralkyl group or an aryl group).
  • Z1 represents an atomic group necessary for forming a 5-membered or 6-membered hetero-ring.
  • the hetero-ring contains sulfur, selenium, nitrogen and/or oxygen atoms as a hetero atom, and this may be condensed and does or does not have substituent(s) on the hetero-ring or condensed-ring.
  • hetero-ring including Z1 examples include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetrazaindene, triazaindene, pentazaindene, benzotriazole, benzimidazole, benzoxazole, benzothiazole, benzoselenazole and naphthoimidazole.
  • Suitable substituents for the rings include an alkyl group (e.g., methyl, ethyl, n-hexyl, hydroxyethyl, carboxyethyl), an alkenyl group (e.g., allyl), an aralkyl group (e.g., benzyl, phenethyl), an aryl group (e.g., phenyl, naphthyl, p-acetamidophenyl, p-carboxyphenyl, m-hydroxyphenyl, p-sulfamoylphenyl, p-acetylphenyl, o-methoxyphenyl, 2,4-diethylaminophenyl, 2,4-dichlorophenyl), an alkylthio group (e.g., methylthio, ethylthio, n-butylthio), an arylthio group (e.g., pheny
  • the amount of the mercapto-containing compound to be added is preferably 10 ⁇ 3 mol or less, per mol of silver halide.
  • mercapto group-having nitrogen-containing heterocyclic compounds which may be applied to the present invention include (A-374) to (A-827) described in JP-A-62-215272, pages 51 to 68.
  • the color couplers for use in the present invention are required to satisfy the general requirements for forming dyes having a sufficient color hue and a high extinction coefficient and are additionally required to have a sufficiently high activity to maintain a sufficient coupling coloring reaction with the oxidation product of a color developing agent such as paraphenylenediamine derivatives, since the developing speed of the emulsion used in the present invention is high.
  • a color developing agent such as paraphenylenediamine derivatives
  • R1, R4 and R5 each represent an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group
  • R2 represents an aliphatic group
  • R3 and R6 each represent a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic-oxy group or an acylamino group
  • R7 and R9 each represents a substituted or unsubstituted phenyl group
  • R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group
  • R10 represents a hydrogen atom or a substituent
  • Q represents a substituted or unsubstituted N-phenylcarbamoyl group
  • Y1, Y2 and Y4 each represents a halogen atom or a group
  • R2 and R3, and R5 and R6 may be bonded to each other to form a 5-, 6- or 7-membered ring.
  • R1, R2, R3 or Y1; R4, R5, R6 or Y2; R7 R8 R9 or Y3; R10, Za, Zb or Y4; and Q or Y5 may form a dimer or a higher polymer.
  • R5 and R6 are preferably bonded to each other to form a 5-membered ring to give oxyindole or indazolin-2-one cyan couplers.
  • R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, Za, Zb, Q1, Y1, Y2, Y3 and Y4 in formulae (Cup-1), (Cup-2), (Cup-3), (Cup-4) and (Cup-5) are the same as those in formulae (I), (II), (III), (IV) and (V) mentioned in JP-A-63-11939, pages 4 to 24.
  • color couplers include compounds (C-1) to (C-40), (M-1) to (M-42) and (Y-1) to (Y-46) described in JP-A-63-11939, pages 11 to 24.
  • the standard amount of the color coupler to be used is from 0.001 to 1 mol per mol of the light-sensitive silver halide. Preferably, it is from 0.01 to 0.5 mol for yellow couplers, from 0.003 to 0.3 mol for magenta couplers, and from 0.002 to 0.3 mol for cyan couplers.
  • the preferred total amount of the silver halide in the material is from 0.1 g/m2 to 1.5 g/m2.
  • the color coupler can be incorporated into the emulsion layer, as dispersed in the layer together with at least one high boiling point organic solvent.
  • the solvents preferably have a boiling point higher than 150°C, and more preferably higher than 170°C.
  • high boiling point solvents as represented by the following general formulae (A) to (E) are used for the purpose.
  • W1, W2 and W3 each represent a substituted or unsubstituted alkyl, cycloalkyl alkenyl, aryl or heterocyclic group;
  • W4 represents W1, OW1or S-W1;
  • n represents an integer of from 1 to 5, and when n is 2 or more, plural W4's may be the same or different.
  • W1 and W2 may form a condensed ring.
  • the photographic material of the present invention can contain, as a color-fogging inhibitor or a color mixing preventing agent, hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers and sulfonamidophenol derivatives.
  • the photographic material of the present invention can contain a known anti-fading agent.
  • organic anti-fading agents which can be used in the present invention include hindered phenols such as hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols and bisphenols, as well as gallic acid derivatives, dioxyphenylmethylenes, aminophenols and hindered amines and ether and ester derivatives of the compounds obtained by silylating or alkylating the phenolic hydroxyl group of the compound.
  • metal complexes such as (bis-salicylaldoximato)nickel complexes and (bis-N,N-dialkyldithiocarbamato)nickel complexes may also be used.
  • Image stabilizers described in JP-A-59-125732 are advantageous for the stabilization of magenta images formed from pyrazolotriazole magenta couplers.
  • benzotriazole ultraviolet absorbents are preferably used.
  • the ultraviolet absorbents can be co-emulsified with the cyan couplers.
  • the amount of the ultraviolet absorbent to be used is an amount that is sufficient for imparting light stability to the cyan dye images. If the absorbent is used in too large amount, it will cause yellowing in the non-exposed area (white background area) of the color photographic material. Accordingly, the amount is generally determined to fall within the range of from 1 ⁇ 10 ⁇ 4 mol/m2 to 2 ⁇ 10 ⁇ 3 mol/m2, especially from 5 ⁇ 10 ⁇ 4 mol/m2 to 1.5 ⁇ 10 ⁇ 3 mol/m2.
  • any one of the both layers adjacent to the cyan coupler-containing red-sensitive emulsion layer contain(s) an ultraviolet absorbent.
  • the ultraviolet absorbent When the ultraviolet absorbent is incorporated into the interlayer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing preventing agent.
  • another protective layer When the ultraviolet absorbent is added to the protective layer, another protective layer may be formed thereon as an outermost layer.
  • the outermost protective layer may contain a mat agent having any desired grain size or a latex having a different grain size in combination.
  • the photographic material of the present invention can contain an ultraviolet absorbent in the hydrophilic colloid layer.
  • the photographic material of the present invention can further contain various other compounds, including stabilizers, stain inhibitors, developing agents or precursors thereof, development accelerators or precursors thereof, lubricants, mordant agents, mat agents, antistatic agents, plasticizers, as well as other additives which are useful for photographic materials. Specific examples of such additives are described in Research Disclosure , Item 17643 (December 1978) and ibid. , Item 18716 (November 1979).
  • the photographic material of the present invention can contain a brightening agent of stilbene, triazine, oxazole or coumarin compounds, in the photographic emulsion layers or in any other hydrophilic colloid layers.
  • a brightening agent of stilbene, triazine, oxazole or coumarin compounds in the photographic emulsion layers or in any other hydrophilic colloid layers.
  • Water-soluble compounds can be used, or water-insoluble compounds can also be used in the form of a dispersion, as brightening agents.
  • the color photographic material of the present invention preferably has a yellow coupler-containing blue-sensitive silver halide light-sensitive layer, a magenta coupler-containing green-sensitive silver halide light-sensitive layer and a cyan coupler-containing red-sensitive silver halide light-sensitive layer formed on a support, and the order of the layers on the support may freely be varied in accordance with the object. Since the high silver chloride silver halide has only a slight intrinsic sensitivity in the blue-sensitive wavelength range (400 to 500 nm), the order of the layers on the support may be easily varied. For instance, red-sensitive layers, green-sensitive layers and blue-sensitive layers may be formed on a support in this order, or alternatively, a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer may be formed thereon in this order.
  • the color sensitivity of the respective light-sensitive layers of the color photographic material of the present invention is selected in accordance with the light source for scanning exposure to be employed for the material, and the material is preferably exposed through the respective color separation filters. For instance, a combination of blue-sensitive, green-sensitive and red-sensitive layers or a combination of green-sensitive, red-sensitive and infrared-sensitive layers are mentioned.
  • the color photographic material of the present invention is preferably exposed by scanning exposure and then processed for color development.
  • the sensitizing dye for use in the present invention is preferably added during the step of chemical sensitization or before the same, or during the formation of the silver halide grains or after the formation of the same.
  • the silver chlorobromide emulsion for use in the present invention contains high silver chloride-tabular grains as in the preferred reflection color photographic material, selection of the time of adding the dye is extremely important. Addition of the dye is to be effected prior to completion of formation of the silver halide precipitate, but the following method may also be employed. Generally, the dye is added after completion of the chemical sensitization but prior to coating. However, the dye may be added together with the chemical sensitizer for simultaneous spectral sensitization and chemical sensitization, as described in US-A-3,628,969 and US-A-4,225,666. Alternatively, the dye may be added prior to chemical sensitization, as described in JP-A-58-113298.
  • the dye may be divided into parts, and a part thereof may be added prior to chemical sensitization and the remaining part thereof may be added after chemical sensitization, which is taught in US-A-4,225,666.
  • the method as taught in US-A-4,183,756 may also be applied to the present invention.
  • the dye may be added to the silver halide grains in any stage of grain formation.
  • the cationic polymer for use in the present invention acts to capture the iodide ion to be dissolved out from the photographic material during development or fixation thereof, thereby accelerating the development processing speed.
  • the polymer acts to capture the bromide ion to be dissolved out from the photographic material during development processing thereof or the bromide ion as existing in the developer or to be carried thereinto from the outside, thereby stabilizing the color developing processing and elevating the development processing speed.
  • the polymer noticeably acts to inhibit fluctuation of the photographic properties of the photographic material processed under variable processing conditions. In particular, the stability of the gradation of the toe or shoulder in the characteristic curve can be improved by the action of the polymer.
  • the said effect of the polymer is especially noticeable when a high silver chloride emulsion having a localized silver bromide phase on the surface of the grain (preferably, silver chlorobromide emulsion having an AgCl content of 98 mol% or more) is used and the photographic material is rapidly processed at a higher temperature.
  • the photographic material of the present invention when the total amount of the silver halide is reduced to 0.9 g/m2 or less, preferably 0.7 g/m2 or less (not less than 0.4 g/m2) as silver, or when the light transmittance of the material is elevated by properly selecting the size and the shape of the silver halide grains, the improved image sharpness and color reproducibility due to the provision of the polymer-containing colored layer is more noticeable.
  • the color photographic material of the present invention generally contains yellow couplers, magenta couplers and cyan couplers which may form yellow, magenta and cyan colors, respectively, by coupling with the oxidation product of an aromatic amine color developing agent.
  • Preferred yellow couplers for use in the present invention include acylacetamide derivatives such as benzoylacetanilide or pivaloylacetanilide.
  • X represents a hydrogen atom or a coupling-releasing group
  • R21 represents a non-diffusive group having a total carbon number of from 8 to 32
  • R22 represents a halogen atom, a lower alkyl group, a lower alkoxy group or a non-diffusive group having a total carbon number of from 8 to 32
  • R23 represents a substituent
  • n and n′ represent 0 or an integer of from 1 to 4
  • n′ represents 0 or an integer of from 1 to 5.
