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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic
• • 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
  • G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
  • G03C7/3005—Combinations of couplers and photographic additives
  • G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
  • G03C7/301—Combinations of couplers having the coupling site in pyrazoloazole rings and photographic additives

Definitions

• the present invention relates to a silver halide color photographic material, and, more particularly, to a light-sensitive material which has excellent color reproducibility and high color developability, and shows a considerably suppressed increase in density of the unexposed part after photographic processing.
• Color images are well known to be formed by reacting couplers with oxidized color developing agents of primary amine type, which have been oxidized using optically exposed silver halides as an oxidizing agent, to produce indophenol, indoaniline, indamine, azo­methine, phenoxazine, phenazine and their analogous dyes.
• magenta color image-forming couplers which have been studied and widely used up to the present are 5-pyrazolones.
• dyes produced from 5-pyrazolone type couplers show an undesired absorption having a yellow component in the neighborhood of 430 nm, which is responsible for color turbidity.
• magenta couplers disclosed in the above-cited patents remain unsatisfactory.
• color images produced therefrom are unsatisfactory; their solubilities in high boiling organic solvents are low; they are difficult to synthesize; they have no more than comparatively low coupling activities in ordinary developers; and dyes produced therefrom have extremely low fastness to light.
• Stains caused in a silver halide color photo­graphic material are undesirable, since that they not only degrade the quality of white areas of the image but also aggravate the turbidity in colored areas of the image and spoil the visual sharpness of the image.
• the reflection density of stains in reflex materials e.g., color paper
• JP-A-62-96944 and JP-A-62-92945 into sensitive materials was disclosed for the purpose of suppressing the generation of stains, those compounds still cannot produce sufficient effects upon the couplers in question.
• An object of the present invention is to provide a light-sensitive material which has sufficiently high color developability and excellent color reproduci­bility, and without an increase in density of the un­exposed part with the lapse of time.
• a silver halide color photographic material which contains at least one coupler represented by the following general formula (I) or (II-A), and at least one compound represented by the following general formula (III) in the same layer: wherein R1 represents an alkyl group, an aryl group, or a heterocyclic group; R2 represents a hydrogen atom, or a substituent group; and X represents a hydrogen atom, or a coupling-off group.
• R represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an oxy radical, or a hydroxyl group
• A represents a nonmetalic atomic group necessary for forming a 5-, 6- or 7-membered ring
• R3 may be linked with R4, R5 may be linked with R6, R may be linked with R3, or R3 may be linked with A to form a 5- or 6-membered ring.
• At least one light-­sensitive silver halide layer contains at least one coupler represented by formula (I) or (II-B) in combi­nation with at least one compound represented by formula (III) above: wherein R1 represents an alkyl group, an aryl group or a heterocyclic group; R2 represents hydrogen, a halogen, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, an acylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, or an alkoxycarbonyl group; X represents hydrogen or a coupling
• magenta couplers represented by the fore­going general formulae (I) and (II-A) are described in detail below.
• R1 represents a substituted or unsubstituted alkyl group such as methyl, ethyl, isopropyl, t-butyl, trifluoromethyl, phenylmethyl, methoxyethyl, 2-phenoxy­ethyl, 2-methylsulfonylethyl, 2-hydroxyethyl, 3,3,3-tri­fluoropropyl, 2-fluoroethyl, 2-chloroethyl, 2-bromo­ethyl, 2-cyanoethyl, 3-oxobutyl, or 3-oxobutyl; a sub­stituted or unsubstituted aryl group such as phenyl, 4-­methylphenyl, 4-t-butylphenyl, 4-acylaminophenyl, 4-­halogenophenyl, or 4-alkoxyphenyl; or a substituted or unsubstituted heterocyclic group such as 2-furyl, 2-­thieny
• R2 represents hydrogen, a halogen atom (e.g., chlorine, bromine); a substituted alkyl group, such as a sulfonamido-substituted alkyl group (e.g., sulfon­amidomethyl, 1-sulfonamidoethyl, 2-sulfonamidoethyl, 1-­methyl-2-sulfonamidoethyl, 3-sulfonamidopropyl), an acylamino-substituted alkyl group (e.g., acylamino­methyl, 1-acylaminoethyl, 2-acylaminoethyl, 1-methyl-2-­acylaminoethyl, 3-acylaminopropyl), a sulfonamido-­substituted phenylalkyl group (e.g., p-sulfonamido­phenylmethyl, p-sulfona
• R1 represents an alkyl group
• R2 represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, a heterocyclicthio group, an alkoxy­carbonyl group, a sulfinyl group or a carbamoyl group.
• X represents hydrogen or a coupling-off group, e.g., a halogen atom (e.g., chlorine, bromine, iodine); a carboxyl group; a group connected to the coupling active site via an oxygen atom (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methane­sulfonylphenoxy, ⁇ -naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy);
• R1, R2, or X may be a divalent group via which the magenta coupler of formula (I) or (II-A) forms a bis compound
• R1 or R2 represents a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1,10-decylene, -CH2CH2-O-CH2CH2-), or a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene, 1,3-phenylene, while X represents a divalent group derived from any of the above-cited monovalent groups.
• a linkage group represented by R1 or R2 includes those formed by combining two or more divalent groups selected from among substituted or unsubstituted alkylene groups (e.g., methylene, ethylene, 1,10-decylene, -CH2CH2OCH2CH2-), substituted or unsubstituted phenylene groups (e.g., 1,4-phenylene, 1,3-phenylene, substituted or unsubstituted aralkylene groups (e.g., preferred as the combined linkage group.
• substituted or unsubstituted alkylene groups e.g., methylene, ethylene, 1,10-decylene, -CH2CH2OCH2CH2-
• substituted or unsubstituted phenylene groups e.g., 1,4-phenylene, 1,3-phenylene, substituted or unsubstituted aralkylene groups (e.g., preferred as the combined linkage group.
• the vinyl group in such a vinyl monomer may contain a substituent group in addition to the moiety represented by formula (I) or (II-A).
• Preferred substi­tuent groups include hydrogen, chlorine, or a lower alkyl group having from 1 to 4 carbon atoms (e.g., methyl, ethyl).
• the monomer containing the coupler moiety represented by the general formula (I) or (II-A) may form a copolymer together with an ethylenically unsaturated monomer incapable of undergoing a coupling reaction with the oxidation product of an aromatic primary amine developing agent, and therefore, which cannot produce a color.
• non-color-producing ethylenically unsaturated monomers include acrylic acid, ⁇ -chloroacrylic acid, ⁇ -alkylacrylic acid (e.g., meth­acrylic acid), and esters or amides derived from these acrylic acids (e.g., acrylamide, n-butylacrylamide, t-­butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-­butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-­ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl meth­acrylate, ⁇ -hydroxymethacrylate), methylenedibisacryl­amide, vinyl esters (e.g.
