Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/32—Colour coupling substances
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material
• • 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
  • G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances

Definitions

• the present invention relates to a silver halide color photographic material and a color photographic print, and more particularly to a color photographic print suitable for use as an ID card, a cashing card, a telephone card, etc.
• Conventional silver halide color photographic materials comprise a silver halide emulsion layer containing a cyan color forming coupler, a silver halide emulsion layer containing a magenta color forming coupler and a silver halide emulsion layer containing a yellow color forming coupler coated on various kinds of supports.
• a transparent plastic film for example, a cellulose triacetate film, a polyethylene terephthalate film, a vinyl resin film, etc.
• a reflective support baryta coated paper, synthetic paper, polyethylene laminated paper, a plastic sheet containing a white pigment, a glass plate, a metal plate (for example, an aluminium plate having an anodized surface), etc. may be employed.
• a white pigment be incorporated into a plastic material or that a white pigment containing layer is provided,on a surface of a plastic material in order to particularly improve whiteness of the supports.
• an object of the present invention is to provide a reflective color photographic light-sensitive material which forms color images having improved sharpness and a color photographic print which has color images of improved sharpness.
• Another object of the present invention is to provide a silver halide color photographic material and a color photographic print each having a reflective support of good smoothness.
• Still another object of the present invention is to provide a support as used for a silver halide color photographic material and a color photographic print on the surface of which a figure, a letter, etc. can be subjected to embossment with heat processing when the material or the print is used as various kinds of cards.
• a silver halide color photographic material comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one red-sensitive silver halide emulsion layer containing a cyan color forming coupler represented by the general formula (1) or (2) shown below, at least one green-sensitive silver halide emulsion layer containing a magenta color forming coupler represented by the general formula (3) or (4) shown below, and at least one blue-sensitive silver halide emulsion layer containing a yellow color forming coupler represented by the general formula (5) shown below and also with a color photographic print comprising a reflective support composed of a vinyl chloride resin containing a white pigment and having thereon in an appropriate order at least one emulsion layer containing a cyan dye obtained by a reaction of a cyan color forming coupler represented by the general formula (1) or (2) shown below with an oxidation product
• R 1 , R 4 and R 5 each represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group
• R 2 represents an aliphatic group
• R 3 and R 6 each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group
• R 7 and R 8 each represents a substituted or unsubstituted phenyl group
• R 9 represents a hydrogen atom or a substituent
• R 2 and R 3 or R 5 and R 6 may be connected with each other to form a 5-membered to 7-membered ring
• Q represents a substituted or unsubstituted N-phenylcarbamoyl group
• R 10 represents the same substituent as that represented by R
• the color photographic print according to the present invention includes a color photographic print obtained by conducting at least a step of processing the silver halide color photographic material of the present invention, after imagewise exposure, with a color developing solution containing an aromatic primary amine color developing agent, and a color photographic print obtained by adhering the above-described color photographic print (but employing a transparent support) on a reflective support composed of a vinyl chloride resin containing a white pigment.
• the group capable of being released represented by X 1 , X 2 , X 3 , X 4 or X 5 include those as described in U.S. Patent 4,540,654, column 4, line 30 to column 5, line 24, herein incorporated by reference. Among them, a chlorine atom for X l or X 2 , a hydrogen atom or a group capable of being released containing a sulfur atom as a releasing atom for X 3 or X 4 and a group capable of being released containing an oxygen atom or a nitrogen atom as a releasing atom for X 5 are preferred.
• the vinyl chloride resin which constitutes the reflective support used in the present invention is a homopolymer or copolymer containing a vinyl chloride monomer as at least one kind of monomers. It is preferred that the vinyl chloride monomer occupies at least 50% by weight of the total monomer component.
• comonomer component examples include, for example, methyl methacrylate, vinyl acetate, acrylonitrile, a fluorinated olefin, a vinyl ether, vinyl bromide, vinyl acetate, maleic acid, dichlorobutadiene, vinyl fluoride, vinylidene fluoride, trifluorochloroethylene, tetrafluoroethylene, vinylidene chloride, acrylonitrile, styrene, butadiene, chloroprene, etc. Two or more of these comonomer components may be employed.
• fillers include starch, wood flour, clay, calcium carbonate, bentonite, etc.
• plasticizers include a phthalic ester (e.g., dibutyl phthalate, dioctyl phthalate,-dicyclohexyl phthalate, di-2-ethylhexyl phthalate, butyllauryl phthalate, dilauryl phthalate, butylbenzyl phthalate), a phosphoric ester (e.g., tricresyl phosphate, trixylenyl phosphate, trioctyl phosphate), a straight chain dibasic acid ester (e.g., dioctyl adipate, dioctyl azelate, dioctyl sebacate), butylphthalyl butylglycolate, etc.