  • R24 represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group
  • R25 represents a hydrogen atom, a halogen atom or an alkoxy group
  • R26 represents -NHCOR27, -NHSO2R27, -SO2NHR27, -COOR27, and (wherein R27 and R28 each represents an alkyl group, an aryl group or an acyl group).
  • pivaloylacetanilide yellow couplers are described in US-A-4,622,287, from column 3, line 15, to column 8, line 39, and US-A-4,623,616, from column 14, line 50 to column 19, line 41.
  • pivaloylacetanilide yellow couplers include compounds (Y-1) to (Y-39) described in the aforesaid US-A-4,622,287, columns 37 to 54. Above all, compounds (Y-1), (Y-4), (Y-6), (Y-7), (Y-15), (Y-21), (Y-22), (Y-23), (Y-26), (Y-35), (Y-36), (Y-37), (Y-38) and (Y-39) are especially preferred.
  • Couplers include compound (34) described in US-A-3,408,194, column 6, compounds (16) and (19) described in US-A-3,933,501, column 8, compound (9) described in US-A-4,046,575, columns 7 to 8, compound (1) described in US-A-4,133,958, columns 5 to 6, compound (1) described in US-A-4,401,752, column 5, and compounds (a) to (g) described in Japanese Patent Application No. 62-263318, pages 29 to 30.
  • Suitable magenta couplers for use in the present invention include oil-protect type indazolone or cyanoacetyl couplers, preferably 5-pyrazolone or pyrazoloazole couplers such as pyrazolotriazoles.
  • 5-pyrazolone couplers wherein the 3-position is substituted by an arylamino or acylamino group are preferred from the view point of the hue and the density of the dyes to be formed therefrom.
  • Specific examples of such couplers are described in US-A-2,311,082, US-A-2,343,703, US-A-2,600,788, US-A-2,908,573, US-A-3,062,653, US-A-3,152,896 and US-A-3,936,015.
  • Preferred releasing groups in 2-equivalent 5-pyrazolone couplers include the nitrogen atom-releasing groups described in US-A-4,310,619 and the arylthio groups described in US-A-4,351,897. Ballast group-having 5-pyrazolone couplers described in EP-B-73,636 are preferred as they give a high color density.
  • Suitable pyrazoloazole couplers include pyrazolobenzimidazoles described in US-A-3,369,879, preferably pyrazolo[5,1-c][1,2,4]triazoles described in US-A-3,725,067, pyrazolotetrazoles described in Research Disclosure , Item 24220 (June, 1985) and pyrazolopyrazoles described in Research Disclosure , Item 24230 (June, 1984).
  • the above-mentioned couplers may all be in the form of polymer couplers.
  • R31 represents a non-diffusive group having a total carbon number of from 8 to 32;
  • R32 represents a phenyl group or a substituted phenyl group.
  • R33 represents a hydrogen atom or a substituent.
  • Z represents a non-metallic atomic group necessary for forming a 5-membered azole ring containing from 2 to 4 nitrogen atoms, and the azole ring may have substituent(s) including condensed ring(s).
  • X2 represents a hydrogen atom or a releasing group.
  • the imidazo[1,2-b]pyrazoles described in US-A-4,500,630 are preferred because of the small yellow side-absorption of the dye formed and the high light-fastness thereof.
  • pyrazolo[1,5-b][1,2,4]triazoles described in US-A-4,540,654 are especially preferred.
  • pyrazolotriazole couplers where a branched alkyl group is directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole ring described in JP-A-61-65245; pyrazoloazole couplers containing a sulfon-amido group in the molecule described in JP-A-61-65246; pyrazoloazole couplers having an alkoxyphenylsulfonamido ballast group described in JP-A-61-147254; and pyrazolotriazole couplers having an alkoxy group or an aryloxy group in the 6-position described in EP-B-226,849 are also preferably used in the present invention.
  • Typical cyan couplers for use in the present invention include phenol cyan couplers and naphthol cyan couplers.
  • Suitable phenol couplers include phenol compounds (including polymer couplers) having an acylamino group in the 2-position of the phenol nucleus and an alkyl group in the 5-position thereof described in US-A-2,369,929, US-A-4,518,687, US-A-4,511,647 and US-A-3,772,002.
  • Typical examples of such compounds include the coupler of Example 2 of CA-A-625,822, compound (1) described in US-A-3,772,002, compounds (I-4) and (I-5) described in US-A-4,564,590, compounds (1), (2), (3) and (24) described in JP-A-61-39045, and compound (C-2) described in JP-A-62-70846.
  • Phenol cyan couplers include 2,5-diacylaminophenol couplers described in US-A-2,772,162, US-A-2,895,826, US-A-4,334,011 and US-A-4,500,653 and JP-A-59-164555.
  • Specific examples of such couplers include compound (V) described in US-A-2,895,826, compound (17) described in US-A-4,557,999, compounds (2) and (12) described in US-A-4,565,777, compound (4) described in US-A-4,124,396 and compound (I-19) described in US-A-4,613,564.
  • Suitable phenol cyan couplers include condensed phenol couplers where a nitrogen-containing heterocyclic ring has been condensed to the phenol nucleus described in US-A-4,327,173, US-A-4,564,586 and US-A-4,430,423, JP-A-61-390441 and JP-A-62-257158.
  • Specific examples of such couplers include couplers (1) and (3) described in US-A-4,327,173, compounds (3) and (16) described in US-A-4,564,586, compounds (1) and (3) described in US-A-4,430,423 and the following compounds .
  • phenol cyan couplers for use in the present invention include ureido couplers described in US-A-4,333,999, US-A-4,451,559, US-A-4,444,872, US-A-4,427,767 and US-A-4,579,813 and EP-B-067,689.
  • couplers include coupler (7) described in US-A-4,333,999, coupler (1) described in US-A-4,451,559, coupler (14) described in US-A-4,444,872, coupler (3) described in US-A-4,427,767, couplers (6) and (24) described in US-A-4,609,619, couplers (1) and (11) described in US-A-4,579,813, couplers (45) and (50) described in EP-B-067,689, and coupler (3) described in JP-A-61-42658.
  • Suitable naphthol cyan couplers for use in the present invention include naphthol compounds having an N-alkyl-N-arylcarbamoyl group at the 2-position of the naphthol nucleus (for example, those described in US-A-2,313,586), those having an alkylcarbamoyl group at the 2-position (for example, those described in US-A-2,474,293 and US-A-4,282,312), those having an arylcarbamoyl group at the 2-position (for example, those described in JP-B-50-14523), those having a carbonamido or sulfonamido group at the 5-position (for example, those described in JP-A-60-237448, JP-A-61-145557, JP-A-61-153640), those having an aryloxy-releasing group (for example, those described in US-A-3,476,563), those having a substituted alkoxy-releasing group (for example, those described in
  • Diphenylimidazole cyan couplers described in EP-A-0,249,453 can also be used in the present invention singly or in combination with the aforesaid cyan couplers.
  • the photographic material of the present invention can contain hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives as color-fogging inhibitors.
  • catechol derivatives for example, those described in JP-A-59-125732 and JP-A-60-262159, as color image stabilizers.
  • the photographic material of the present invention can contain an ultraviolet absorbent in the hydrophilic colloid layer.
  • an ultraviolet absorbent for instance, aryl group-substituted benzotriazole compounds (for example, those described in US-A-3,533,794), 4-thiazolidone compounds (for example, those described in US-A-3,314,794 and US-A-3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, those described in US-A-3,705,805 and US-A-3,707,375), butadiene compounds (for example, those described in US-A-4,045,229) or benzoxidol compounds (for example, those described in US-A-3,700,455) can be used for this purpose.
  • Ultraviolet-absorbing couplers for example, ⁇ -naphthol cyan dye-forming couplers
  • ultraviolet-absorbing polymers may also be used.
  • the color photographic material of the present invention preferably has plural layers of a subbing layer, at least three silver halide light-sensitive layers, an inter-layer, an ultraviolet absorbing layer and a protective layer, coated on the reflective support, and therefore the improved effect of the antihalation layer is noticeable.
  • the cationic polymer-containing layer can be provided without layer condition problems by forming the inter-layer (substantially not containing light-sensitive silver halide grains) adjacent to the polymer-containing layer.
  • an interlayer not containing light-sensitive silver halide grains is preferably provided between the two layers.
  • the interlayer comprises a hydrophilic colloid which may contain a color mixing inhibiting agent, an ultraviolet absorbing agent, a coupler for preventing color mixing, a stain inhibiting agent, a polymer latex and/or a dye.
  • the thickness of the interlayer is preferably from 0.1 »m to 3 »m, and more preferably from 0.1 »m to 2 »m.
  • the photographic material of the present invention can contain, if desired, various surfactants as coating aids, an emulsifying and dispersing agent or an anti-blocking agent to improve photographic properties (for example, acceleration of developability, elevation of contrast and elevation of sensitivity), for static charge prevention and for the improvement of slide properties.
  • various surfactants as coating aids, an emulsifying and dispersing agent or an anti-blocking agent to improve photographic properties (for example, acceleration of developability, elevation of contrast and elevation of sensitivity), for static charge prevention and for the improvement of slide properties.
  • such surfactants include non-ionic surfactants, for example, saponins (steroid type), alkyleneoxide derivatives (e.g., polyethylene glycol, polyethylene glycol/polypropylene glycol condensed product, polyethylene glycol alkylethers or polyethylene glycol alkylarylethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamides or amides, siliconepolyethyleneoxide adducts), glycidol derivatives (e.g., alkenylsuccinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, and alkyl esters of saccharides; anionic surfactants containing an acid group such as a carboxyl, sulfo, phospho, sulfate or phosphate group, for example, alkylcarboxylic acid salts, alkylsulfonic acid salts,
  • combinations of the cationic polymer dispersion used in the present invention and the above-mentioned cationic surfactants are effective for improving layer properties, film quality and adhesiveness to the adjacent layer.
  • the color photographic material of the present invention can contain various other additives. Additives which can be used in the present invention are described in Research Disclosure , Item 17643 (December, 1978) and Item 18716 (November, 1979). The relevant parts of the foregoing references are discussed below.
  • the present invention is suited for color photographic materials, especially printing color photographic materials.
  • a color developer is used for development of the photographic material of the present invention.
  • the color developer for use in the present invention is preferably an alkaline aqueous solution comprising essentially an aromatic primary amine color developing agent.
  • color developing agents for the developer are phenylenediamine compounds, although aminophenol compounds are useful.
  • the compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethyl-aniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and sulfates, hydrochlorides and p-toluenesulfonates thereof. Two or more of these compounds may be used in combination, in accordance with the object thereof.
  • “Scanning exposure system” as referred to herein means an image exposure performed by a scanning system.
  • a “Scanning system” means a system of restructuring an image to be reproduced on a plane by combining image elements as resolved in accordance with a determined rule into a time-dependent sequence in accordance with a reversely determined rule. Details of the system are described in, for example, Image Electronics Handbook (edited by Image Electronics Association of Japan), Introduction, 3rd Chap., pages 45 to 55.