• Two or more non-color-producing ethylenically unsaturated monomers can be used together.
• a combination of n-­butyl acrylate with methyl acrylate, of styrene with methacrylic acid, of methacrylic acid with acrylamide, and of methyl acrylate with diacetone acrylamide can be used.
• non-color-producing ethylenically unsaturated monomers to be copolymerized with a solid water-­insoluble coupler monomer can be selected so as to produce desirable physical and/or chemical properties of the resulting copolymers, for example, solubility, compatibility with a binder (such as gelatin) contained in a photographic colloidal composition, flexibility, thermal stability, and so on.
• a binder such as gelatin
• Polymer couplers to be used in the present invention may be either soluble or insoluble in water, and are particularly preferably in the form of a latex.
• couplers represented by the foregoing general formulae (I) and (II-A) those containing an aryl group, especially a substituted phenyl group (e.g., a phenyl substituted by an alkoxy group at the ⁇ -­position), as R1 are preferred over others.
• the coupler represented by formula (I) or (II-A) is added in an amount of from 2 x 10 ⁇ 3 to 1 mol/Agmol, preferably from 1 x 10 ⁇ 2 to 5 x 10 ⁇ 1 mol/Agmol, to the light-sensitive silver halide layer.
• R represents hydrogen, an alkyl group (e.g., methyl, ethyl, butyl, isoamyl, octyl, hexadecyl), an alkenyl group (e.g., vinyl, allyl, 5-methyl-1-hexenyl, 1-octadecenyl), an alkynyl group (e.g., propynyl, 4-­methyl-2-pentynyl, 5-tridecynyl, 1-octadecynyl), an oxy radical or hydroxyl.
• hydrogen is preferred as R.
• R3, R4, R5 and R6 may be the same or different, and each represents hydrogen, or an alkyl group (e.g., methyl, ethyl, propyl, octyl, hexadecyl).
• A represents a nonmetallic atomic necessary for forming a 5-, 6 or 7-membered ring, with specific examples including (wherein R7 and R8 may be the same or different, and each represents hydrogen, an alkyl group, an acyl group, a sulfonyl group, a sulfinyl group, or an alkoxycarbonyl group).
• R7 and R8 may be the same or different, and each represents hydrogen, an alkyl group, an acyl group, a sulfonyl group, a sulfinyl group, or an alkoxycarbonyl group).
• a 5- or 6-membered ring e.g., cyclopentyl, cyclohexyl, cyclohexyl, pyran, piperazine, piperidine, morpholine
• R3 may be formed by combining R3 with R4, R5 with R6, R with R3, or R3 with A.
• a nonmetallic atomic group forming a 5- or 6-membered ring particularly those forming a piperidine ring, are preferred.
• R3, R4, R5 and R6 it is desirable that at least two of them, more preferably all of them, are an alkyl group.
• R hydrogen or an alkyl group is preferred, and hydrogen is particularly preferred.
• JP-A-49-53572 JP-A-49-­53573, JP-A-49-53574, JP-A-49-53575, JP-A-49-7180, JP-B-­51-1420 (the term "JP-B” as used herein means an "examined Japanese patent publication"), British Patents 1,326,889, 1,354,313 and 1,410,846, and U.S. Patents 4,268,593 and 4,452,884.
• These compounds are added in a proportion of 5 to 200 mol%, preferably 10 to 50 mol%, to the coupler.
• Image stabilizers which are preferably used together with the compounds of the present invention, include compounds represented by the general formula (IV), and metal complexes.
• R3 represents hydrogen, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, or (wherein R9, R10 and R11 may be the same or different, and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group or an aryloxy group).
• R4, R5, R6, R7 and R8 may be the same or different, and each represents hydrogen, an alkyl group, an alkenyl group, an aryl group, an acylamino group, an alkylamino group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an aryloxycarbonyl group, a halogen atom or -O-R3′, wherein R3′ has the same meaning as R3.
• R3 and R4 may combine with each other to form a 5-membered ring, a 6-membered ring or a spiro ring.
• R4 and R5, or R5 and R6 may combine with each other to form a 5-membered ring, a 6-membered ring or a spiro ring.
• R4, R5, R6, R7 and R8 are given below.
• R4, R5, R6, R7 and R8 may be the same or different, and each represents hydrogen, an alkyl group (e.g., methyl, n-butyl, n-octyl, sec-dodecyl, t-butyl, t-amyl, t-hexyl, t-octyl, t-octadecyl, ⁇ , ⁇ -dimethyl­benzyl, 1,1,-dimethyl-4-hexyloxycarbonylbutyl), an alkenyl group (e.g., vinyl, allyl), an aryl group (e.g., phenyl, naphthyl, p-methoxyphenyl, 2,4-t-butylphenyl), an acylamino group (e.g., acetylamino, propionylamino, benzamino), an alkylamino group (e.g., N-methylamino,
• R3 may combine with R4 or R5 to form a 5-membered, 6-membered or spiro ring.
• a ring formed by combining R3 with R4 include a chroman ring, a coumarane ring, and methylenedioxy­benzene.
• R4 and R5, or R5 and R6 may combine with each other to form a 5-membered, 6-membered or spiro ring, including an indane ring and a spiroindane ring.
• R3, R3′, R4, R5, R6, R7 and R8 have the same meanings as those in formula (IV), respectively.
• R11′ through R 21′ may be the same or different, and each represents hydrogen, an alkyl group or an aryl group.
• the compound of the present invention should be used together with metal complexes.
• Metal complexes which can be used in the present invention are compounds containing copper, cobalt, nickel, palladium or platinum as the central metal, and at least one bidentate or higher organic ligand.
• nickel is particular­ly preferred.
• coordination atoms which are coordinately bonded to the central metal nitrogen, sulfur, oxygen and phosphorus are preferred.
• M represents Cu, Co, Ni, Pd, or Pt.
• R23 and R27 may be the same or different, and each represents hydrogen, an alkyl group, an aryl group, or a hydroxyl group. Further, R23 and R27 be linked, R24 represents hydrogen, an alkyl group, or an aryl group.
• R25 and R26 may be the same or different, and each represents hydrogen, an alkyl group, or an aryl group. Further, R25 and R26 may be linked to form an aromatic ring or a 5- to 8-membered ring.
• R30 and R31 have the same meanings as R25 and R26.
• R28 and R29 which may be the same or different, each represents an alkyl group, an aryl group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an alkylamino group, or an arylamino group.
• substituent groups present in the general formulae (V-1) to (V-4) those having an alkyl moiety or an aryl moiety may be further substituted by a substituent group.
• X1 represents a compound capable of coordinately bonding to M.