• stabilizers e.g., dioctyl adipate, dioctyl azelate,
• Filler may be added in an amount of from about 20 parts to 100 parts by weight per 100 parts by weight of the resin material.
• the white pigments which can be added to the vinyl chloride resin include titanium white, zinc white, calcium carbonate, barium sulfate, white lead, white organic pigments or dyes, brightening agents, etc.
• Preferred examples of the aforementioned brightening agents include the following compounds.
• the white pigments can be employed individually or as a mixture of two or more thereof.
• the total amount of the white pigment added is preferably from 1 part by weight to 30 parts by weight and more preferably from 5 parts by weight to 15 parts by weight per 100 parts by weight of the vinyl chloride resin material.
• the vinyl chloride resin as used in the present invention exhibits resistance to heat deformation, preferably to at least 50°C, more preferably to at least 70°C from the standpoint of preventing a dimensional change during the drying step after preparation and development steps of light-sensitive materials or during use thereof.
• an average reflectivity of the reflective support used in the present invention in a visible range is from 80 to 98%.
• the thickness of the reflective support is preferably from 50 ⁇ m to 500 ⁇ m and more preferably from 100 ⁇ m to 300 um.
• a subbing treatment may be conducted in order to improve adhesion of both materials.
• various kinds of methods are known and a suitable method can be appropriately selected therefrom.
• a surface of a support is etched with acetone to make a rough surface, wood flour (cellulose component) is coated to fill in a concave portion of the surface and to cover a convex portion of the surface and thereby an affinity with gelatin is provided (because of a good affinity between cellulose and protein) and then a subbing solution containing pearl essence is coated thereon as described in Japanese Patent Publication No. 3583/60, a method wherein at least one layer composed of a mixture of cellulose nitrate and a vinyl acetate-vinyl chloride copolymer is coated as a subbing agent as described in Japanese Patent Publication No.
• EP 0065329Al (the term "OPI" as used herein refers to a "p ⁇ blished unexamined application"), a method wherein a straight chain polyphosphoric acid ester resin is coated on a support as described in British Patent 742,370, a method wherein a hardened gelatin subbing layer is subjected to corona discharge treatment and then a light-sensitive silver halide emulsion layer is coated as described in British Patent 1,472,854, a method wherein an epoxidated rubbery polymer and a film-forming unsaturated polyester are coated as subbing agents as described in British Patent 1,179,563, a method wherein first a solution of a isobutyl methacrylate polymer dissolved in a solvent which does not affect a vinyl chloride polymer and then a usual subbing layer composed of gelatin and cellulose nitrate is coated thereon as described in U.S. Patent 2,388,817, and a method wherein a subbing solution having the composition shown below
• a development inhibitor releasing compound (DIR compound) is added to the color photographic light-sensitive material according to the present invention for the purpose of further improving sharpness.
• Suitable DIR compounds include DIR couplers as described in U.S. Patents 3,933,500, 4,187,100 and 4,477,563 - , British Patent 1,504,094 and Japanese Patent Application (OPI) Nos. 206834/84, 210440/84 and 92556/85.
• dyes formed from pivaloyl acetanilide type couplers are preferred. These dyes have excellent features that the long wavelength side of their spectral absorptions is sharply cut and . that their fastness is.excellent. Further, they are easily dispersed in a hydrophilic colloid using a small amount of an organic solvent or using a water-insoluble and organic solvent soluble polymer, in comparison with benzoyl acetanilide type couplers, and thus they enable provision of a color-forming layer which is thin and has strong physical property.
• the yellow dyes which are preferably employed in the present invention are those represented by the following general formula (5-1): wherein R 14 and R 15 , which may be the same or different, each represents a hydrogen atom or a substituent which is ordinarily used for a yellow coupler, provided that both R 14 and R 15 are not hydrogen atoms at the same time; and (CD) represents a coupling residue of an aromatic primary amine developing agent.
• Suitable examples of the substituents represented by R 14 and R 15 include an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom, an alkoxycarbamoyl group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, etc.
• the coupler used may be a polymer coupler including a bis couple
• (CD) preferably represents a coupling residue of a phenylenediamine derivative represented by the following general formula (6): wherein R 11 and R 12 each represents a substituted or unsubstituted alkyl group; and R 13 represents one to four hydrogen atoms or one to four substituents.