  • a laser ray, CRT or LED (luminescence emitting diode) can be used for image exposure.
  • the color photographic paper has at least three silver halide light-sensitive layers on a support, such as, the preferred reflection color photographic material, and the emitted wavelength of maximum strength from CRT is matched with the respective maximum wavelength of the different spectral sensitivities of each silver halide compound in the layers, in scanning exposure of the paper.
  • a support such as, the preferred reflection color photographic material
  • the emitted wavelength of maximum strength from CRT is matched with the respective maximum wavelength of the different spectral sensitivities of each silver halide compound in the layers, in scanning exposure of the paper.
  • at least three laser rays selected from e.g. He-Cd laser, Ar-gas laser, He-Ne gas laser and GaAs, GaAsxPrx and InP semiconductor lasers are preferably used.
  • the light emission of the respective image elements comprises repetition of light emission of from several ms to several »s, a sufficiently high quantity of light can be obtained from CRT of a relatively low output.
  • the apparatus for the system is compact and inexpensive.
  • a high quality color CRT and black-and-white CRT are advantageougly used.
  • a suitable CRT has a high resolving power, little strain, is able to obtain a picture on the whole fluorescent surface and has little spot halo.
  • a black-and-white CRT which has a fluorescent body capable of emitting in blue, green and red wavelength ranges so as to elevate the density of the image elements, is especially preferred.
  • image elements are inputted from a memory means of already inputted digital information, for example, a floppy disk, or are directly inputted without such means and the thus inputted information is displayed on a black-and-white CRT as photographic images, CG images, line images and/or character images, whereupon the images are formed on the surface of the light-sensitive layer of a color photographic paper via an optical lens and a shutter through blue, green and red filters in order.
  • the fluorescent body to be used is one which intensely emits fluorescent light under high voltage and high current density conditions and which has excellent current saturation characteristics and temperature stability.
  • the fluorescent body can be selected from those used for projection tubes. Suitable industrially stable available fluorescent bodies which can be employed in the present invention include, Y2O3:Eu and Y2O2S:Eu for red, Zn2SiO4:Mn and Gd2O2S:Tb, in particular, Y2SiGeO5:Tb and Y2Al5O12:Tb for blue, and ZnS:Ag and Cl or ZnS:Ag or Al for blue.
  • the exposure time for the respective blue image, green image and red image obtainable through the blue, green and red filters is inversely proportional to the spectral sensitivity of the respective light-sensitive layers of the color photographic paper by high-intensity and short-time multi-exposure.
  • the number of image elements is generally from about (500 to 1000) ⁇ (500 to 1500)
  • the emitting time for one image element is from about 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 7 s
  • from 10 to 100 emissions are effected for one exposure to the respective light-sensitive layers.
  • the beam diameter of the emission for one image element is from about 20 to 100 »m.
  • Exposure may also be effected by the use of the abovesaid FOT or CRT.
  • a particular means for color separation between blue, green and red colors for example, a liquid crystal filter can be used for contact exposure.
  • the color photographic material is imagewise exposed by a combination of a black-and-white CRT exposure system and a photographic image exposure system as combined by light path changing-over switch means.
  • FIG. 1 A flow sheet illustrating a process for forming prints by a CRT exposure system of the present invention is illustrated in Fig. 1.
  • Character image-inputting means (12) is composed of a console having a CRT and a keyboard. Character information is inputted by operating the keyboard and watching the CRT. The inputted character information can be memorized in a memory medium (for example, a floppy disk). Initiation of CRT exposure can be indicated by the means (12).
  • Figure image-inputting means (13) comprises a digitizer, by which line images and computer graphics (CG) images can be inputted. The data of the inputted figure images can be memorized in a floppy disk. Initiation of CRT exposure can be indicated by means (13).
  • a photographic image may be exposed by a separate photographic image-exposing system, or alternatively, information or a photographic image inputted by an electronic steel camera can be inputted by means of a digitizer.
  • Picture-synthesizing means (11) is composed of a microcomputer, where the data is read out in a determined order from the portrait image-inputting means (10), character image-inputting means (12) and/or figure image-inputting means (13) and they are laid out in a determined position and are thereafter inputted into the CRT controller (14).
  • the CRT controller (14) functions to control the color monitor (15) and the black-and-white CRT (16) for exposure.
  • the synthesized image data is outputted in only the color monitor (15) and a positive image is displayed on the display surface.
  • the synthesized image is reversed to a negative image and outputted to the black-and-white CRT (16). Then, electron beams are shifted to the direction opposite to the normal direction so that the synthesized image is reversed (turned right to left).
  • the black-and-white CRT image is inserted by synchronizing optical filters B, G and R with the emission on the black-and-white CRT display surface through optical lens (18), whereupon the filters are also synchronized with shutter (17). Accordingly, the color photographic paper (19) is printed for a determined period of time by a three-color face-ordered exposure system. Afterwards, the thus printed paper is subjected to a determined color development process through the photographic processing device (20).
  • the fluorescent body used for the black-and-white CRT is one having a wavelength of maximum luminance which corresponds to the main wavelength of the spectral sensitivity of the respective three light-sensitive layers of the color photographic paper to be processed.
  • the fluorescent body also has a short afterimage time or has no afterimage and has a small flare on the display surface.
  • a CRT exposure system can be combined with a photographic exposure system to give synthesized images comprising photographic picture images and CG images, line images and character images.
  • the luminous flux as emitted from image elements by the fluorescent body on the CRT surface is hardly focused.
  • the color photographic paper to be employed in the system has plural light-sensitive layers on a reflective support, the layers each containing a dispersion of different couplers and silver halide grains.
  • the degree of diffusion of the luminous flux to be emitted from the image elements of CRT frequently differs in the respective light-sensitive layers.
  • Japanese letters have more edges and thinner lines than alphabet letters so that the reproduction of the former letters is generally difficult. Accordingly, a special means is required for elevating the resolving power and edge contrast and for inhibiting color bleeding in the edges of letters, in the reproduction of Japanese letters.
  • the color photographic paper according to the present invention has been improved with respect to the said requirements.
  • the color photographic paper is therefore especially suited for use in cards and post cards.
  • the paper When a post card is prepared from the printed image of the photographic paper according to the present invention, the paper preferably has a conventional support having a thickness of 220 »m or less.
  • the post card print preferably has a weight of 6 g or less, a length of from 140 to 150 mm and a width of from 90 to 100 mm.
  • a print obtained from the color photographic paper according to the present invention is cut to have a weight of 6 g or less, and it is attached to a post card support with an adhesive. The thus attached sheet may be cut into a determined size for the post card.
  • a seal print may also be obtained from the color photographic paper according to the present invention, for example, in accordance with the techniques of Japanese Patent Application Nos. 61-231481 and 62-4765.
  • the color photographic paper according to the present invention may also be processed into cards, in accordance with the technique described in, for example, JP-A-62-58248.
  • the color developer generally contains a pH buffer such as alkali metal carbonates, borates or phosphates, and development inhibitors or an anti-foggant such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
  • the developer may further contain, if desired, various kinds of preservatives, such as hydroxylamine, diethylhydroxylamine, sulfates, hydrazines, hydrazides, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo[2,2,2]-octanes).
  • hydrazines and hydrazides are preferred. These compounds correspond to those of the formula (II) described in Japanese Patent Application No. 63-11295. Specific examples thereof include the compounds shown in the same Application No. 62-11295, pages 27 to 47.
  • the amount of the compound to be added is preferably from 0.01 to 50 g, especially from 0.1 to 30 g, per liter of developer.
  • the amount of hydroxylamines to be added is preferably from 0 to 10 g, especially from 0 to 5 g, per liter of the developer.
  • the amount of compound added is preferably small, provided that the stability of the color developer can be maintained.
  • Another compound may be added to the color developer for use in the present invention including ethylene glycol or diethylene glycol; a development accelerator such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts or amines; dye-forming couplers; competing couplers; a foggant such as sodium boronhydride; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a thickener; as well as various kinds of chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids or phosphonocarboxylic acids, e.g., ethylenediamine-tetraacetic acid, nitrilo-triacetic acid, diethylenetriamine-pentaacetic acid, cyclohexanediamine-tetraacetic acid, hydroxyethylimino-diacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N,
  • the processing temperature of the material of the present invention with the color developer is preferably from 30°C to 50°c, more preferably from 33°C to 42°C.
  • the amount of the replenisher used in processing is 2000 ml or less, preferably 1500 ml or less, per m2 of the photographic material being processed.
  • the amount of the replenisher is preferably small in order to decrease the water liquid to be drained.
  • the photographic material of the present invention is preferably developed with a color developer substantially not containing benzyl alcohol.
  • benzyl alcohol is disadvantageous since it causes environmental pollution, deterioration of storage stability of color images formed and increases staining of the material processed by a rapid development procedure.
  • the color developing system preferably contains a restoring agent for the oxidation product of the color developing agent and a capturing agent for the oxidation product of the restoring agent, as described in JP-A-63-113537.
  • the color developer to be used for processing the photographic material of the present invention preferably does not substantially contain iodide ion.
  • the "color developer substantially not containing iodide ion” means that the content of the iodide ion in the developer is less than 1 mg/l.
  • the color developer for use in the present invention also preferably does not substantially contain sulfite ion.
  • the "color developer substantially not containing a sulfite ion” means that the sulfite ion content in the developer is 0.02 mol/l or less.
  • the color developer generally has a pH value of from 9 to 12, preferably from 10 to 11.
  • the amount of the replenisher to the developer is generally 3 l or less per m2 of the material being processed. By lowering the bromide ion concentration in the replenisher, the amount may be 500 ml or lower. When the amount of the replenisher to be added is lowered, it is desirable to prevent the evaporation and aerial oxidation of the processing solution by reducing the contact surface area of the processing tank with air. In addition, the amount of the replenisher to be added may also be reduced by suppressing the accumulation of bromide ion in the developer.
  • the photographic emulsion layer is generally bleached.
  • Bleaching may be carried out simultaneously with fixation (bleach-fixation) or separately from the latter. In order to accelerate the photographic processing, bleaching may be followed by bleach-fixation.
  • bleach-fixation in two continuous processing tanks fixation prior to bleach-fixation or bleaching followed by bleach-fixation may also be used to process the photographic material of the present invention, in accordance with the object thereof.
  • Suitable bleaching agents include, for example, compounds of polyvalent metals such as iron (III), cobalt(III), chromium (VI) or copper(II), as well as peracids, quinones and nitro compounds.
  • the bleaching agent include ferricyanides; bichromates; organic complexes of iron(III) or cobalt (III), for example, complexes with aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, cyclohexanediamine-tetraacetic acid, methylimino-diacetic acid, 1,3-diaminopropane-tetraacetic acid or glycolether-diamine-tetraacetic acid, as well as with citric acid, tartaric acid or malic acid; persulfates; bromates; permanganates; and nitrobenzenes.
  • aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriamine-pentaacetic acid, cyclohexanediamine-tetraacetic acid, methylimino-diacetic acid, 1,3-diaminopropane-tetraacetic
  • aminopolycarboxylic acid iron(III) complexes such as ethylenediamine-tetraacetic acid/iron (III) complex as well as persulfates are preferred in view of the rapid processability thereof and of the prevention of environmental pollution.
  • the aminopolycarboxylic acid/iron(III) complexes are especially useful both in a bleaching solution and in a bleach-fixing solution.
  • the bleaching solution or bleach-fixing solution containing such bleaching agents generally has a pH value of from 5.5 to 8, but the solution may have a lower pH value for rapid processing.
  • advantageous bleaching accelerators for use in the present invention include compounds containing a mercapto group or a disulfide group such as those described in US-A-3,893,858, DE-B-1,290,812, JP-A-53-95630 and Research Disclosure , Item 17129 (July 1978); thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described in US-A-3,706,561; iodides described in JP-A-58-16235; polyoxyethylene compounds described in DE-B-2,748,430; and polyamine compounds described in JP-B-45-8836.
  • a mercapto group or a disulfide group such as those described in US-A-3,893,858, DE-B-1,290,812, JP-A-53-95630 and Research Disclosure , Item 17129 (July 1978); thiazolidine derivatives described in JP-A-50-140129; thiourea derivatives described in US-
  • mercapto group- or disulfide group-containing compounds are preferred as having sufficient accelerating effect, and in particular, the compounds described in US-A-3,893,858, DE-B-1,290,812 and JP-A-53-95630 are especially preferred. In addition, the compounds described in US-A-4,552,834 are also preferred.
  • the bleaching accelerator can be incorporated into the photographic material. The bleaching accelerators are especially advantageously used for bleach-fixation of picture-taking color photographic materials.
  • Suitable fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodides. Among them, thiosulfates are generally used, and in particular, ammonium thiosulfate is most widely used.
  • Preferred preservatives for the bleach-fixing solution include sulfites, bisulfites and carbonyl-bisulfite adducts.
  • the silver halide color photographic material of the present invention is generally rinsed with water and/or stabilized, after being desilvered.
  • the amount of the water to be used in the rinsing step can be set in a broad range, in accordance with the characteristics of the photographic material being processed (for example, depending upon the raw material components, such as the coupler) or the use of the material, as well as the temperature of the rinsing water, the number of the rinsing tanks (the number of the rinsing stages), the replenishment system of normal current or countercurrent and other various kinds of conditions.
  • the relationship between the number of the rinsing tanks and the amount of the rinsing water in a multi-stage countercurrent rinsing system can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers , Vol. 64, pages 248 to 253 (May, 1955).
  • the amount of the rinsing water to be used can be reduced noticeably, but because of the prolongation of the residence time of the water in the rinsing tank, bacteria would propagate in the tank so that the floating substances generated by the propagation of bacteria would adhere to the surface of the material as it was processed.
  • the method of reducing calcium and magnesium ions which is described in Japanese Patent Application No. 62-288838, can be effectively used for overcoming the foregoing problem during the processing the photographic material of the present invention.
  • the pH value of the rinsing water to be used for processing the photographic material of the present invention is from 4 to 9, preferably from 5 to 8.
  • the temperature of the rinsing water and the rinsing time can be variably set in accordance with the characteristics of the photographic material being processed as well as the use thereof. In general, the temperature is from 15 to 45°C and the time is from 20 s to 10 min, and preferably the temperature is from 25 to 40°C and the time is from 30 s to 5 min.
  • the photographic material of the present invention may also be processed directly with a stabilizing solution in place of being rinsed with water. Suitable stabilization methods include, for example, those described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.
  • the material can also be stabilized, following the rinsing step.
  • a stabilizing bath containing formalin and a surfactant can be used as a final bath for color photographic materials.
  • the stabilizing bath may also contain various chelating agents and fungicides.
  • the overflow from the rinsing and/or stabilizing solutions because of addition of replenishers thereto may be re-used in the other steps such as the desilvering step.
  • the silver halide color photographic material of the present invention can contain a color developing agent for the purpose of simplifying and accelerating the processing of the material.
  • a color developing agent for incorporation of color developing agents into the photographic material, various precursors of the agents are preferably used.
  • suitable precursors include the indoaniline compounds described in US-A-3,342,597, the Schiff base compounds described in US-A-3,342,599 and Research Disclosure Items 14850 and 15159, the aldole compounds described in Research Disclosure Item 13924, the metal complexes described in US-A-3,719,492 and the urethane compounds described in JP-A-53-135628.
  • the silver halide color photographic material of the present invention can contain various kinds of 1-phenyl-3-pyrazolidones, if desired, for the purpose of accelerating the color developability thereof. Specific examples of these compounds are described in JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
  • the processing solutions for the photographic material of the invention are used at 10°C to 50°C.
  • a processing temperature of from 35°C to 38°C is standard, but the temperature may be made higher so as to accelerate the processing or to shorten the processing time, or on the contrary, the temperature may be made lower so as to improve the quality of images formed and to improve the stability of the processing solutions used.
  • the cobalt intensification or hydrogen peroxide intensification described in DE-B-2,226,770 and US-A-3,674,499 may be employed in processing the photographic material of the present invention.
  • the materials are processed with a color developer which does not substantially contain benzyl alcohol and which contains bromide ion in an amount of 0.002 mol/l or less, within a development time of 2 min 30 s or less.
  • the complete process from color development to drying via desilvering and rinsing can be effected within 120 s, in the photographic processing procedure for the preferred reflection color photographic material of the present invention.
  • the "color developer which does not substantially contain benzyl alcohol” means that it contains benzyl alcohol in an amount of 2 ml/l or less, preferably 0.5 ml/l or less, and most preferably, it contains no benzyl alcohol.
  • a waterproof titanium oxide-containing white pigment resin layer comprising the composition mentioned below was formed on the surface of a white raw paper made of 100% LBKP for photographic paper (hardwood, bleached sulfate pulp) (weight 175 g/m2, thickness about 180 »m), to prepare supports (A) and (A-I) to (A-VI).
  • the same titanium oxide powder as that used in the preparation of support (A) was dipped in an ethanol solution of 2,4-dihydroxy-2-methylpentane and then heated. After the evaporation of ethanol, a surface-treated titanium oxide white pigment was obtained. The alcohol adhered to the titanium oxide in an amount of about 1% by weight to coat the surface of the grains. The back surface of the white raw paper was coated with the same polyethylene composition (ii) as that used for the preparation of support (A) to form a waterproof resin layer thereon.
  • Supports (A-II) and (A-V) were prepared in the same manner as above, but using the compositions indicated in Table A-1 below.
  • a composition comprising 50 parts by weight of dipentaerythritol propyleneoxide (12 mols)-hexaacrylate ester adduct and 50 parts by weight of rutile-type titanium oxide was blended and dispersed in a ball mill for 20 h or more and the resulting blend was coated and dried on the raw paper mentioned below in a dry film thickness of 20 »m.
  • the raw paper used here was prepared by coating a 20 »m polyethylene composition layer on the same white raw paper as that used in the preparation of support (A), the back surface of the paper being coated with a 20 »m polyethylene layer (density 0.960 g/ml, MI 25 g/10 min).
  • the thus coated layer was treated by irradiation with an electron ray in an amount corresponding to an absorption dose of 5 M.rad under an accelerated voltage of 200 kV, to prepare support (A-VI).
  • the surface of the waterproof resin layer as coated on each of the supports thus prepared was etched to a depth of about 0.05 »m from the surface thereof by ion-sputtering, and the white pigment grains thus exposed were observed with an electron microscope so as to evaluate the degree of dispersion of the white pigment grains in the layer.
  • the projected area ratio (Ri) of each grain was determined for the continuous six unit areas (each having a size of 6 »m x 6 »m), and the standard deviation (s) as well as the mean grain possessory area ratio (%) ( R ) were obtained from the following formulae:
  • Each of supports (A) and (A-I) to (A-V) was subjected to corona discharge and a subbing layer (gelatin layer) was provided thereon. Next, a colored layer, silver halide light-sensitive layers, interlayers and a protective layer were formed on the support, as mentioned below.
  • Color photographic paper samples (A-a) to (A-g) and (A-1) to (A-6) were thus prepared.
  • the numeral for the amount coated is expressed by the unit of g/m2.
  • the silver halide emulsion is expressed by the amount of silver therein.
  • Second Layer Blue-sensitive Silver Halide Emulsion Layer
  • each sample thus prepared was sensitometrically wedgewise exposed with a commercial sensitometer (color temperature in light source 3,200°K), using blue, green and red filters. On the other hand, each sample was exposed for determination of its resolving power (CTF) and then processed by the process mentioned below.
  • CTF resolving power
  • the density was obtained from the strip thus developed, and Dmin (minimum density in non-image area) was obtained.
  • the whiteness was evaluated by visual observation and on the basis of Dmin (yellow) as obtained from the blue filter density. The results are shown in Table 4 below.
  • the photographic processing process employed here comprised the following steps:
  • the processing solutions used in the steps had the following compositions.
  • the color photographic paper samples (Samples (c) to (g) and Samples (1) to (7)) having the support according to the present invention have improved whiteness and resolving power, as compared with comparative samples having the conventional support.
  • the color photographic paper samples (Samples (1) to (7)) having the colored layer according to the present invention have a synergetically improved resolving power.
  • Sample (6) is noted to have a sufficient resolving power and an excellent whiteness, as it has a support containing a large amount of titanium oxide grains with a small fluctuation coefficient and it has a colored layer containing a cationic latex polymer having at least one hydrogen-having ammonium group at the cation site.
  • Samples (h) and (8) to (10) were prepared in the same manner as in Example 1, using supports (A), (A-I), (A-III) and (A-VI).
  • the layer constitution of the samples was as follows. Unless otherwise specifically indicated, the amount coated is expressed by the unit of g/m2. The silver halide is expressed by the amount of silver therein.
  • Second Layer Blue-sensitive Silver Halide Emulsion Layer
  • Example A-1 Each of these samples was wedgewise exposed for sensitometry and further exposed for determination of the resolving power, in the same manner as in Example A-1.
  • color negative originals formed by photographing a person image, a Mackbeth Color Chart or a living flower on Fuji Color SUPER HR-100 were printed on each sample.
  • the silver halide color photographic materials of the present invention (Samples 8 to 10) had improved image sharpness without lowering the degree of the whiteness thereof.
  • the apparent whiteness (visual whiteness degree) may be further strengthened.
  • Processing solutions used in the steps of the procedure had the following compositions.
  • Wood pulp comprising 20 parts of LBSP (hard wood bleached sulfurous acid pulp) and 80 parts of LBKP (hard wood bleached sulfate pulp) was beaten with a disc refiner to a Canadian freeness of 300 ml. 1.0 part of sodium stearate, 1.0 part of anion polyacrylamide, 1.5 parts of aluminum sulfate and 0.5 part of polyamidepolyamine-epichlorohydrin were added thereto. (The "part” is by absolute dry weight to wood pulp.) The resulting mixture was made into a paper (weight: 180 g/m2) by the use of a Fourdrinier machine, whereupon polyvinyl alcohol (PVA) was added as a sizing agent in an amount of 1 g/m2. The density of the paper made was adjusted to be 1.0 g/m2 by the use of a machine calender. The paper made to have a pH value of 4.3.