• Specific examples of such compound include H2O and organic or inorganic amines (e.g., pyridine, triethylamine, ammonia).
• A represents oxygen, sulfur or -NR110-, wherein R110 represents hydrogen, an alkyl group, an aryl group, a hydroxyl group, or an alkoxy group.
• A3 represents a hydroxyl group, an alkoxy group, an alkylthio group, or -NR120R130, wherein R120 and R130 may be the same or different, and each represents hydrogen or an alkyl group.
• the compound represented by formulae (IV) is added in a proportion of from 10 to 400 mol%, preferably from 30 to 300 mol%, to the coupler represented by the general formula (I) or (II-A).
• the metal complex of formulae (V-1) to (V-4) is added in a proportion of from 1 to 100 mol%, preferably from 3 to 40 mol%, to the coupler represented by the general formula (I) or (II-­A).
• magenta coupler relating to the present invention and a discoloration inhibitor are first dissolved in a high boiling organic solvent, and then dispersed into at least one hydrophilic organic colloid to constitute the photographic light-sensitive layer.
• Couplers into silver halide emulsion layers is generally effected by using known methods as described, e.g., in U.S. Patent 2,322,027.
• the compound of the present invention is incorporated into a hydrophilic colloid contained in the sensitive material at the stage of the production of the sensitive material.
• the incorporation is effected by dissolving the compound in a high boiling organic solvent with a boiling point of 170°C or above under atmospheric pressure, or a mixed solvent composed of the foregoing oil and a low boiling solvent, and then emulsifying and dispersing the resulting solution in a water solution of a hydrophilic colloid such as gelatin.
• This emulsified dispersion is not particularly restricted as to particle size of oil droplets contain­ing the compounds of the present invention, but the particle size ranges preferably from 0.05 to 0.5 ⁇ m, more preferably from 0.1 to 0.3 ⁇ m.
• oils include phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthalate), phosphoric acid esters (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate, monophenyl-p-t-butylphenyl­phosphate), citric acid esters (e.g., tributyl acetyl­citrate), benzoic acid esters (e.g., octyl benzoate), alkylamides (e.g., diethyllaurylamide, dibutyllauryl­amide), fatty acid esters (e.g., dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g., phthalic acid alkyl
• Patent 4,540,657 phenols (e.g., and ethers (e.g., phenoxyethanol, diethylene glycol monophenyl ether).
• Low boiling solvents used as auxiliary solvents are those having a boiling point ranging from about 30°C to 150°C under atmospheric pressure, with specific examples including lower alkyl acetates such as ethyl acetate, isopropyl acetate and butyl acetate, ethyl propionate, methanol, ethanol, secondary butyl alcohol, cyclo­hexanol, fluorinated alcohol, methyl isobutyl ketone, ⁇ -­ethoxyethylacetate, methyl cellosolve acetate, acetone, methyl acetone, acetonitrile, dioxane, dimethyl­formamide, dimethyl sulfoxide, chloroform, and cyclo­hexane.
• oily solvents for additives such as couplers (including those which are solid at room temperature, such as waxes) but also latex polymers can be employed.
• the additives themselves e.g., couplers, color stain inhibitors, ultraviolet absorbents and so on, may serve as oily solvents, too.
• the latex polymers those prepared using monomers, such as acrylic acids, methacrylic acids and their esters (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate), acrylamide, t-butylacrylamide, methacrylamide, vinyl esters (e.g., vinyl acetate, vinyl propionate), acrylonitrile, styrene, divinylbenzene, vinyl alkyl ethers (e.g., vinyl ethyl ether), maleic acid esters (e.g., methyl maleate), N-vinyl-2-­pyrrolidone, N-vinylpyridine, 1- and 4-vinylpyridines and so on, independently or in combination of two or more thereof can be employed.
• monomers such as acrylic acids, methacrylic acids and their esters (e.g., methyl acrylate, ethyl acrylate, butyl methacrylate), acrylamide, t-butyl
• Examples of a surface active agent used in dispersing an oily solution, in which the compound of the general formula (I), (II-A), (III) or (IV) is dissolved alone or together with a coupler, into an aqueous protective colloid solution in the present invention include saponin, sodium alkylsulfosuccinates, and sodium alkylbenzenesulfonates.
• anionic surface active agents having a sulfo group are used independently or in combination thereof.
• the present invention is not particularly restricted as to other couplers to be used in the color photographic light-sensitive material, and the following couplers can be used.
• Couplers represented by formulae (Y-I) and (Y-­II), respectively.
• R11 represents a substituted or unsubstituted N-­phenylcarbamoyl group
• Z11 represents a group capable of splitting off upon the reaction with the oxidation product of an aromatic primary amine developing agent: wherein R11 represents a substituted or unsubstituted N-­phenylcarbamoyl group, Z11 represents a group capable of splitting off in the reaction with the oxidation product of an aromatic primary amine developing agent, R12 represents hydrogen or a substituent group, and s is an integer of 1 to 5.
• Representative chemical structures of the yellow couplers represented by formulae (Y-I) and (Y-II) include those illustrated in the U.S. Patents 3,894,875 (1-2), 3,408,194 (2-3), 4,404,274 (3-17), 4,022,620 (3-­7), 4,057,432 (1-4) wherein the figures in the parentheses indicate the numbers of the columns wherein the foregoing chemical structures are described in detail.
• Representative chemical structures of the cyan couples represented by the general formula (C-I) include those illustrated in U.S. Patents 2,920,961 (1), 3,772,002 (1-3), 3,864,366 (2-6), 4,124,396 (2), 4,333,996 (2-8), 4,565,777 (3-5), 4,564,586 (2-4), wherein the figures in the parentheses indicate the numbers of the columns in which the foregoing chemical structures are described in detail.
• Each of the foregoing couplers may assume the form of a polymer, including a dimer.
• a color developer which can be used in the present invention is described below.
• the color developer contains a known aromatic primary amine developing agent.
• developing agents which are preferably used are p-phenylenediamine derivatives. Representative examples of such p-­phenylenediamine derivatives are cited below. However, the invention is not to be construed as being limited to these examples.
• p-phenylenediamine derivatives may assume the form of a salt, such as sulfate, hydrochloride, sulfite, p-toluenesulfonate, or so on.
• a preferred amount of the aromatic primary amine developing agent added to 1 liter of a developer ranges from about 0.1 g to about 20 g, particularly from about 0.5 g to about 10 g.
• a sulfite such as potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium metasulfite, potassium metasulfite, or a carbonyl/sulfinic acid adduct can be added, if needed.