• the alkyl group represented by R 11 or R 12 is preferably an alkyl group having from 1 to 4 carbon atoms. Suitable examples of the substituents for the alkyl group include a hydroxy group, an alkylsulfonamido group, an alkoxy group, etc. Specific examples of R 11 or R 12 include an ethyl group, a ⁇ -hydroxyethyl group, a B-methanesulfonamidoethyl group, a ⁇ -methoxyethyl group, etc. Further, a representative example of the substituent represented by R 13 is an alkyl group (for example, a methyl group, etc.).
• magenta dyes used in the present invention those represented by the following general formula (4-1) or (4-2) are preferred.
• (CD) represents a coupling residue of an aromatic primary amine developing agent and R 16 and R 17 , which may be the same or different, each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an .
• aryloxy group a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group.
• R 16 or R 17 may be a divalent group to form a bis compound.
• the magenta dye represented by the general formula (4-1) or (4-2) may be in the form of a polymer dye in which the dye moiety represented by the general formula (4-1) or (4-2) exists at the main chain or the side chain of the polymer and particularly a polymer derived from a vinyl monomer having the moiety represented by the general formula (4-1) or (4-2) is preferred.
• R 16 or R 17 represents a linking group connected to a vinyl group.
• the linking group represented by R 16 or R 17 in the cases wherein the part represented by the general formula (4-1) or (4-2) is included in a vinyl monomer includes an alkylene group (including a substituted or unsubstituted alkylene group, e.g., a methylene group, an ethylene group, a 1,10-decylene group, -CH 2 CH 2 0CH 2 CH 2 -, etc.), a phenylene group (including a substituted or unsubstituted phenylene group, e.g., a 1,4-phenylene group, a 1,3-phenylene group, etc.) -NHCO-, -CONH-, -0-, -OCO-, and an aralkylene group (e.g., etc.) or a combination thereof.
• an alkylene group including a substituted or unsubstituted alkylene group, e.g., a methylene group, an ethylene group, a 1,10
• linking groups include -NHCO-, -CH 2 CH 2 -, -CH 2 CH 2 NHCO-, -CONHCH 2 CH 2 NHCO-, -CH 2 CH 2 0CH 2 CH 2 NHCO-, and
• a vinyl group in the vinyl monomer may further have a substituent in addition to the moiety represented by the general formula (4-1) or (4-2).
• substituents include a chlorine atom or a lower alkyl group having from 1 to 4 carbon atoms (e.g., a methyl group, an ethyl group, a butyl group, etc.).
• the polymer derived from a vinyl monomer having the dye moiety may be a copolymer with a non-color forming ethylenic monomer.
• non-color forming ethylenic monomers include an acrylic acid such as acrylic acid, a-chloroacrylic acid, a-alacrylic acid (e.g., methacrylic acid, etc.), etc., an ester or an amide derived from an acrylic acid (e.g., acrylamide, n-butylacrylamide, tert-butylacrylamide, diacetoneacrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, vinyl propionate, vinyl laurate, etc.), acrylonitrile, methacrylonitrile, an aromatic vinyl compound (e.g., styrene and a derivative thereof, vinyltoluene, divinylbenzen
• Two or more non-color forming ethylenically unsaturated monomers can be used together.
• a combination of n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methyl acrylate and diacetoneacrylamide, etc. can be used.
• the non-color forming ethylenically unsaturated monomer which is used to copolymerize with a solid water-insoluble monomer coupler can be selected in such a manner that the copolymer to be formed has good physical properties and/or chemical properties, for example, solubility, compatibility with a binder in a photographic colloid composition such as gelatin, flexibility, heat stability, etc.
• magenta dyes according to the present invention are characterized by a good spectral absorption characteristic wherein the characteristic second absorption on the short wavelength side is not present or, if present, is small and the absorption on the long wavelength side is sharply cut, and in excellent fastness to high humidity and heat. Further, in the case of using polymer magenta dyes, they can be dispersed as a latex and thus an organic solvent having a high boiling point is not necessary, or is used only in a reduced amount. As the result, it is possible to decrease the thickness of the color forming layer and to increase the physical strength thereof.
• the cyan dyes used in the present invention are most typically dyes which are obtained upon an oxidation coupling reaction of phenol type couplers with paraphenyl- enediamine color developing agents. These phenol type cyan couplers may be used together with naphthol type cyan couplers. Specific examples of naphthol type couplers include those as described, for example, in U.S. Patent 2,474,293 and preferably those as described, for example, in U.S. Patents 4,052,212, 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenol couplers include those as described, for example, in U.S. Patents 2,396,929, 2,801,171 2,772,162 and 2,895,826.
• Cyan couplers which are stable against humidity and temperature are advantageously used in the present invention.