  • PVA polyvinyl alcohol
  • the acid paper thus formed was used as a paper substrate, and a waterproof resin layer (25 »m thick) containing 15% by weight of trimethylolethane-surface-treated anatase-type titanium oxide was formed on the substrate in accordance with the method used to prepare the above-mentioned support (A-II), to prepare support (A-VII).
  • Wood pulp comprising 20 parts of LBSP and 80 parts of LBKP was beaten with a disc refiner to a Canadian freeness of 300 ml.
  • Polyamide-polyamine-epichlorohydrin (fixing agent KYMENE 557, commercial product of DIC-HERCULES CHEMICALS Inc.) was added to the foregoing in an amount of 0.5% (by weight to absolute dry pulp - the same shall apply hereunder) and then cationic polyacrylamide (POLYSTRON 705, commercial product of Arakawa Chemical) and anionic polyacrylamide (POLYACRON ST-13, commercial product of Hamano Industries) each in an amount of 0.5% were added.
  • alkylketene dimer (AQUAPEL, commercial product of DIC-HERCULES CHEMICALS Inc.) was added thereto in an amount of 0.5%.
  • the resulting mixture was made into a paper(weight: 180 g/m2) by the use of a Fourdrinier machine, whereupon PVA was added as a sizing agent in an amount of 1 g/m2.
  • the density of the paper was adjusted to be 1.0 g/cm3 by the use of a machine calender.
  • the neutral paper thus formed was used as a paper substrate, and a waterproof white pigment-containing resin layer was formed thereon by the same method used in preparing the above-mentioned support (A-VII).
  • Each of supports (A-VII) and (A-VIII) was subjected to corona discharge, and a colored layer having the composition mentioned below was formed thereon.
  • Example A-2 the same second to ninth layers as those in Example A-2 were formed on the first layer and dried to prepare color photographic material Samples (11) and (12), where 1,2-bis(vinylsulfonyl)ethane was used as the hardening agent.
  • Example A-7 Each sample was cut into 12 cm wide strips and rolled. Each sample was then imagewise exposed and rolled, and the cut edge was rubbed under the same condition. Next, each sample was color-developed in the same manner as in Example A-2. Each rolled print thus obtained was stored for 5 days at 40°C, and the cut edge was observed to determine whether or not it was stained. (That is, the side edge of the rolled sample was visually observed and checked.) The results are shown in Table A-7 below.
  • Sample (i) was prepared as follows: Support (B) was prepared in the same manner as Support (A-VII), except that the same waterproof white pigment-containing resin layer as that used for preparing the above-mentioned Sample (A) was formed. Sample (i) was prepared in the same manner as Sample (11), except that Support (B) was used in place of Support (A-VII).
  • the photographic material of the present invention gives photographic prints having excellent whiteness, image sharpness and highlight detail color tone reproducibility. In addition, the prints obtained from the photographic material of the present invention are hardly stained by photographic processing.
  • the dye crystal composition shown below was kneaded and ground by a sand mill.
  • the ground mixture was dispersed in 25 ml of an aqueous solution of 10% lime-processed gelatin containing 1 g of citric acid dissolved therein and sands used for the sand mill were removed using a glass filter.
  • the dyes adsorbed to the sands on the glass filter were recovered by using warm water and added to the dispersion to provide 100 ml of the dispersion containing 7% gelatin with the addition of water.
  • Example A-1 and Example A-3 were subjected to a corona discharging treatment, and after forming thereon a gelatin subbing layer, a first layer (colored layer) shown in Table A-8 below was formed and then the second layer to the ninth layer as in Example A-2 were formed thereon to provide Samples 13 to 16.
  • the cross section of a piece of Sample 13 was observed using a transmission type electron microscope.
  • the mean grain size of the fine dye powder in Sample 13 was about 0.3 »m. Also, the fine dye powder existed in the first layer and was not observed in the adjacent layers.
  • Example A-1 each of the samples was subjected to the sensitometric stage exposure and the exposure for measuring the resolving power and then subjected to quick processing as shown in Example A-2.
  • the occurrence of residual color and yellow stain in each sample was less than that of Samples 11 and 12 in Example 3.
  • the results obtained are shown in Table A-9.
  • compositions of the dye crystals shown below were kneaded with a dispersion aid, ground by a ball mill, and the ground composition was dispersed in 25 ml of an aqueous solution of 10% lime-processed bone gelatin containing 1 g of citric acid dissolved therein.
  • the beads used for grinding were removed from the mixture using a filter, the dyes adsorbed to the beads and the filter were recovered by warm water and added to the dispersion to provide 100 ml of the aqueous dispersion containing 7% gelatin.
  • the mean grain sizes of the fine crystal grains of the dyes in Dispersion Methods B, C, D and E were 0.1 »m, 0.3 »m, 0.15 »m, 0.2 »m, respectively. That is, the mean grain sizes were all 0.3 »m or less and haze was slight or absent.
  • Samples 17 and 18 each contained the dispersion of the fine dye grains according to this invention prepared by Dispersion Methods B and C, respectively. Furthermore, the second layer to the ninth layer as in Example A-2 were also formed thereon. In this case, however, the ninth layer of Sample 19 contained fine grains of Dye IV-24 formed by Dispersion Method D.
  • Example A-10 Each of the samples thus prepared was subjected to the sensitometric stage exposure and the exposure for measuring the resolving power as in Example A-2 and then subjected to quick color photographic processing as in Example A-2. The density of each sample thus processed was measured and the results obtained are shown in Table A-10 below.
  • a commercial Safelight Filter for color paper was mounted on an electric bulb of 10 W (100 V) and after irradiating one piece of each sample by the electric bulb in the direction perpendicular to the light-sensitive surface thereof for 20 min, the piece of the sample was subjected to color photographic processing together with another piece of the sample.
  • a waterproof titanium oxide-containing white pigment resin layer comprising the composition mentioned below was formed on the surface of a white raw paper made of 100% LBKP for photographic paper (hardwood, bleached sulfate pulp) (weight 175 g/m2, thickness about 180 »m), to prepare supports (B-I).
  • the same titanium oxide powder as that used in preparation of support (B-1) was dipped in an ethanol solution of 2,4-dihydroxy-2-methylpentane and then heated. After the evaporation of ethanol, a surface-treated titanium oxide white pigment was obtained. The alcohol adhered to the titanium oxide in an amount of about 1% by weight to coat the surface of the grains. The back surface of the white raw paper was coated with the same polyethylene composition (ii) as that used for the preparation of support (B-I) to form a waterproof resin layer thereon.
  • Support B-III was prepared in the same manner as support B-II, except that titanium oxide containing 3% by weight of zinc oxide was used in an amount of 12 parts by weight to 88 parts by weight of the polyethylene composition, in place of the anatase-type titanium oxide white pigment in support B-II.
  • a composition comprising 50 parts by weight of dipentaerythritol propyleneoxide (12 mols)-hexaacrylate ester adduct and 50 parts by weight of rutile-type titanium oxide was blended and dispersed in a ball mill for 20 h or more and the resulting blend was coated and dried on the raw paper mentioned below in a dry film thickness of 20 »m.
  • the raw paper used here was prepared by coating a 20 »m polyethylene composition layer on the same white raw paper as that used in preparation of support (B-I), the back surface of the paper being coated with a 20 »m polyethylene layer (density 0.960 g/ml, MI 25 g/10 min).
  • the thus coated layer was treated by irradiation with an electron ray in an amount corresponding to an absorption dose of 5 (M.rad) under an accelerated voltage of 200 kV, to prepare support (B-IV).
  • the second to eighth layers include two kinds of (a) and (b) as indicated in Table B-1 above.
  • Sample (a) is a silver bromide-rich material
  • sample (b) is a silver chloride-rich material.
  • the compositions of sample (a) and sample (b) are mentioned below.
  • Second Layer Blue-sensitive Silver Halide Emulsion Layer
  • sample (b) The same additives as those used in the preparation of sample (a) were used for sample (b), except the compounds (Sen-6) and (Sen-7) which were as follows.
  • Sample (E) as exposed in a commercial video printer was taken out therefrom before the development step, without being fogged with light, and processed in accordance with the following procedure. (Stabilization was effected by a four-tank counter-current system from tank (4) to tank (1).)
  • the sharpness of the thus finished samples (A) to (G) was evaluated by determining the density profile of the character as printed in each sample with a microdensitometer.
  • the microdensitometer used was a reflection mode of a commercial FMP-S Type transmission-reflection microdensitometer.
  • the measurement conditions were as follows.
  • the objective lens had five magnifications. Fiber illumination with incident angle of 45 degrees was used. Two different filters each for visual ray and red ray were used.
  • the size of the measurement slit was 10 »m ⁇ 100 »m.
  • the object to be printed was a Japanese character of 13th degree Ming-style type. This was scanned in the position and direction as indicated in Fig. 2.
  • the resolving power and response function may be used as a criterion of sharpness, but the acutance as employed herein was the optimum function in the present case because of the following two reasons. The first is that the evaluation value can be expressed by one numeral. The second is that the acutance can be calculated by measuring the object itself to be examined, and printing of any other particular pattern for evaluation is unnecessary.
  • Sample (E) of Example B-5 and Sample (F) of Example B-6 were prepared.
  • a printer comprising a combination of the CRT exposure system of Fig. 1 and the portrait exposure system with light path switch-over means as described in JP-A-62-184446, a portrait was combined with Japanese characters.
  • the characters were inputted from the character-inputting means and were displayed on the black-and-white CRT through the CRT controller, and printed on each of samples (E) and (F) to prepare a New Year's Card.
  • the spectral sensitivity curve of sample (F) is shown in Fig. 4-a; and that of sample (E) in Fig. 4-b.
  • a mixture of fluorescent substances of P-22R and P45 (code numbers of EIA; Electronic Industries Association) were used, and the relative emission strength is shown in Fig. 5.
  • Fig. 6 shows spectral transmittance curves of B, G, R and Y filters used in the present example.
  • sample (F) was developed with the developer (for processing (i) mentioned above) as filled in a commercial Video Printer.
  • sample (E) was, after printing, developed with the processing solutions (for processing (ii) mentioned above) as filled in a modified Video Printer where the rack and other parts had been reformed so as to be suited for the processing (ii).
  • the thus obtained print having both portrait and characters was cut into a size of about 150 mm (length) ⁇ about 100 mm (width).
  • An aqueous adhesive was applied to the back surface of the resulting print and this was attached to a postal card (as described in the Example of JP-A-63-104050). This was cut into a size of 145 m ⁇ 98 mm to give a print-attached postcard having a dry weight of 5.8 g.
  • Sample (A) of Example B-1 was also processed in the same manner as Sample (F) to obtain a print-attached postcard.
  • those obtained from samples (F) and (E) exhibited excellent image quality of the character images.
  • the latter postcards from samples (F) and (E) had a combination of a portrait photograph and character images which were comparable to the character images obtained by offset printing using lith film and a PS plate.