• JP-A-63-43139 poly­amines disclosed in JP-A-63-21647 and JP-A-63-26655, polyamines disclosed in JP-A-63-44655, nitroxy radicals disclosed in JP-A-63-53551, alcohols disclosed in JP-A-­63-43140 and JP-A-63-53549, oximes disclosed in JP-A-63-­56654, and/or tertiary amines disclosed in Japanese Patent Application No. 61-265149 is advantageous.
• the developer may contain various metals disclosed in JP-A-57-44148 and JP-A-57-53749, salicylic acids disclosed in JP-A-59-­180588, alkanolamines disclosed in JP-A-54-3532, polyethyleneimines disclosed in JP-A-56-94349, and aromatic polyhydroxy compounds disclosed in U.S. Patent 3,746,544, if desired.
• the addition of the aromatic polyhydroxy compounds is preferred.
• the color developer used in the present invention is adjusted to a pH of 9 to 12, preferably a pH of 9 to 11.0.
• the color developer can contain other known compounds as developer components.
• buffering agents include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), and potassium 5-sulfo-2-­hydroxybenzoate (potassium 5-sulfosalicylate).
• the invention is not to be construed as being limited to these compounds.
• the amount of the buffering agents to be added to the color developer is preferably 0.1 mol/l or more, particularly from 0.1 to 0.4 mol/l.
• various kinds of chelating agents may be contained in the color developer in order to prevent calcium and magnesium from precipitating, or in order to enhance the stability thereof.
• chelating agents which can be used are cited below, but the invention is not to be construed as being limited to such examples.
• nitrilotriacetic acid diethylenetriaminepentaacetic acid, ethylenedi­aminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N′,N′-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-di­ aminopropanetetraacetic acid, glycoletherdiaminetetra­acetic acid, ethylenediamine-o-hydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy­ethylidene-1,1-diphosphonic acid, and N,N′-bis(2-­hydroxybenzyl)ethylenediamine-N,N′-diacetic acid.
• chelating agents may be used in a combi­nation of two or more thereof, if needed.
• These chelating agents can be added in any amount sufficident to mask metal ions in the color developer. For instance, they may be added in an amount of 0.1 to 10 g per liter of the color developer.
• the color developer can contain any development accelerator, if needed.
• Development accelerators can produce a parti­cularly remarkable effect in the present invention when a color developer which is substantially free from benzyl alcohol is used.
• the color developer used in the present invention can contain any antifoggant, if desired.
• antifoggants which can be used include alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants.
• organic antifoggants include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroiso­indazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-­thiazolylmethyl-benzimidazole, indazole, hydroxyaza­indolizine, and adenine.
• the color developer to be used in the present invention preferably contains a brightening agent.
• Suitable brightening agents are 4,4′ diamino-­2,2′-disulfostilbene type compounds, and a preferred addition amount thereof ranges from 0 to 5 g/l, particularly from 0.1 to 4 g/l.
• the color developer may contain various kinds of surface active agents such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids, if desired.
• the processing using the color developer of the present invention is performed at a temperature ranging from 20°C to 50°C, preferably from 30°C to 40°C.
• the time of the processing ranges from 20 seconds to 5 minutes, preferably from 30 seconds to 2 minutes.
• a replenisher is added in a smal amount, of from 20 to 600 ml, preferably from 50 to 300 ml, and more preferably from 100 ml to 200 ml, per square meter of the sensitive material processed.
• a desilvering step performed in the present invention is described in detail below.
• a bleach-fix bath is used.
• the effect of the present invention becomes more remarkable the shorter a desilvering time is. More specifically, the desilvering time is 6 minutes or shorter, preferably between 30 seconds and 4 minutes, more preferably between 30 seconds and 60 seconds.
• a bleach-fix bath which can be used in the present invention is described in detail below.
• Examples of a bleaching agent which can be used in the bleach-fix bath of the present invention include organic complex salts of iron, cobalt, nickel, manganese and chromium.
• organic complex salts formed by Fe(III) and aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, and diethylenetriamine­pentaacetic acid, aminopolyphosphonic acids, phosphono­carboxylic acids, organic phosphonic acids, citric acid, tartaric acid, and malic acid, are preferred.
• aminopolycarboxylic acid complex salts of Fe(III) are particularly preferred for rapid processing and prevention of environmental pollution.
• useful aminopolycarboxylic acids for forming the organic complex salts include ethylenediaminetetraacetic acid, diethylenetriamine­pentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, and glycoletherdiamine­tetraacetic acid. These compounds may assume the form of a sodium, potassium, lithium or ammonium salt.
• bleaching agents ethylenediaminetetraacetato)­iron(III), (diethylenetriaminepentaacetato)iron(III), (cyclohexanediaminetetraacetato)iron(III), (1,3-diamino­propanetetraacetato)iron (III) and (methyliminodi­ acetato)iron(III) complexes are preferred for high bleaching power.
• ferric ion complexes may be used in the form of complex salts, or may be formed in the bath by adding thereto both ferric salts, such as ferric sulfates, ferric chloride, ammonium ferric sulfate, and ferric phosphate, and chelating agents of amino­polycarboxylic acid type. Moreover, these chelating agents may be used in excess of amounts required for forming the ferric ion complexes.
• a suitable amount of the foregoing bleaching agent added ranges from 0.01 to 1.0 mole, preferably from 0.05 to 0.50 mole, per liter of the bath.
• the bleach-fix bath and/or the pre-bath thereof can contain various compounds as a bleach accelerator.
• bleach accelerators which are preferred for great accelerating effect include the compounds containing a mercapto group or a disulfide linkage, described in U.S. Patent 3,893,858, German Patent 1,290,812, JP-A-53-95630 and Research Disclosure , No. 17129 (July 1978), thiourea compounds disclosed in JP-B-­45-8506, JP-A-52-20832, JP-A-53-32735 and U.S. Patent 3,706,561, and halogen ions such as iodide and bromide.
• the bleach-fix bath used in the present invention can contain a rehalogenating agent such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides (e.g., ammonium iodide).
• a rehalogenating agent such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride), or iodides (e.g., ammonium iodide).
• an inorganic or organic acid an alkali metal or ammonium salt thereof, which has a pH buffering ability, such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphonic acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and a corrosion inhibitor such as ammonium nitrate, or guanidine.
• a pH buffering ability such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphonic acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, and a corrosion inhibitor such as ammonium nitrate, or guanidine.
• Fixers which can be preferably used in the bleach-fix bath include known thiosulfates such as sodium thiosulfate, and ammonium thiosulfate. Also, a special bleach-fix bath which contains, e.g., a combination of a fixer with a large amount of a halide such as potassium iodide described in JP-A-55-155354 can be employed. The amount of the fixer added ranges from 0.3 to 2 moles, preferably from 0.5 to 1.0 mole, per liter of the bath.
• the bleach-fix bath of the present invention is adjusted to a pH of 3.5 to 6.5, preferably 4 to 5.5.