• Typical examples of these couplers include phenol cyan couplers having an alkyl group more than a methyl group at the meta-position of the phenol nucleus as descried in U.S. Patent 3,772,002, cyan couplers as described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, West German Patent Application (OLS) No. 3,329,729 and European Patent 121,365, etc., and cyan couplers as described in U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767, etc.
• the cyan dyes according to the present invention can cover a wavelength range of 600 mg to 700 m ⁇ by using two or more dyes represented by the general formula (1) or (2) in combination.
• the cyan dyes have good features that they provide cyan color images having small absorption on the short wavelength side and that they are excellent in fastness to high humidity and heat.
• (CD) may represent Further, (CD) may represent a coupling residue of a p-phenylenediamine derivative such as etc.
• the dyes which form images according to the present invention are preferably used in combination with one or more kinds of organic solvents having a high boiling point of at least 160°C represented by the general formula (7), (8), (9), (10) or (11) as shown below. Details of these organic solvents are' described in Japanese Patent Application (OPI) No. 215272/87, pages 138 to 144. Further, it is particularly preferred that the dyes are used in combination with water-insoluble, organic solvent-soluble polymers as described in Japanese Patent Publication No. 30474/73, U.S. Patent 3,619,195 and International Application No. PCT/JP 87/00492 filed July 9, 1987, etc. Moreover, the dyes may be used in combination with loaded polymeric latexes as described in U.S.
• W 1 , W 2 and W 3 each represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
• W 4 represents W 1 , -O-W 1 or -S-W 1 ;
• n represents an integer from 1 to 5, when n is two or more, two or more W 4 's may be the same or different; and W 1 and W 2 in the general formula (11) may be connected with each other to form a condensed ring.
• water-insoluble, organic solvent-soluble polymers include polyvinyl acetate, polyvinyl propionate, and polymethyl. methacrylate, but the present invention should not be construed as being limited thereto.
• These polymers may be employed together with the above described organic solvent having a high boiling point of at least 160°C.
• the dyes according to the present invention are used in combination with color fading preventing agents or antioxidizing agents represented by the general formula (12) or (13) shown below.
• R 20 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or a hydrolyzable protective group
• R 21 , R 22 , R 23 , R 24 and R 25 which may be the same or different, each represents a hydrogen atom or a substituent
• R 30 represents a hydrogen atom, an aliphatic group, an acyl group, a sulfonyl group, a sulfinyl group, an oxy radical group or a hydroxy group
• A represents a non-metallic atomic group necessary to form a 5-membered, 6-membered or 7-membered ring
• R 26 , R 27 , R 28 and R 29 which may be the same or different, each represents a
• substituents represented by R 21 or R 25 include a hydrogen atom and an alkyl group
• alkyl group include a straight chain or branched chain alkyl group having from 1 to 8 carbon atoms, particularly include a methyl group, an n-butyl group, a t-butyl group, a t-pentyl group and a n-octyl group.
• substituents represented by R 22 , R 23 or R 24 include a hydrogen atom, an alkyl group, -NHR 31 , an alkoxy group, -COO-R 32 , etc., and R 31 represents a nitrogen-containing heterocyclic group and R 32 represents an alkyl group or an aryl group.
• the above-mentioned alkyl, alkoxy. or aryl group means a substituted or unsubstituted alkyl, alkoxy or aryl group.
• R 20 and R 21 or two of R 21 , R 22 , R 23 , R 24 and R 25 which are present in the ortho-positions each other may be connected with each other to form a 5-membered, 6- membered or 7-membered ring.
• R26 and R 27 , R 28 and R 29 or R 30 and R 26 may be connected with each other to form a 5-membered, 6-membered or 7-membered ring.
• the color print according to a preferred embodiment of the present invention can be obtained by subjecting, after imagewise exposure, color printing paper which comprises a thin reflective support having thereon a yellow color forming layer containing a blue-sensitive silver halide emulsion and a yellow color forming coupler, a magenta color forming layer containing a green-sensitive silver halide emulsion and a magenta color forming coupler, and a cyan color forming layer containing a red-sensitive silver halide emulsion and a cyan color forming coupler, and optionally further an antihalation layer, an intermediate layer, a yellow filter layer, a protective layer, etc., if appropriate for the desired photographic material to color development processing.
• the silver halide emulsion which is used in the present invention is usually prepared by mixing an aqueous solution of a water-soluble silver salt (for example, silver nitrate) with an aqueous solution of a water-' soluble halide (for example, potassium bromide, sodium chloride, potassium iodide or a mixture thereof) in the presence of an aqueous solution of a water-soluble polymer (for example, gelatin,, etc.).