  • These print-attached postcards from samples (F) and (E) had a high quality appearance.
  • character-combined photograph prints can be provided, which have excellent image sharpness and excellent tone reproducibility of highlight details.
  • the dye crystal composition shown below was kneaded and finely ground by a sand mill.
  • the ground composition was dispersed in 25 ml of an aqueous solution of 10% lime-processed gelatin containing 1 g of citric acid dissolved therein and sands used for grinding were removed using a glass filter.
  • the dyes adsorbed to sands on the glass filter were recovered using warm water and added to the dispersion to provide 100 ml of the solid fine grain dispersion of the dyes containing 7% gelatin.
  • Example B-2 After applying a corona discharging treatment onto the support as Support B-II in Example B-3 and forming thereon a subbing layer, a colored layer was formed thereon using the aforesaid solid fine grain dispersion of the dyes as the first layer in Example B-2.
  • 2,4-dichloro-5-hydroxy-1,3,4-triazine sodium salt was used as a hardening agent.
  • composition of the first layer was as follows.
  • the mean grain size of the solid fine grains of the dyes observed by a transmission type electron microscope (200 kV) was about 0.25 »m and aggregates having grain sizes of larger than about 3 »m were not observed.
  • Example B-6 Furthermore, the second layer to the eighth layer as in Examples B-2, B-4, and B-6 were formed thereon to provide Sample H.
  • Sample H was subjected to the sensitometry as in Example B-2 and also the printing time for printing CRT images was determined using the aforesaid video printer as in Example 6 and the Ac value was determined as in Example B-6. The results obtained are shown in Table B-11 below.
  • Sample H shows the excellent Ac value as compared with Sample F at the same exposure time.
  • the first layer (colored layer) containing the solid fine grain dispersion was formed using the solid fine grain dispersion of the dyes shown in Example B-9. Then, the second layer to the eighth layer of Sample (b) as in Example B-5 were formed thereon to provide Samples I, J, K and L, respectively.
  • Example B-5 each sample was processed by Processing (ii) as shown in Example B-5, the exposure time for printing in the aforesaid video printer was determined as Example B-5 and the Ac value was determined as in Example B-5.
  • Table B-12 The results obtained are shown in Table B-12 below.
  • the method of the present invention can provide a silver halide photographic material capable of giving photographic prints having less stain by processing, having excellent whiteness, having excellent sharpness of images, and being excellent in tone reproducibility of details of the highlight.
  • a waterproof titanium oxide-containing white pigment resin layer comprising the composition mentioned below was formed on the surface of a white raw paper made of 100% LBKP for photographic paper (hardwood, bleached sulfate pulp) (weight 175 g/m2, thickness about 180 »m), to prepare support (C-I).
  • titanium oxide white pigment 10 parts by weight were surface-treated with silicon oxide, and aluminium oxide was added to 90 parts by weight of polyethylene composition (i) (density 0.920 g/ml, melt index (MI) 5.0 g/10 min) and kneaded.
  • polyethylene composition (i) density 0.920 g/ml, melt index (MI) 5.0 g/10 min
  • MI melt index
  • the resulting blend was coated on the raw paper by melt-extrusion coating to form a 30 »m waterproof resin layer thereon.
  • the back surface of the white raw paper was coated with only a polyethylene composition (ii) (density 0.950 g/ml, MI 8.0 g/10 min) to form a 20 »m waterproof resin layer thereon.
  • the same titanium oxide powder as that used in preparation of support (C-I) was dipped in an ethanol solution of trimethylol ethane and then heated. After the evaporation of ethanol, a surface-treated titanium oxide white pigment was obtained. The alcohol adhered to the titanium oxide in an amount of about 1% by weight to coat the surface of the grains. The back surface of the white raw paper was coated with the same polyethylene composition (ii) as that used for the preparation of support (C-I) to form a waterproof resin layer thereon.
  • Support C-III was prepared in the same manner as support C-II, except that titanium oxide containing 3% by weight of zinc oxide was used in an amount of 12 parts by weight to 80 parts by weight of the polyethylene composition, in place of the anatase-type titanium oxide white pigment in support C-II.
  • a composition comprising 50 parts by weight of dipentaerythritol propyleneoxide (12 mols)-hexaacrylate ester adduct and 50 parts by weight of rutile-type titanium oxide was blended and dispersed in a ball mill for 20 h or more and the resulting blend was coated and dried on the raw paper mentioned below in a dry film thickness of 20 »m.
  • the raw paper used here was prepared by coating a 20 »m polyethylene composition layer on the same white raw paper as that used in preparation of support (C-I), the back surface of the paper being coated with a 20 »m polyethylene layer (density 0.960 g/ml, MI 25 g/10 min).
  • the thus coated layer was treated by irradiation with an electron ray in an amount corresponding to an absorption dose of 5 M.rad under an accelerated voltage of 200 kV, to prepare support (C-VI).
  • Supports (C-I), (C-II) and (C-III) contained ultramarine in an amount of about 0.3% by weight to the total of the polyethylene and white pigment grains; and support (C-IV) contained the same in an amount of about 0.15% by weight.
  • Silver halide emulsions (1) to (6) were prepared as mentioned below.
  • Ex DyeB( as CR-compound) was added to the emulsion (i) in an amount of 2.3 ⁇ 10 ⁇ 4 mol per mol of the silver halide at 58°C, and then sodium thiosulfate, chloroauric acid and ammonium rhodanide were added for optimum chemical sensitization for obtaining a surface latent image type emulsion. Afterwards, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (as stabilizer) was added. The resulting emulsion was called emulsion (1).
  • Emulsions (2) to (6) were prepared in the same manner as emulsion (1), whereupon the temperature for the grain formation and the CR-compound were varied as indicated in Table C-2 below. When silver bromide was added, the amount of the chloroauric acid was halved for effecting the optimum chemical sensitization.
  • Plural layers each having the composition mentioned below were formed on a paper support both surfaces of which were coated with polyethylene (support C-II) to prepare a multilayer color photographic paper sample.
  • the coating compositions were prepared by blending a silver halide emulsion, chemicals and a coupler-containing emulsion. The method of preparing the compositions is discussed below.
  • magenta, cyan and interlayer emulsions were prepared in the same manner.
  • Stabilizer (Ex-3d) was added to the blue-sensitive emulsion layer in an amount of 2.5 ⁇ 10 ⁇ 4 mol per mol of the silver halide.
  • the gelatin hardening agent used for each layer was 1-hydroxy-3,5-dichloro-s-triazine sodium salt.
  • compound (Ex-3c) was added to the red-sensitive emulsion layer in an amount of 2.6 ⁇ 10 ⁇ 3 mol per mol of the silver halide.
  • compositions of the layers constituting each of samples (1) to (4) are mentioned below.
  • the numeral indicates the amount coated by the unit g/m2.
  • the silver halide coated is expressed by the amount of silver therein.
  • Second Layer Blue-sensitive Layer
  • each of the samples was sensitometrically wedgewise exposed with a commercial sensitometer (color temperature of light source 3200°K) through a green filter.
  • the exposure time was 1/10 s, and the exposure amount was 250 CMS.
  • Sample (4) is noted to be superior to sample (1), as the blue-sensitivity, green-sensitivity and red-sensitivity were well balanced at a high level and the fog was suppressed.
  • ExDyeR in emulsion (6) was replaced by ExDyeR-1, and the same result was also obtained.
  • color photographic paper samples (5), (6) and (7) were prepared in the same manner as the photographic material of sample (3) prepared in Example C-1. These samples were subjected to the same sensitometry as that carried out in Example C-2. In addition, the same rectangular wave pattern for CTF determination used in Example C-2 was applied to the surface of each of samples (5), (6) and (7) and the resolving power of each sample was determined in the same manner as in Example C-2. The results obtained are shown in Table C-6 below.
  • Table C-6 demonstrate that the color photographic paper samples (6) and (7) having support (C-III) and (C-IV), respectively are superior to sample (5) having support (C-I) with respect to the sensitivity and resolving power.
  • Emulsions (8) and (9) were prepared as follows: First, emulsion (i) was prepared in the same manner as in Example C-2, and the above-mentioned ExDyeR-1 (as CR-compound) was added thereto in an amount of 1.5 ⁇ 10 ⁇ 4 mol/mol-Ag at 42°C. Next, fine silver halide grains were added and heated and then sodium thiosulfate, chloroauric acid and ammonium rhodanide were added following the process of preparing emulsion (6) in Example C-2.
  • sample (8) and sample (9) were prepared, respectively.
  • Photographic material samples (1) to (4) prepared in Example C-2 and samples (8) and (9) prepared in Example C-4 were tested in accordance with the procedure mentioned below.
  • Each of the six kinds of samples was set in a commercial video printer and color name cards composed of a portrait image, a CG image and a character image were prepared.
  • the flow sheet of the videoprinter is shown in Fig. 1.
  • the portrait image is displayed in the color monitor and the black-and-white CRT as digital information
  • the CG image and the character image are synthesized in the image synthesizing means and are also displayed in the color monitor and the black-and-white CRT through the CRT controller.
  • the yellow image, green image and red image as displayed in the black-and-white CRT were passed through the lens system and printed on the sample via the three color filters of (B+Y) filter, G filter and R filter which have the spectral transmittance as shown in Fig.
  • the image quality of the character images obtained from samples (2) to (4) and samples (8) and (9) was superior to that of the character images obtained from sample (1), especially with respect to the sharpness and the edge contrast.
  • Each of samples (3) and (4) was cut into a roll having a width of 102 mm.
  • the resulting roll was charged in a printer equipped with CRT exposure system and photographic image exposure system, following the description of JP-A-62-184446.
  • a portrait image was printed on the roll by a photographic image exposure system while character images were simultaneously printed thereon by a CRT exposure system.
  • Example C-2 the thus printed roll was passed through the photographic processing device to complete the color development mentioned in Example C-2, whereby a photographic print with written characters was obtained. This was cut to a size of 98 mm ⁇ 148 mm to obtain a print for a postcard.
  • the image quality of the character images printed was comparable to that obtained by conventional lithographic printing.
  • the thus prepared print was attached to a lottery postal card to form a print-attached lottery postal card, following the description of JP-A-63-70858.
  • the dye crystal composition shown below was kneaded and finely ground by a sand mill.
  • the ground mixture was dispersed in 25 ml of an aqueous solution of 10% lime-processed gelatin containing 1 g of citric acid dissolved therein and sands used for the sand mill were removed using a glass filter.
  • the dyes adsorbed to the sands on the glass filter were recovered using warm water and added to the dispersion to provide 100 ml of the solid fine grain dispersion of dyes containing 7% gelatin.
  • Example C-2 After applying a corona discharging treatment onto the support C-II as in Example C-2 and forming thereon a gelatin subbing layer, a colored layer was formed thereon the first layer having the composition shown below as in Example C-2.
  • 2,4-dichloro-5-hydroxy-1,3,4-triazine sodium salt was used as a hardening agent.
  • the mean grain size of the solid fine grains of the dyes by a transmission type electron microscopic observation was about 0.25 »m and aggregates of larger than about 3 »m were not observed.