• various kinds of organic or inorganic acids, bases and buffering agents can be used.
• Specific examples of acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, propionic acid, and citric acid
• alkalis include sodium hydroxide, potassium hydroxide, aqueous ammonia, and various amines. The invention is not to be construed as being limited to these examples.
• the bath When the pH of the bleach-fix bath is higher than the above-described range, the bath is inferior in desilvering power and provides images inferior in stability, whereas when the bath has a lower pH than the above-described range it suffers from deterioration of stability, and converts the cyan dyes produced to their corresponding leuco bodies to a considerable extent.
• the bleach fix bath may contain various kinds of brightening agents, defoaming agents, surface active agents, polyvinyl pyrrolidone, and organic solvents such as methanol.
• the bleach-fix bath and a fixing bath which can be used in the present invention can contain as a preservative a sulfinic acid ion releasing compound, such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite), hydrogen sulfites (e.g., ammonium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite), and metabisulfites (e.g., potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite).
• a compound is preferably added in an amount of about 0.02 to 0.50 mol/l, particularly 0.04 to 0.40 mol/l, on a sulfinic acid ion basis.
• sulfites are generally used as preserv­ative, other preservatives such as ascorbic acid, adducts of carbonyl compounds and bisulfites, and carbonyl compounds may be added.
• buffering agents may optionally be added.
• the silver halide color photographic material of the present invention is, in general, subjected to a washing step and/or a stabilizing step.
• the volume of washing water required can be determined depending on the characteristics of photosensitive materials to be processed (e.g., the kind of couplers incorporated therein), end-use purposes of photosensitive materials to be processed, the temperature of washing water, the number of washing tanks (stage number), the method of replenishing washing water (e.g., whether a current of water flows in the countercurrent direction, or not), and other conditions. Of these conditions, the relation between the number of washing tanks and the volume of washing water in the multistage countercurrent process can be determined according to the methods described in Journal of the Society of Motion Picture and Television Engineers , volume 64, pages 248 to 253 (May 1955).
• a preferred step number in the multistage countercurrent process is generally from 2 to 6, particularly from 2 to 4.
• the volume of washing water can be sharply reduced. For instance, it becomes feasible to decrease it to 0.5 to 1 liter per square meter of the sensitive material processed.
• the process has disadvan­tages, e.g., in that bacteria propagate in the tanks because of the increase in staying time of water in the tanks, and suspended matter produced from the bacteria sticks to photosensitive materials processed therein.
• the method of reducing the contents of calcium and magnesium which is disclosed in JP-A-62-288838, can be employed to great advantage for solving the above-described problem.
• bacteri­cides such as isothiazolone compounds and thiabendazoles disclosed in JP-A-57-8542, chlorine-containing germi­cides such as a sodium salt of chlorinated isocyanuric acid, benzotriazoles disclosed in JP-A-61-267761, copper ion, and other germicides described in Hiroshi Horiguchi, Bohkin Bohbai Zai no Kagaku (which means "Chemistry of Antibacteria and Antimolds"), Biseibutsu no Mekkin Sakkin Bohbai Gijutsu (which means "Arts of Sterilizing and Pasteurizing Microbe and Proofing against Mold”), compiled by Eisei Gijutsu Kai, and Bohkin- and Bohbai-zai Jiten (which means "Thesaurus of Antibacteria and Antimolds”), comEpiled by Nippon Bohkin Bohbai Gakkai.
• the washing water can contain a surface active agent as a draining agent, and a chelating agent represented by EDTA as a water softener.
• Washing water to be used in the processing of the photosensitive material of the present invention is adjusted to pH 4 to 9, preferably to pH 5 to 8.
• the washing temperature and a washing time can be chosen varied depending on the characteristics and the intended use of the photosensitive material to be washed, and are generally in a range of 20 sec. to 10 min. at 15°C to 45°C, preferably 30 sec. to 5 min. at 25°C to 40°C.
• the photosensitive material of the present invention is processed with a stabilizing bath.
• compounds having an image-stabilizing function such as aldehyde compounds represented by formaldehyde, buffering compounds for adjusting the film pH to a value suitable for stabilization of the produced dyes, and ammonium compounds.
• the stabilizing bath can contain the above described various bactericides and antimolds for the purposes of prevention of propagation of bacteria in the bath, and imparting an antimolding ability to the sensitive materials processed thereby.
• surface active agents may be added to the stabilizing bath.
• any known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-­59-184343, JP-A-60-220345, JP-A-60-238832, JP-A-60-­239784, JP-A-60-239749, JP-A-61-4054 and JP-A-61-118749, can be applied to the stabilization step of the present invention.
• chelating agents such as 1-hydroxyethylene-1,1-diphos­phonic acid, ethylenediaminetetramethylenephosphonic acid, magnesium compounds and bismuth compounds.
• Solutions used in the washing and/or the stabilization step can be further used in the pre-step. For instance, washing water overflowing the washing bath, which has been reduced in volume by using a multistage countercurrent process, is conducted into the prebath, that is, the bleach-fix bath, and the bleach-­fix bath is replenished with a concentrated solution to achieve the reduction of waste solutions.
• the silver halide color photographic material of the present invention can be applied to color paper, color reversal paper, direct-positive color photographic materials, color positive films, color negative films, color reversal films, and so on.
• the present invention when applied to color paper and color reversal paper, the present invention can produce desirable effects.
• any silver halide including silver iodobromide, silver bromide, silver chlorobromide, and silver chloride can be used. More specifically, a silver chlorobromide emulsion having a chloride content of 60 mol% or more, especially 80 mol% or more, and a silver chloride emulsion are preferred in the case of, e.g., color paper, wherein a rapid processing or a low replenishment processing is carried out.
• a silver chlorobromide emulsion having a bromide content of 50 mol% or more, especially 70 mol% or more, and a silver bromide emulsion (which each may have an iodide content of 3 mol% or less) are preferred when high sensitivity is needed, and it is necessary to suppress the generation of fog at the time of producing, preserving and/or processing the sensitive material.
• silver iodobromide emulsions and silver chloroiodobromide emulsions, each having an iodide content of 3 to 15 mol% are preferably used.
• the silver halide grains may have a multi-phase structure, such that the interior and the surface of the grains may differ or the grains may have a junction structure, or the silver halide grains may be uniform throughout. In particular, a double layer structure is preferred. Also, various structures may be present together.
• the size distribution of the silver halide grains to be used in the present invention may be narrow or broad, and is preferably of "monodisperse".
• the term "monodisperse" system as used herein refers to a dispersion system in which the value obtained by dividing the standard deviation (from the size distri­bution curve of the silver halide emulsion grains) by the average grain size (variation coefficient) is below 20%, preferably below 15%.