• a mixed silver halide for example, silver chlorobromide, silver chloroiodobromide, silver iodobromide, etc. are representative examples.
• the silver halide which is preferably employed in the present invention is silver chloroiodobromide, silver iodochloride or silver iodobromide, each containing 3 mol% or less silver iodide.
• Silver halide grains may have different layers in the inner portion and the surface portion, multi-phase structures containing junctions, or may be uniform throughout the grains. Further, a mixture of these silver halide grains having different structures may be employed. For instance, with respect to silver chlorobromide grains having different phases, those having nuclei or a single layer or plural layers which are rich in silver bromide as compared with the mean halogen composition in their inner portion, or those having nuclei or a single layer or plural layers which are rich in silver chloride as compared with the mean halogen composition in their inner portion may be employed. Therefore, surface layers of the grains are rich in silver bromide as compared with the mean halogen composition or contrary to this, surface layers are rich in silver chloride.
• Average grain size of silver halide grains is preferably from 0.1 u to 2 ⁇ , and particularly from 0.15 ⁇ to 1 u. Grain size distribution may be either narrow or broad.
• a so-called monodispersed silver halide emulsion having narrow grain size distribution which comprises at least 90%, particularly at least 95% by number or by weight of the total silver halide grains having a -size within the range of the average grain size ⁇ 40% is preferably employed in the present invention.
• two or more monodispersed silver halide emulsions which have different grain sizes from each other can be mixed in one emulsion layer or can be coated in the form of superimposed layers which have substantially the same spectral sensitivity.
• two or more polydispersed silver halide emulsions or combinations of a monodispersed emulsion and a polydispersed emulsion may be employed in a mixture or in the form of superimposed layers.
• Silver halide grains which can be used in the present invention may have a regular crystal structure, for example, a cubic, octahedral, dodecahedral or tetradecahedral structure, etc., an irregular crystal structure, for example, a spherical structure, etc., or a composite structure thereof.
• tabular silver halide grains can be used.
• a silver halide emulsion wherein tabular silver halide grains having a ratio of diameter/thickness of not less than 5, preferably not less than 8 account for at least 50% of the total silver halide grains present calculated based on projected area of the silver halide grains can be employed.
• mixtures of silver halide grains having different crystal structures may be used.
• These silver halide emulsions may be those of surface latent image type . in which latent images are formed mainly on the surface thereof, or those of internal latent image type in which latent images are formed mainly in the interior thereof.
• Dyes are employed in the present invention for various purposes, for example, as filter dyes, for irradiation prevention, for antihalation, etc.
• examples of such dyes which are preferably used are oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes and azo dyes.
• cyanine dyes, azo- methin dyes, triarylmethane dyes and phthalocyanine dyes are also useful.
• Oil-soluble dyes may be added to a hydrophilic colloid layer by emulsification using an oil droplet-in-water dispersing method.
• inorganic or organic hardening agents are employed in order to harden the hydrophilic colloid layers applied on the support.
• active halogen compounds for example, 2,4-dichloro-6-hydroxy-l,3,5-triazine, etc.
• active vinyl compounds for example, 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis- vinylsulfonylacetamidoethane, a vinyl type polymer having a vinylsulfonyl group in its side chain, etc.
• N-carbamoylpyridinium salts and halo- amidinium salts are excellent in view of their high hardening speed.
• a color developing solution used for development processing of the color photographic light-sensitive material of the present invention to obtain a color print is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component.
• an aromatic primary amine color developing agent As a color developing agent, while an aminophenol type compound is useful, a p-phenylenediamine type compound is preferably used.
• These - diamines are preferably employed in the form of salts since the salts are generally more stable than their free forms.
• the color developing solution generally contains pH buffering agents such as carbonates, borates or phosphates of alkali metals, etc., and development inhibitors or antifogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds, etc.
• pH buffering agents such as carbonates, borates or phosphates of alkali metals, etc.
• development inhibitors or antifogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds, etc.
• the color developing solution may also contain, for example, preservatives such as hydroxylamine, derivatives thereof (for example, N,N-dialkyl substituted derivatives, etc.), sulfites, etc.; organic solvents such as triethanolamine, derivatives thereof, diethylene glycol, etc.; development accelerators such as benzylalcohol, polyethyleneglycol, quaternary ammonium salts, amines, etc.; competing couplers; nucleating agents such as sodium borohydride, etc.; auxiliary developing agents such as l-phenyl-3-pyrazolidone, etc.; viscosity imparting agents; various chelating agents as represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids, etc.; and antioxidants as described in West German Patent Application (OLS) No. 2,622,950.