  • Example C-2 When the sample was immersed in a color developer as used in Example C-2, the dyes were decolored within about 15 s and when the sample was immersed in a bleach-fixation solution as in Example C-2, decoloring was observed to a considerable extent.
  • Example C-2 Furthermore, the second layer to eighth layer as shown in Example C-2 were formed on the first layer of the sample to provide Sample 10. The sample was subjected to the sensitometric exposure and CTF measurement as Samples 1 to 4 in Example C-2 and the results obtained are shown in Table C-9.
  • Example C-6 dye crystals shown in Table C-10 below and a dispersion aid were kneaded, the dye crystals were ground by a ball mill, and the ground crystals were dispersed in 25 ml of an aqueous solution of 10% lime-processed bone gelatin containing 1 g of citric acid dissolved therein.
  • the beads used for grinding were removed by filtration, and the dyes adsorbed to the filter and the beads were recovered and added to the dispersion to provide 100 ml of the solid fine grain dispersion of dyes containing 7% gelatin.
  • Example C-3 On each of the supports Support C-III and C-IV in Example C-3 was formed a first layer using the aforesaid solid fine grain (fine crystal) dispersion prepared above. Furthermore, the second layer to the eighth layer as in Samples 6 and 7 in Example C-2 were formed thereon to provide Samples 11 to 15, respectively.
  • Sample 16 was subjected to the sensitometry as applied to Sample 9 in Examples C-4 and C-5 and also the printing times at blue light, green light, and red light were determined using a commercial video printer. The results obtained are shown in Table C-11 below.
  • the printing times for Sample 16 are the same as or faster than those for Sample 9. Also, the fog in Sample 16 was 0.08 less in the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer.
  • a color print having not only photographic picture images with excellent image sharpness but also line images and character images with high edge contrast can be obtained rapidly and easily.
  • a so-called mini-laboratory system composed of a CRT exposure system printer and a photographic processing device can efficiently be used for processing the photographic material of the invention, and a print having not only photographic picture images with excellent image quality but also CG images, line images and/or character images with improved image sharpness can be formed easily in a short period of time of about 4 min or less.
  • the photographic material of the invention is therefore especially convenient for forming printed postal cards.

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Claims (39)

  1. Farbphotographisches Material, das umfaßt mindestens eine lichtempfindliche Silberhalogenidschicht, die auf einem reflektierenden Träger angeordnet ist, der weiße pigmentkörnchen in einer wasserundurchlässigen Harzschicht enthält, wobei die pigmentkörnchen in der wasserundurchlässigen Harzschicht in einer Dichte von 10 Gew.-% oder mehr vorliegen, und eine gefärbte Schicht, die durch photographische Behandlung (Entwicklung) entfärbt werden kann, die zwischen dem Träger und der lichtempfindlichen Silberhalogenidschicht angeordnet ist,
    dadurch gekennzeichnet, daß der Dispersionsgrad der weißen pigmentkörnchen in der Schicht 0,20 oder weniger beträgt, bestimmt als Fluktuations-Koeffizient (s/R) des possessorischen Flächenanteils (%) pro Einheitsfläche von 6 »m x 6 »m, worin R für den mittleren possessorischen Flächenanteil pro Einheitsfläche und s für die Standardabweichung des possessorischen Flächenanteils pro Einheitsfläche stehen.
  2. Farbphotographisches Material nach Anspruch 1, worin die wasserundurchlässige Harzschicht auf eine Trägerbasis aufgebracht ist.
  3. Farbphotographisches Material nach Anspruch 2, worin die Trägerbasis ein neutrales Papier ist.
  4. Farbphotographisches Material nach Anspruch 1, worin die weißen Pigmentkörnchen oberflächenbehandelt oder nicht oberflächenbehandelt und feine Körnchen sind, ausgewählt aus der Gruppe, die besteht aus Titanoxid, Bariumsulfat, Calciumsulfat, Siliciumoxid, Zinkoxid, Titanphosphat und Aluminiumoxid.
  5. Farbphotographisches Material nach Anspruch 1, worin die weißen Pigmentkörnchen in der wasserundurchlässigen Harzschicht in einer Dichte von bis zu 60 Gew.-% vorliegen.
  6. Farbphotographisches Material nach Anspruch 1, worin die weißen Pigmentkörnchen in der Oberfläche der wasserundurchlässigen Harzschicht oder in einer Dicke von bis zu 10 »m ab der Oberfläche der Schicht dispergiert sind.
  7. Farbphotographisches Material nach Anspruch 1, worin die weißen Pigmentkörnchen der wasserundurchlässigen Harzschicht in Gegenwart eines oberflächenaktiven Agens einverleibt wurden, um den Fluktuationskoeffizient des possessorischen Oberflächenanteils der Körnchen zu kontrollieren (zu steuern).
  8. Farbphotographisches Material nach Anspruch 1, worin die gefärbte Schicht mindestens einen Vertreter aus der Gruppe Farbstoff und kolloidales Silber enthält.
  9. Farbphotographisches Material nach Anspruch 1, worin die gefärbte Schicht einen Farbstoff und ein kationisches Polymer enthält.
  10. Farbphotographisches Material nach Anspruch 9, worin das kationische Polymer ein nicht-färbendes Polymer ist, das mindestens eine Wasserstoff enthaltende Ammoniumbase in dem Kationen-Anteil aufweist, die als Anionenaustausch-Polymer fungiert.
  11. Farbphotographisches Material nach Anspruch 10, worin das kationische Polymer dargestellt wird durch die Formel (I)
    Figure imgb0434
     worin bedeuten:
    A   eine Monomereinheit, abgeleitet aus der Copolymerisation eines copolymerisierbaren Monomers, das mindestens zwei copolymerisierbare ethylenisch ungesättigte Gruppen aufweist, von denen eine in der Seitenketten-Gruppe des Monomers vorliegt;
    B   eine Monomereinheit, abgeleitet aus der Copolymerisation eines copolymerisierbaren ethylenisch ungesättigten Monomers;
    R₁   ein Wasserstoffatom, eine niedere Alkylgruppe oder eine Aralkylgruppe;
    Q   eine Einfachbindung oder eine Alkylengruppe, eine Arylengruppe, eine Aralkylengruppe,
    Figure imgb0435
     worin L für eine Alkylengruppe, eine Arylengruppe, eine Aralkylengruppe und R für eine Alkylgruppe stehen;
    G   
    Figure imgb0436
     worin R₂, R₃, R₄, R₅, R₆, R₇, R₈ und R₉, die gleich oder verschieden sind, jeweils stehen für ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe oder eine Aralkylgruppe und X⊖ ein Anion darstellt;
    wobei jeweils zwei oder mehr der Reste Q, R₂, R₃ und R₄ oder Q, R₅, R₆, R₇, R₈ und R₉ miteinander verbunden sein können unter Bildung einer Ringstruktur zusammen mit dem benachbarten Stickstoffatom; wobei in der Gruppe der Formel
    Figure imgb0437
     mindestens einer der Reste R₂, R₃ und R₄ ein Wasserstoffatom sein muß; und
    x, y und z jeweils einen Molprozentsatz, wobei x 0 bis 60 beträgt, y 0 bis 60 beträgt und z 30 bis 100 beträgt;
    und wobei alle die genannten Gruppen substituiert oder unsubstituiert sind, und
    die folgenden Polymeren:
    Figure imgb0438
    Figure imgb0439
  12. Farbphotographisches Material nach Anspruch 1, worin die gefärbte Schicht eine Festkorn-Dispersion eines Farbstoffes enthält, der in einer wäßrigen Lösung mit einem pH-Wert von nicht höher als 7,0 bis zu einem solchen Grade unlöslich ist, daß der dispergierte Zustand in einem hydrophilen Kolloid aufrechterhalten werden kann, und der in einer wäßrigen Lösung mit einem pH-Wert von mindestens 9,0 löslich ist.
  13. Farbphotographisches Material nach Anspruch 12, dadurch gekennzeichnet, daß der Farbstoff mindestens ein Farbstoff ist, der ausgewählt wird aus der Gruppe, die besteht aus Verbindungen der folgenden Formeln (II), (III), (IV), (V) oder (VI);
    Figure imgb0440
    Figure imgb0441

            A₂ = L₁(̵L₂=L₃)̵n A₂   (IV)

    Figure imgb0442
    Figure imgb0443
     worin bedeuten:
    A₂   (wobei zwei A₂-Gruppen gleich oder verschieden sind), einen sauren Kern (Ring) mit mindestens einem Substituenten, ausgewählt aus einer Carboxyphenylgruppe, einer Sulfamoylphenylgruppe, einer Sulfonamidophenylgruppe, einer Carboxyalkylgruppe und einer Hydroxyphenylgruppe (wobei die sauren Kerne(Ringe) außerdem einen weiteren Substituenten zusätzlich zu der obengenannten Gruppe aufweisen können), wobei der saure Kern(Ring) ausgewählt wird aus der Gruppe 2-Pyrazolin-5-on, Rhodanin, Hydantoin, Thiohydantoin, 2,4-Oxazolindion, Isoxazolindinon, Barbitursäure, Thiobarbitursäure, Indandion und Hydroxypyridon;
    B₂   einen basischen Kern(Ring), der mindestens einen Substituenten aufweist, ausgewählt aus einer Carboxygruppe, einer Sulfamoylgruppe und einer Sulfonamidogruppe (wobei die basischen Kerne(Ringe) außerdem einen weiteren Substituenten zusätzlich zu der obengenannten Gruppe aufweisen können), wobei die basischen Kerne(Ringe) ausgewählt werden aus der Gruppe Pyridin, Chinolin, Indolenin, Oxazol, Benzoxazol, Naphthoxazol und Pyrrol;
    R₄₀   ein Wasserstoffatom oder eine Alkylgruppe;
    R₄₁ und R₄₂   jeweils eine substituierte oder unsubstituierte Alkylgruppe, eine substituierte oder unsubstituierte Arylgruppe, eine Acylgruppe oder eine Sulfonylgruppe, wobei R₄₁ und R₄₂ miteinander kombiniert sein können unter Bildung eines 5- oder 6-gliedrigen Ringes;
    R₄₃ und R₄₆   jeweils ein Wasserstoffatom, eine Hydroxygruppe, eine Alkylgruppe, eine Alkoxygruppe oder ein Halogenatom;
    R₄₄ und R₄₅   jeweils ein Wasserstoffatom; oder
    R₄₁ und R₄₄ oder R₄₂ und R₄₅   eine Nicht-Metallatomgruppe bilden, die für die Bildung eines 5- oder 6-gliedrigen Ringes durch die Kombination derselben erforderlich ist;
    L₁, L₂ und L₃   jeweils eine substituierte oder unsubstituierte Methingruppe;
    X₃ und Y₃   jeweils eine Elektronen anziehende Gruppe, wobei entweder X₃ oder Y₃ mindestens eine Carboxyphenylgruppe, Sulfamoylphenylgruppe, Sulfonamidophenylgruppe, Carboxyalkylgruppe oder Hydroxyphenylgruppe aufweist;
    m   die Zahl 0 oder 1;
    n   die Zahl 0, 1 oder 2; und
    p   die Zahl 0 oder 1, wobei dann, wenn p = 0, R₄₃ eine Hydroxygruppe oder eine Carboxygruppe darstellt und R₄₄ und R₄₅ ein Wasserstoffatom und die folgenden Farbstoffe darstellen:
    Figure imgb0444
    Figure imgb0445
    Figure imgb0446
    Figure imgb0447
    Figure imgb0448
    Figure imgb0449
    Figure imgb0450
    Figure imgb0451
    Figure imgb0452
    Figure imgb0453
    Figure imgb0454
    Figure imgb0455
    Figure imgb0456
    Figure imgb0457
    Figure imgb0458
    Figure imgb0459
    Figure imgb0460
  14. Farbphotographisches Material nach Anspruch 1, worin die Silberhalogenidschicht die dem Träger am nächsten angeordnete Silberhalogenidschicht ist.