• two or more monodisperse silver halide emulsions (preferably having their respective variation coefficient in the above-described range), which have substantially the same color sensitivity, but different grain size, or plural kinds of grains having the same size but different sensitivities can be coated as a mixture in the same layer, or separately in superposed layers.
• a combination of two or more of polydisperse silver halide emulsions, or a combination of monodisperse and polydisperse emulsions can be used as a mixture, or coated separately in superposed layers.
• the silver halide grains to be used in the present invention may have a regular crystal form, such as a cube, an octahedron, a rhombic dodecahedron, or a tetradecahedron. Grains having different regular crystal forms may be present as a mixture. They also may have an irregular crystal form, such as a sphere. Also, the grains may have a composite form of the above-­described forms.
• the silver halide emulsion grains may assume a tabular form, particularly having a length/thickness ratio of from 5 to 8.
• emulsion wherein 50% or more (on a projection area basis) of the grains assume a tabular form having a length/thickness ratio of 8 or more may be used.
• a mixture of emulsion grains having these various crystal forms may be used.
• These various emulsions may form a latent image predominantly at the surface of the grains, or may mainly form a latent image inside the grains.
• the photographic emulsions used in the present invention can be prepared using the methods described in Research Disclosure , vol. 176, Item No. 17643 (I, II, III) (Dec. 1978).
• the emulsions used in the present invention are generally ripened physically and chemically, and further sensitized spectrally. Additives used in these steps are described in Research Disclosure , Vol. 176, No. 17643 (Dec. 1978) and Vol. 187 No. 18716 (Nov. 1979) as set forth in the following table.
• Photographic additives which can be used in the present invention are also described in these two publications, as summarized in the following table.
• Additives RD 17643 RD 18716 1. Chemical sensitizers p. 23 p. 648, right column 2. Sensitivity-increasing agents " 3. Spectral sensitizers p. 23-24 p. 648, right column 4. Supersensitizers p. 649, right column 5. Brightening agents p. 24 6. Antifoggant and Stabilizers p. 24-25 p. 649, right column 7. Couplers p. 25 8. Organic solvents p. 25 9. Light absorbers, Filter dyes, and UV-ray absorbers p. 25-26 p. 649, right column to p.
• the resulting emulsi­fied dispersion was mixed homogeneously with the emulsions EMl and EM2, and further the gelatin concentration therein was adjusted so that the resulting emulsion had the composition described below.
• the coating composition for the first layer was prepared.
• Coating compositions for the second to the seventh layers were prepared in the same manner as that for the first layer.
• sodium salt of 1-­hydroxy-3,5-dichloro-s-triazine was contained as gelatin hardener.
• Cpd-2 was used as viscosity increasing agent.
• Polyethylene-laminated paper (containing a white pigment (TiO2) and a bluish dye on the first layer side).
• Second layer (Color stain inhibiting layer)
• Monodisperse silver chlorobromide emulsion (EM5) sensitized spectrally with red sensitizing dyes (ExS-4, ExS-5) 0.07 Monodisperse silver chlorobromide emulsion (EM6) sensitized spectrally with red sensitizing dyes (ExS-4, ExS-5) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 0.32 Color image stabilizer (Cpd-8/Cpd-9/Cpd-12 3/4/2 by weight) 0.17 Polymeric dispersion medium (Cpd-11) 0.28 Solvent (Solv-2) 0.20
• Cpd-13 and Cpd-14 were additionally used as irradiation inhibiting dyes.
• Alkanol XC produced by du Pont
• sodium alkylbenzene­sulfonate sodium alkylbenzene­sulfonate
• succinic acid ester produced by Dai-Nippon Ink & Chemicals, Inc.
• Megafac F-120 produced by Dai-Nippon Ink & Chemicals, Inc.
• Cpd-15 and Cpd-16 were used as silver halide stabilizing agent.
• Emulsion Name Crystal Form Grain Size ( ⁇ m) Br Content (mol%) Variation Coefficient EM1 Cube 1.0 80 0.08 EM2 Cube 0.75 80 0.07 EM3 Cube 0.5 83 0.09 EM4 Cube 0.4 83 0.10 EM5 Cube 0.5 73 0.09 EM6 Cube 0.4 73 0.10
• the above-described light-sensitive materials each was exposed to light through an optical wedge, and subjected to photographic processing including the following steps. Processing Step Temperature Time Color Development 38°C 1 min. 40 sec. Bleach-Fix 30 to 34°C 1 min. 00 sec. Rinsing (1) 30 to 34°C 20 sec. Rinsing (2) 30 to 34°C 20 sec. Rinsing (3) 30 to 34°C 20 sec. Drying 70 to 80°C 50 sec.
• the rinsing steps were performed in accordance with a countercurrent replenishing process, in which the rinsing bath (3) was replenished with a rinsing solution, and the solution overflowing the rinsing bath (3) was introduced into the rinsing bath (2), and the solution overflowing the rinsing bath (2) was introduced into the rinsing bath (1).
• compositions of the processing solutions used were as follows.
• Ion exchange water (calcium and magnesium ion concentrations were each below 3 ppm).
• Photographic characteristics of these light-­sensitive materials were evaluated through measurements of the gradation, the maximum density (D max ) and the minimum density (D min ).
• the gradation was expressed in terms of the difference between the density corres­ponding to the sensitivity point and the density corresponding to the point greater than the sensitivity point by 0.5 in a logarithmic exposure scale.
• yellow reflection densities in the unexposed areas were measured.
• the sensitive materials were allowed to stand for 90 days under conditions of 60°C and 15% RH. Then yellow reflection densities in the unexposed areas were measured again, and thereby the sensitive materials were examined for increments of stains with time after the photographic processing.
• the resulting emulsi­fied dispersion was mixed homogeneously with the emulsions EM7 and EM8, and further the gelatin concentration therein was adjusted so that the resulting emulsion had the composition described below.
• the coating composition for the first layer was prepared.
• Coating compositions for the second to the seventh layers were prepared in the same manner as for the first layer.
• sodium salt of 1-­hydroxy-3,5-dichloro-s-triazine was contained as gelatin hardener.
• Cpd-2 was used as viscosity increasing agent.
• Polyethylene-laminated paper (containing a white pigment (TiO2) and a bluish dye on the first layer side).
• Second Layer (Color mixing inhibiting layer)
• Monodisperse silver chlorobromide emulsion (EM11) sensitized spectrally with red sensitizing dyes (ExS-4, ExS-5) 0.07 Monodisperse silver chlorobromide emulsion (EM12) sensitized spectrally with red sensitizing dyes (ExS-4, ExS-5) 0.16 Gelatin 0.92 Cyan coupler (ExC-1) 0.15 Cyan coupler (ExC-2) 0.18 Color image stabilizer (Cpd-7/Cpd-8/Cpd-10 3/4/2 by weight) 0.17 Polymeric dispersion medium (Cpd-11) 0.14 Solvent (Solv-1) 0.20
• Cpd-12 and Cpd-13 were additionally used as irradiation inhibiting dyes.