• preservatives such as hydroxylamine, derivatives thereof (for example, N,N-dialkyl substituted derivative
• color development is usually conducted after black-and-white development.
• the photographic emulsion layer is usually subjected to a bleach processing.
• the bleach processing can be carried out simultaneously with or separately from a fix processing. Further, in order to perform a rapid processing, a processing method in which a bleach-fix processing is conducted after a bleach processing can be employed.
• As bleaching agents iron (III) salts of ethylenediaminetetraacetic acid, iron (III) salts of diethylenetriaminepentaacetic acid and persulfates are preferred in view of rapid processing and less environmental pollution..Further, ethylenediaminetetraacetic acid iron (III) complex salts are particularly useful both in an independent bleaching solution and in a mono-bath bleach-fixing solution.
• thiosulfates are ordinarily employed as fixing agents.
• sulfites, bisulfites, cabonylbisulfite adducts, etc. are preferably employed as preservatives.
• water wash processing and/or stabilization processing are usually conducted.
• various known compounds may be employed for the purpose of preventing precipitation or saving water, etc.
• a water softener such as an inorganic phosphoric acid, an aminopolycarboxylic acid, an organic aminopolyphosphonic acid, or an organic phosphoric acid, etc.
• a sterilizer or antimold for the purpose of preventing the propagation of various bacteria, algae and molds
• a metal salt such as a magnesium salt, an aluminum salt, a bismuth salt, etc.
• a surface active agent for the purpose of reducing drying load or preventing drying marks
• various hardening agents etc.
• the compounds as described in L.E. West, Photo. Sci. Enq., Vol. 6, pages 344 to 359 (1965) may be added. Particularly, the addition of chelating agents and antimolds is effective.
• the color photographic light-sensitive material according to the present invention may contain, if appropriate, various l-phenyl-3-pyrazolidones for the purpose of accelerating color development.
• Typical examples of the compounds include those as described in Japanese Patent Application (OPI) Nos. 64339/81, 144547/82, 211147/82, 50532/83, 50536/83, 50533/83, 50534/83, 50535/83 and 115438/83, etc.
• various kinds of processing described above can be conducted in a temperature range of from 10°C to 50°C.
• a standard temperature is from 33°C to 38°C, it is possible to carry out the processing at higher temperatures in order to accelerate the processing whereby the processing time is shortened, or on the other hand, at lower temperatures in order to achieve improvement in image quality and to maintain stability of the processing solutions.
• the photographic processing may be conducted utilizing color' intensification using cobalt or hydrogen peroxide as described in West German Patent Application (OLS) No. 2,226,770 or U.S. Patent 3,674,499.
• the variation of composition in each processing solution can be prevented by using a replenisher for each processing solution, whereby a constant finish can be achieved.
• the amount of replenisher can be reduced to one half or less of the standard amount of replenishment for the purpose of reducing cost.
• Direct positive color prints can be obtained with respect to the color photographic light-sensitive materials by using an internal latent image type emulsion which was not previously fogged as a silver halide emulsion, and performing a fogging treatment after imagewise exposure but before or during a color development step.
• a method conducting fogging exposure or a method using a nucleating agent are effective. More specifically, a light fogging method and a chemical fogging method (a method using a nucleating agent together with a nucleating accelerator) as described, for example, in U.S. Application Serial No. 60,790 filed June 12, 1987, pages 55 to 88, or European Patent Application No. 87 108489.3 filed June 12, 1987, pages 55 to 88 (corresponding to Japanese Patent Application No. 136949/86) can be utilized.
• the color photographic prints obtained by development processing of the color photographic light-sensitive materials according to the present invention have advantageously not only good fastness to light, humidity and heat but also excellent sharpness of color images.
• the support composed of a vinyl chloride resin used in the present invention is excellent in flexibility and strength and its degree of elasticity depending' on change in humidity is small and can be ignored in comparison with other photographic supports.
• the color photographic light-sensitive materials and the color photographic prints according to the present invention are particularly suitable for employing as ID cards, cashing cards and telephone cards, etc.
• a support which was composed of a hard vinyl chloride resin (a-copolymer containing at least 50 mol% of vinyl chloride monomer component, with the remainder thereof being vinylidene chloride and methyl methacrylate, and further containing 12 parts by weight of Ti0 2 per 100 parts of total weight of the copolymer) and had a thickness of 150 ⁇ m and an average reflectance in the visible range of 85% or more, provided with subbing treatment, the first layer to the seventh layer described below were coated to prepare a color photographic light-sensitive material which was designated Sample 101.