  15. Farbphotographisches Material nach Anspruch 8, worin die Menge des Farbstoffs 1 bis 500 mg/m² beträgt.
  16. Farbphotographisches Material nach Anspruch 8, worin die Menge des kolloidalen Silbers 0,01 bis 0,5 g/m² beträgt.
  17. Farbphotographisches Material nach Anspruch 1, worin die Dicke der gefärbten Schicht 0,1 bis 10 »m beträgt.
  18. Farbphotographisches Material nach Anspruch 1, worin die Dicke der wasserundurchlässigen Harzschicht 5 bis 200 »m beträgt.
  19. Farbphotographisches Material nach Anspruch 1, worin die lichtempfindliche Silberhalogenidemulsionsschicht ein Silberhalogenid enthält, das 15 Mol-% oder mehr Silberchlorid enthält.
  20. Farbphotographisches Material nach Anspruch 1, worin die lichtempfindliche Silberhalogenidschicht ein Silberhalogenid enthält, das 98 Mol-% oder mehr Silberchlorid enthält.
  21. Farbphotographisches Material nach Anspruch 1, worin die lichtempfindliche Silberhalogenidschicht ein Silberhalogenid enthält, die nicht mehr als 1 Mol-% Silberjodid enthält.
  22. Farbphotographisches Material nach Anspruch 1, worin das farbphotographische Material ein farbphotographisches Reflexions-Material ist, bei dem mindestens eine lichtempfindliche Silberhalogenidschicht einen Farbkuppler enthält, die wasserundurchlässige Harzschicht auf der Seite des Trägers angeordnet ist, der mit der lichtempfindlichen Silberhalogenidschicht beschichtet ist, und die lichtempfindliche Silberhalogenidschicht eine Emulsion von Silberchloridbromid enthält, das einen mittleren Silberchloridgehalt von 90 Mol-% oder mehr und eine im Innern und/oder auf der Oberfläche des Emulsionskorns angeordnete Silberbromidphase aufweist.
  23. Farbphotographisches Material nach Anspruch 22, worin die Oberfläche des Emulsionskorns goldsensibilisiert ist.
  24. Farbphotographisches Material nach Anspruch 22, worin der reflektierende Träger weiße Pigmentkörnchen in einer wasserundurchlässigen Harzschicht in einer Menge von 12 Gew.-% oder mehr enthält und der Dispersionsgrad der weißen Pigmentkörnchen 0,15 oder weniger beträgt, bestimmt als Fluktuationskoeffizeint (s/R) des projizierten possessorischen Flächenanteils (%) pro Einheitsfläche von 6 »m x 6 »m, wobei R für den mittleren possessorischen Flächenanteil pro Einheitsfläche und s für die Standardabweichung des possessorischen Flächenanteils stehen.
  25. Farbphotographisches Material nach Anspruch 23, worin eine Verbindung, die eine Thiosulfonylgruppe aufweist, der Silberchloridbromidemulsion vor, während oder nach der Goldsensibilisierung der Emulsion zugesetzt worden ist.
  26. Farbphotographisches Material nach Anspruch 22, worin die lichtempfindliche Silberhalogenidschicht ein Silberhalogenid enthält, das 98 Mol-% oder mehr Silberchlorid enthält.
  27. Farbphotographisches Material nach Anspruch 22, worin die lichtempfindliche Silberhalogenidschicht ein Silberhalogenid enthält, das nicht mehr als 1 Mol-% Silberjodid enthält.
  28. Verfahren zur Erzeugung eines Farbbildes, dadurch gekennzeichnet, daß das farbphotographische Material nach Anspruch 1 oder 22 vervielfältigt (kopiert) wird unter Verwendung eines Abtastbelichtungssystems und dann einer Farbentwicklungsbehandlung unterworfen wird.
  29. Verfahren zur Erzeugung eines Farbbildes, das die Stufe umfaßt: bildmäßiges Belichten eines farbphotographischen Materials, das mindestens eine lichtempfindliche Schicht aufweist, die auf einem ein wasserdichtes Harz enthaltenden reflektierenden Träger vorgesehen ist, unter Verwendung eines Abtastbelichtungssystems, wobei der reflektierende Träger weiße Pigmentkörnchen in der wasserundurchlässigen Harzschicht, die auf der Seite angeordnet ist, die mit der lichtempfindlichen Schicht beschichtet ist, in einer Dichte von 10 Gew.-% oder mehr enthält, dadurch gekennzeichnet, daß der Dispersionsgrad der weißen Pigmentkörnchen in der wasserundurchlässigen Harzschicht 0,20 oder weniger beträgt, bestimmt als Fluktuations-Koeffizient (s/R) des projizierten possessorischen Flächenanteils (%) pro Einheitsfläche von 6 »m x 6 »m, worin R für den mittleren projizierten possessorischen Flächenanteil pro Einheitsfläche und s für die Standardabweichung des projizierten possessorischen Flächenanteils pro Einheitsfläche stehen.
  30. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin das farbphotographische Material umfaßt:
    mindestens drei Arten von lichtempfindlichen Silberhalogenidschichten, die jeweils einen Farbkuppler enthalten, ausgewählt aus einem Blaugrünkuppler, einem Purpurrotkuppler und einem Gelbkuppler, die auf dem Träger angeordnet sind, und
    eine gefärbte Schicht, die während des Farbentwicklungsprozesses entfärbt werden kann und die zwischen dem Träger und der lichtempfindlichen Silberhalogenidschicht-Einheit angeordnet ist.
  31. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin die bildmäßige Belichtung eines Strich-Originals oder eines Zeichen (Buchstaben)-Originals unter Verwendung eines CRT-Belichtungssystems durchgeführt wird.
  32. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin das farbphotographische Material bildmäßig belichtet wird durch Verwendung einer Kombination aus einem Schwarz-Weiß-CRT-Belichtungssystem und einem photographischen Bild-Belichtungssystem in Kombination mit einer Lichtdurchgangs-Umschalteinrichtung.
  33. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin die lichtempfindliche Schicht eine hydrophile Kolloidschicht ist, die Silberhalogenidkörnchen enthält, die hauptsächlich auf der Oberfläche des Korns ein latentes Bild erzeugen.
  34. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin die lichtempfindliche Schicht eine hydrophile Kolloidschicht ist, die Silberchlorid oder Silberchloridbromid enthält.
  35. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin die lichtempfindliche Silberhalogenidschicht ein Silberhalogenid enthält, das 15 Mol-% oder mehr Silberchlorid enthält.
  36. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin die lichtempfindliche Silberhalogenidschicht ein Silberhalogenid enthält, das 98 Mol-% oder mehr Silberchlorid enthält.
  37. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 29, worin die lichtempfindliche Silberhalogenidschicht ein Silberhalogenid enthält, das nicht mehr als 1 Mol-% Silberjodid enthält.
  38. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 30, worin die gefärbte Schicht einen Farbstoff enthält.
  39. Verfahren zur Erzeugung eines Farbbildes nach Anspruch 30, worin die gefärbte Schicht eine Feststoffdispersion eines Farbstoffes enthält, der in einer wäßrigen Lösung bis zu einem solchen Grad unlöslich ist, daß der dispergierte Zustand in einem hydrophilen Kolloid mit einem pH-Wert von nicht höher als 7,0 aufrechterhalten werden kann, und der in einer wäßrigen Lösung mit einem pH-Wert von mindestens 9,0 löslich ist.
EP19890106744 1988-04-15 1989-04-14 Lichtempfindliches photographisches Silberhalogenidmaterial Expired - Lifetime EP0337490B1 (de)

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
JP9280488 1988-04-15
JP92804/88 1988-04-15
JP145492/88 1988-06-13
JP14549288 1988-06-13
JP15179188 1988-06-20
JP151791/88 1988-06-20
JP255425/88 1988-10-11
JP63255425A JPH07111558B2 (ja) 1988-04-15 1988-10-11 ハロゲン化銀写真感光材料
JP27894/89 1989-02-07
JP1027894A JP2533367B2 (ja) 1988-06-20 1989-02-07 反射型カラ―感光材料とそのカラ―画像形成法
JP30405/89 1989-02-09
JP1030405A JP2879106B2 (ja) 1988-06-13 1989-02-09 カラー画像形成法

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EP0337490A2 EP0337490A2 (de) 1989-10-18
EP0337490A3 EP0337490A3 (en) 1990-08-08
EP0337490B1 true EP0337490B1 (de) 1995-12-20

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DE (1) DE68925144T2 (de)

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JPH03221949A (ja) * 1990-01-29 1991-09-30 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料の処理方法
JP2684274B2 (ja) 1991-11-27 1997-12-03 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP2893100B2 (ja) 1991-11-27 1999-05-17 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JPH0675343A (ja) 1992-07-06 1994-03-18 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びカラー画像形成方法
JPH0627587A (ja) * 1992-07-06 1994-02-04 Fuji Photo Film Co Ltd カラー写真感光材料
JPH0627616A (ja) * 1992-07-09 1994-02-04 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH0675348A (ja) * 1992-07-09 1994-03-18 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5252424A (en) * 1992-09-04 1993-10-12 Eastman Kodak Company Photographic paper
JP3026243B2 (ja) 1993-06-08 2000-03-27 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
JP3372994B2 (ja) 1993-06-11 2003-02-04 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料の処理方法
EP0643328B1 (de) * 1993-09-09 2001-05-09 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial und Farbbildherstellungsverfahren
JP3515602B2 (ja) * 1994-01-27 2004-04-05 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料及びカラー画像形成方法
JP3406093B2 (ja) 1994-10-07 2003-05-12 富士写真フイルム株式会社 ハロゲン化銀感光材料
JP3584119B2 (ja) 1996-04-05 2004-11-04 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料
DE60143154D1 (de) 2001-04-17 2010-11-11 Fujifilm Corp Photographisches Silberhalogenidmaterial enthaltend einen Methinfarbstoff
WO2005073804A1 (en) 2004-01-30 2005-08-11 Fuji Photo Film Co., Ltd. Silver halide color photographic light-sensitive material and color image-forming method

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EP0337490A3 (en) 1990-08-08
EP0337490A2 (de) 1989-10-18
DE68925144T2 (de) 1996-06-13
DE68925144D1 (de) 1996-02-01

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