• Alkanol XC produced by du Pont
• sodium alkylbenzene­sulfonate sodium alkylbenzene­sulfonate
• succinic acid ester produced by Dai-Nippon Ink & Chemicals, Inc.
• Megafac F-120 produced by Dai-Nippon Ink & Chemicals, Inc.
• Cpd-14 and Cpd-15 were used as silver halide stabilizing agent.
• the foregoing light-sensitive material was imagewise exposed, and then subjected to a running processing test with a paper processing machine which included the following steps.
• the running processing test was contained till the color developer was replenished in twice as much amount as the tank volume. Processing Step Temperature (°C) Time (sec.) Amount Replenished* (ml) Tank Volume (l) Color development 38 45 161 17 Bleach-Fix 30 to 36 45 161 17 Rinsing (1) 30 to 37 20 - 10 Rinsing (2) 30 to 37 20 - 10 Rinsing (3) 30 to 37 20 - 10 Rinsing (4) 30 to 37 30 248 10 Drying 75 to 80 60 * per 1 m2 of the light-sensitive material processed.
• the replenishment of the rinsing solution was performed in the direction from the rinsing tank (4) to the rinsing tank (1) according to a four-tank counter replenishing process.
• compositions of the processing solutions used were as follows.
• Ion-exchanged water in which calcium and magnesium ion concentrations were each below 3 ppm.
• light-sensitive materials were prepared in the same manner as for the foregoing material, except that the magenta couplers set forth in Table 2 were employed as the magenta coupler in the third layer, respectively, and the compounds represented by the general formula (III) of the present invention were further added in a proportion of 30 mol% to the couplers, respectively.
• the light-sensitive materials of the present invention showed not only slight changes of photographic characteristics by running processing, but also a considerably depressed increase in stain density with time after the processing.
• the layers of from the first layer (the lowest layer) to the seventh layer (the uppermost layer) were coated in this order to prepare a light-sensitive material.
• Coating compositions for these layers were prepared in the manner described below. The structural formulae and other details of the couplers, the color image stabilizers and other ingredients used therein are described below.
• a coating composition for the first layer was prepared as follows: A mixture of 200 g of a yellow coupler, 93.3 g of a discoloration inhibitor, 10 g of a high boiling point solvent (p), 5 g of a solvent (g) was added to 600 ml of ethyl acetate as an auxiliary solvent, and dissolved therein by heating to 60°C. The resulting solution was mixed with 3,300 ml of a 5% aqueous gelatin solution containing 330 ml of a 5% aqueous solution of Alkanol B (trade name of alkylnaphthalenesulfonate produced by du Pont), and emulsified with a colloid mill to prepare a color dispersion.
• Alkanol B trade name of alkylnaphthalenesulfonate produced by du Pont
• the ethyl acetate was distilled away from the color dispersion under reduced pressure.
• the resulting dispersion was added to 1,400 g of an emulsion (containing 96.7 g of silver and 170 g of gelatin) to which a sensitizing dye for a blue-sensitive emulsion layer and 1-methyl-2-mercapto-5-acetylamino-1,3,4-­triazole had been added, and thereto was further added 2,600 g of a 10% aqueous gelatin solution.
• the coating composition was prepared.
• Second Layer (Color Mixing Inhibiting Layer):
• Silver bromide emulsion (primitive, 0.05 ⁇ m grain size) Silver 10 Color mixing inhibitor (s) 55 Solvent (p) 30 Solvent (q) 15 Gelatin 800
• Gelatin 620 n 2-(2-Hydroxy-3,5-di-tert-amylphenyl)benzotriazole o: 2-(2-Hydroxy-3,5-di-tert-butylphenyl)benzotriazole p: Di(2-ethylhexyl)phthalate q: Dibutyl phthalate r: 2,5-Di-tert-amylphenyl-3,5-di-tert-butylhydroxybenzoate s: 2,5-Di-tert-octylhydroquinone t: 1,4-Di-tert-amyl-2,5-dioctyloxybenzene
• the following compounds were used as sensitizing dye for each emulsion layer.
• Green sensitive emulsion layer Green sensitive emulsion layer
• Red-sensitive emulsion layer
• 1-methyl-2 mercapto-5-acetylamino-­1,3,4-triazole was used as a stabilizer for each layer.
• dipotassium 4-(3-carboxy-5-hydroxy-4-(3-­carboxy-5-oxo-1-(4-sulfonatophenyl)-pyrazoline-4-­ylidene)-1-propenyl)-1-pyrazolyl)benzenesulfonate, and tetrasodium N,N′-(4,8-dihydroxy-9,10-di-oxo-3,7-di-­sulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate) were used as irradiation preventing dyes.
• 1,2-bis(vinylsulfonyl)ethane was used as hardener.
• the following layers from the first to the eleventh were coated on a paper support laminated by polyethylene on both sides thereof to prepare a light-­sensitive material.
• the polyethylene laminated on the first layer side contained titanium white as a white pigment and a trace amount of ultramarine blue as a bluish dye.
• Second Layer (Slow Red-sensitive Layer):
• Silver iodobromide (having an iodide content of 3.5 mol%, and an average grain size of 0.5 ⁇ m) sensitized spectrally with red sensitizing dyes (ExS-1 and ExS-2) 0.15 Gelatin 1.00 Cyan coupler (ExC-1) 0.30 Discoloration inhibitor (Cpd-1, Cpd-2 and Cpd-3, 4:4:2 by weight) 0.15 Coupler solvent (Solv-1 and Solv-2, 1:1 by weight) 0.06
• Silver iodobromide (having an iodide content of 8.0 mol%, and an average grain size of 0.60 ⁇ m) sensitized spectrally with red sensitizing dyes (ExS-1 and ExS-2) 0.11 Gelatin 0.50 Cyan coupler (ExC-1) 0.10 Discoloration inhibitor (Cpd-1, Cpd-2 and Cpd-3, 4:4:2 by weight)) 0.05 Coupler solvent (Solv-1 and Solv-2, 1:1 by weight) 0.04
• Silver iodobromide (having an iodide content of 2.5 mol%, and an average grain size of 0.5 ⁇ m) sensitized spectrally with blue sensitizing dye (ExS-4) 0.15 Gelatin 0.50 Yellow coupler (ExY-1) 0.20 Stain inhibitor (Cpd-8) 0.001 Coupler solvent (Solv-2) 0.05
• Silver iodobromide (having an iodide content of 2.5 mol%, and an average grain size of 1.4 ⁇ m) sensitized spectrally with green sensitizing dye (ExS-4) 0.20 Gelatin 0.50 Yellow coupler (ExY-1) 0.20 Stain inhibitor (Cpd-8) 0.001 Coupler solvent (Solv-2) 0.05
• Fine-grained silver chlorobromide (having a chloride content of 97 mol% and an average grain size of 0.2 ⁇ m) 0.07 Gelatin 1.00 Gelatin hardener (H-1) 0.17 Solv-1 Di(2-ethylhexyl)phthalate Solv-2 Trinonyl phosphate Solv-3 Tricresyl phosphate Solv-4 Dibutyl phthalate Solv-5 Trioctyl phosphate H-1 1,2-Bis(vinylsulfonylacetamido)ethane
• the replenishment in the first and the third water washing steps was performed in accordance with acountercurrent replenishing process, wherein the washing bath of the first water washing (2) was supplied with washing water, the overflowing solution therefrom introduced into the washing bath of the first water washing (1), the washing bath of the third water washing (3) was supplied with washingwater, teh overflowing solution therefrom was introduced into the washing bath of the third water washing(2), and the overflowing solution therefrom was introduced into the washing bath of the third water washing (1).