• the support used was in conformity with a standard of JIS-K-6734-Class C, No. 1, as described in JIS published by Japanese Standards Association.
• Coated amounts shown below are g/m 2 , and coated amounts of silver halide shown below ' are measured as silver.
• the skeleten may change into a structure due to a resonance effect.
• dyes were used as spectral sensitizing dyes in the emulsion layers, respectively.
• Green-sensitive Emulsion Layer Red-sensitive Emulsion Layer:
• Samples 102 and A' were prepared in the same manner as described for Sample 101 except for changing couplers as shown in Table 1 below.
• composition of each processing solution used in the above-described processing steps is as follows:
• Sharpness is a value to indicate clearness of outlines of images and ability to duplicate fine images.
• the value known as CTF was used herein.
• CTF means a degree of decrease in amplitude against a spatial frequency as a rectangular wave. Sharpness at 15 lines/mm of spatial frequency thus- measured are shown in Table 2 below. The larger value indicates the better sharpness.
• Silver Halide Emulsion (7) for a blue-sensitive silver halide emulsion layer was prepared in the following manner.
• Solution 8 was heated at 60°C, Solution 9 and Solution, 10 were added thereto and then Solution 11 and Solution 12 were added simultaneously over a period of 60 minutes thereto.
• Solution 11 and Solution 12 were added simultaneously over a period of 60 minutes thereto.
• Solution 13 was added and then after 9 minutes Solution 14 and Solution 15 were added simultaneously over a period of 25 minutes.
• the temperature was dropped and the mixture was desalted.
• Water and gelatin for dispersion were added thereto and pH was adjusted to 6.0 whereby a mono-dispersed cubic silver chlorobromide emulsion .(having an average grain size of 1.00 um, a coefficient of variation of 0.11 and a silver bromide content of 1 mol%) was obtained.
• Spectral Sensitizer (S-1) shown below was added in an amount of 5 x 10 -4 mol per mol of silver halide.
• Silver Halide Emulsion (8) for a green-sensitive silver halide emulsion layer and Silver Halide Emulsion (9) for a red-sensitive silver halide emulsion layer were prepared in the same manner as described above except changing amounts of chemicals used in Solution 8 and Solution 10, kinds and amounts of spectral sensitizers, and temperatures and times for addition.
• Spectral Sensitizer (S-2) shown below was used for Silver Halide Emulsion (8) and Spectral Sensitizer (S-3) shown below was used for Silver Halide Emulsion (9).
• the compound described below was added in an amount of 2.6 x 10- 3 mol per mol of silver halide.
• 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer in the amounts of 8.5 x 10- 5 mol, 7.7 x 10 -4 mol and 2.5 x 10- 4 mol per mol of silver halide present in the layer, respectively.
• Samples 103 and 104 were prepared in the same manner as described for Samples 101 and 102, respectively, except that the silver halide emulsions used in the first layer, the third layer and the fifth layer were changed to Silver Halide Emulsions (7), (8) and (9), respectively. These samples were stepwise exposed in the same manner as described in Example 1 and then subjected to development processing consisting of color development, bleach-fixing and rinse steps as shown below.
• composition of each processing solution used in the above-described processing steps are as follows:
• Emulsions A to H were prepared as follows.
• Emulsion A Emulsion A
• aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 40 minutes to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 ⁇ m in average grain size.
• Four mg of sodium thiosulfate and 4 mg of chloroauric acid (4 hydrate) were added to the emulsion per mol of silver, followed by heating at 75°C for 80 minutes to effect . chemical sensitization.
• the thus obtained silver bromide grains were used as cores, and were allowed to further grow in the same precipitating environment as the first step for 40 minutes to finally obtain an octahedral monodispersed core/shell silver bromide emulsion of 0.6 ⁇ m in average grain size (coefficient of variation : 14 % ). After washing with water and desalting of the emulsion, 0.9 mg of sodium thiosulfate was added thereto per mol of . silver, followed by heating at 65°C for 60 minutes to effect chemical sensitization. Thus, internal latent image type silver halide emulsion A was obtained.
• silver halide emulsion C of 0.7 ⁇ m in average grain size was obtained.
• aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 40 minutes to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 ⁇ m in average grain size.
• Four mg of sodium thiosulfate and 4 mg of chloroauric acid (4 hydrate) were added to this emulsion per mol of silver, followed by heating at 75°C for 80 minutes to effect chemical sensitization.