• compositions of the processing solutions used were as follows.
• PH was adjusted with hydrochloric acid or potassium hydroxide.
• E9 Layer Protective layer E8 Layer Ultraviolet absorbing layer
• E7 Layer Blue-sensitive emulsion layer E6 Layer Interlayer E5 Layer Yellow filter layer
• E4 Layer Interlayer E3 Layer Green-sensitive emulsion layer
• E2 Layer Interlayer E1 Layer Red-sensitive emulsion layer Support B1 Layer Backing layer
• compositions of these layers are described below.
• the coverages are expressed in g/m2, and the coverages of silver halide emulsions and colloidal silvers are those based on silver.
• the amounts of spectral sensitizing dyes are addition amounts expressed in mol per mol of silver halide in the same layer.
• Polyethylene-laminated paper (the polyethylene laminate on the E1 layer side contained a white pigment (TiO2) and a bluish dye (ultramarine)).
• Step Time Temperature Amount replenished Color Development 90 sec. 38°C 300 ml/m2 Bleach-Fix 40 sec. 35°C 300 ml/m2 Water Washing (1) 40 sec. 30°-36°C Water Washing (2) 40 sec. 30°-36°C Water Washing (3) 15 sec. 320 ml/m2 Drying 30 sec. 75°-80°C
• the replenishment of washing water was performed in accordance with a countercurrent replenishing process, wherein the washing bath (3) was replenished with washing solution, and the solution overflowing the washing bath (3) was introduced into the washing bath (2), and the solution overflowing the washing bath (2) was introduced into the washing bath (1).
• the amount of the processing solution carried by the photosensitive material from the prebath was 35 ml/m2. Accordingly, the replenishing factor was 9.1.
• composition of the processing solutions used were as follows.
• the pH was adjusted with potassium hydroxide or hydrochloric acid.
• the pH was adjusted with aqueous ammonia or hydrochloric acid.
• Pure water was used as both tank solution and replenisher.
• pure water refers to water obtained by performing an ion exchange treatment for removing all cations other than H+ and all anions other than OH ⁇ from city water until all ion concentra­tions were reduced to 1 ppm or less.
• Coating compositions were prepared in the following manners.
• a silver chlorobromide emulsion (having a cubic crystal form, an average grain size of 0.88 ⁇ m and a variation coefficient of 0.08 in the grain size distribution, and containing bromide at the grain surface in a proportion of 0.2 mol% in the grain as a whole) was prepared, and thereto were added the blue-sensitive spectral sensitizing dyes illustrated below in equal amounts of 2.0 x 10 ⁇ 4 mole per mole of silver. Thereafter, the emulsion was subjected to sulfur sensitization. The foregoing emulsified dispersion and this emulsion were mixed and dissolved, and adjusted to have the coating composition for the first layer described below. Coating compositions for the second to the seventh layers were prepared in the same manner as for the first layer. In each layer, sodium salt of 1-hydroxy-­3,5-dichloro-s-triazine was used as gelatin hardener.
• the following compound was additionally incorporated in an amount of 2.6 x 10 ⁇ 3 mole per mole of silver halide.
• the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer contained 1-(5-methylureidophenyl)-5-mercaptotetrazole in amounts of 8.5 x 10 ⁇ 5 mole, 7.7 x 10 ⁇ 4 mole and 2.5 x 10 ⁇ 4 mole, respectively, per mole of silver halide.
• the following dyes were added to the emulsion layers in order to prevent the irradiation.
• compositions of the constituent layers are described below.
• the coverages of the ingredients used are expressed in terms of g/m2, with the coverages of silver halides expressed on a silver basis.
• Polyethylene-laminated paper which contained a white pigment (TiO2) and a bluish dye (ultramarine) in the polyethylene on the first layer side).
• Second layer (Color stain inhibiting layer):
• UV-1 Ultraviolet absorber
• Cpd-5 Color mixing inhibitor
• Solv-5 Solvent
• UV-1 Ultraviolet absorber
• Cpd-5 Color mixing inhibitor
• Solv-5 solvent
• Photosensitive materials were prepared in the same manner as the above-described one, except that the compounds of the present invention in a proportion of 10 mol% to the coupler, or/and image stabilizers were incorporated in the third layer, or the green-sensitive layer, as shown in Table 3, respectively, and subjected to the following photographic processing.
• Step Temperature Processing Time Color Development 35°C 45 sec. Bleach-Fix 35°C 45 sec. Water Washing (1) 35°C 30 sec. Water Washing (2) 35°C 30 sec. Water Washing (3) 35°C 30 sec. Drying 75°C 60 sec.
• Ammonium thiosulfate solution (700 g/l) 100 ml Ammonium sulfite 18 g Ammonium ethylenediaminetetraacetatoferrate(III) dihydrate 55 g Disodium ethylenediaminetetraacetate 3 g Ammonium bromide 40 g Glacial acetic acid 8 g Water to make 1,000 ml pH (25°C) 5.5
• each sensitive material was examined for yellow reflection density in the unexposed area (stain), and then allowed to stand for 20 days under the condition of 80°C and 15% RH. Thereupon, the yellow reflection densities of the unexposed areas were measured again, and thereby increases in stain with the lapse of time after the processing were determined.

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• 1988
  • 1988-12-07 JP JP63307750A patent/JPH01250955A/ja active Pending
  • 1988-12-08 EP EP88120563A patent/EP0319985A3/en not_active Withdrawn
  • 1988-12-08 US US07/281,373 patent/USH851H/en not_active Abandoned

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