• the thus obtained silver bromide grains were used as cores, and were allowed to further grow by adding a 2 mol/l sodium chloride aqueous solution and a 1 mol/l silver nitrate aqueous solution at 75°C for 40 minutes to obtain a cubic core/shell silver chlorobromide emulsion of 0.6 ⁇ m in average grain size (coefficient of variation: 15%). After washing with water and desalting of the emulsion, 0.5 mg of sodium thiosulfate was added thereto per mol of silver, then heated at 55°C for 60 minutes to effect chemical sensitization, whereby silver halide emulsion D was obtained.
• aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 90 minutes to obtain a silver bromide emulsion containing octahedral grains of 0.8 um in average grain size (core grains).
• 0.65 g of 3,4-dimethyl-l,3-thiazoline-2-thione was added to the aqueous gelatin solution and pH and pAg were maintained at 6 and 8.7 respectively during the step of precipitation.
• aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution under vigorous stirring at 75°C over a period of 60 minutes to obtain a silver bromide emulsion.
• 100 mg of 3,4-dimethyl-l,3-thiazoline-2-thione and 15 g of benzimidazole per mol of silver were added to a precipitation tank. After the completion of precipitation, crystals of 1.1 ⁇ m in average grain size were obtained. Then, 5.4 mg of sodium thiosulfate and 3.9 mg of potassium chloroaurate were added to the emulsion per mol of silver, followed by heating at 75°C for 80 minutes to effect chemical sensitization.
• aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution containing potassium bromide under vigorous stirring at 75°C over a period of about 60 minutes to obtain a silver bromide emulsion.
• 150 mg of 3,4-dimethyl-l,3-thiazoline-2-thione as a silver halide solvent and 15 g of benzimidazole per mol of silver were added to the aqueous gelatin solution. After the completion of precipitation, uniform grain size octahedral silver bromide crystals of 0.8 ⁇ m in average grain size were obtained.
• aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to a gelatin aqueous solution containing 0.3 g of 3,4-dimethyl-l,3-thiazoline-2-thione per mol of silver under vigorous stirring at 75°C over a period of 20 minutes to obtain a monodispersed silver bromide emulsion containing octahedral grains of 0.4 pm in average grain size.
• 6 mg of sodium thiosulfate and 6 mg of chloroauric acid (4 hydrate) were added to the emulsion per mol of silver, followed by heating at 75°C for 80 minutes to effect chemical sensitization.
• the thus obtained silver bromide grains were used as cores, and were allowed to further grow in the same precipitating environment as the first step for 40 minutes to finally obtain an octahedral . monodispersed core/shell silver bromide emulsion of 0.7 ' um in average grain size. After washing with water and desalting of the emulsion, 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (4 hydrate) were added thereto per mol of silver, followed by heating at 60°C for 60 minutes to effect chemical sensitization. Thus, internal latent image type silver halide emulsion H was obtained.
• Coating solutions for the second layer to the seventh layer were also prepared in the same manner as the coating solution for the first layer.
• Sodium salt of 1-hydroxy-3,5-dichloro-s-triazine was used as a gelatin hardener for each layer.
• Spectral sensitizers used for individual emulsions are shown below.
• the following dyes were employed. as irradiation preventing dyes in the emulsion layers, respectively.
• the coating solutions for the first layer to the seventh layer were coated after adjusting the balance of surface tension and viscosity thereof simultaneously on the support to prepare multilayer silver halide direct positive color photographic printing paper A to H.
• the direct positive color photographic printing paper A to H thus prepared were imagewise exposed at color temperature of 4,800°K in an amount of 100 CMS at 1/10 second and then subjected to Processing Step A (pH of the color developing solution: 10.2) shown below and Processing Step B (same a Processing Step A except adjusting pH of the color developing solution to 11.0), respectively.
• Processing Step A pH of the color developing solution: 10.2
• Processing Step B standarde a Processing Step A except adjusting pH of the color developing solution to 11.0
• the stabilizing baths were replenished according to a so-called countercurrent replenishing system of adding the replenisher to stabilizing bath (3), introducing the overflow from the stabilizing bath (3) into stabilizing bath (2), and the overflow from the stabilizing bath (2) into stabilizing bath (1).
• composition of each processing solution used in the above described processing steps is as follows:
• the pH was adjusted with potassium hydroxide or hydrochloric acid.
• the pH was adjusted with aqueous ammonia or hydrochloric acid.
• the pH was adjusted with potassium hydroxide or hydrochloric acid.
• the color photographic material was processed according to the prescribed development processing steps. A reversal color photographic print having excellent sharpness and no irregularity of image density was obtained.

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• 1987
  • 1987-04-20 JP JP62095440A patent/JPH07119964B2/ja not_active Expired - Fee Related
  • 1987-12-01 DE DE3789800T patent/DE3789800D1/de not_active Expired - Lifetime
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