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
  • G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen

Definitions

• the present invention relates to silver halide color photosensitive materials, and more particularly to silver halide color photosensitive materials which contain a dispersion containing minute and stable lipophilic fine grains and couplers to have the high color density and an improvement in the degree of stains generated in the non-colored part (which is referred to as the white ground) after the lapse of time.
• the formation of color photographic images is carried out by a method comprising developing the exposed silver halide grains using an aromatic primary amine compound as a developing agent and coupling the thus obtained oxidation product of the aromatic primary amine compound with color-forming couplers to give a yellow dye image, a magenta dye image and a cyan dye image.
• the above method usually employs cyan couplers, magenta couplers and yellow couplers.
• pyrazoloazole type magenta couplers show the better sharpness than 5-pyrazolone type magenta couplers both in the shorter wavelength side and the longer wavelength side, and so the former is most preferable in respect of color reproduction but unfavorable to have such a defect that the magenta color stain due to the above-mentioned source (2) easily occurs.
• the developing solution usually consists of a color developing agent, a stop solution, a bleaching solution, a fixing or blix solution and so on.
• the composition of the developing solution is changed by the decomposition of the developing agent in the long processing kept at a high treating temperature of 31°C to 43°C, the oxidation of said agent by contact with air, the accumulation of substances eluted from photo­sensitive materials, the carrying over of the developing solution attached to photosensitive materials to the next bath, and so on to bring about what is called a running solution. So the shortage of some agents used must be supplied and substances not wanted must be removed from the bath to regenerate the solution. However, this is not satisfactory.
• the conventionally known methods of preventing various stains include those of using alkylhydroquinones (e.g., U.S. Patents 3,935,016 and 3,960,570), chroman, coumaran (e.g., U.S. Patent 2,360,290), phenolic compounds (e.g., JP-A-51-9449), and sulfinic acid polymers (e.g., JP-A-56-151937).
• JP-A as used herein means an "unexamined published Japanese patent application”).
• JP-A-56-67842 discloses that photosensitive materials contain compounds obtained by the reaction of nitrogen-containing organic bases or quaternarynitrogen atom-containing compounds with sulfinic acid, an object of which is to provide silver halide photosensitive materials which are stable and suitable for rapid processing by adding and mixing aromatic primary amine compounds as precursors and another object of which is to stabilize the photographic property of the photosensitive materials before development.
• the objects thereof are essentially different from those of the present invention as stated hereinafter.
• JP-A-62-143048 discloses that sulfinic acid compounds containing oil-soluble groups are effective to the above-mentioned stains. It is certain that said sulfinic acid compounds are effective, but have the following problems:
• the object of the present present invention is to provide silver halide color photosensitive materials which result in color photographs having high color image density and little stains in the non-colored part (white ground).
• Another object of the present invention is to provide silver halide color photosensitive materials which result in color photographs having good color-­reproducibility and high image quality.
• a still further object of the present invention is to provide silver halide color photosensitive materials having a highly stable emulsion.
• each of R1 and R2 represents an aliphatic, aromatic or heterocyclic group having 8 or more carbon atoms; each of M1 and M2 represents a hydrogen atom or an inorganic or organic salt-forming atom or atomic group; also M1 represents a protective group to be hydrolyzed with alkali, and sodium dodecyl­benzenesulfonate is excluded from the compounds of formula (II).
• the favorable compounds of formula (II) particularly have a solubility of no more than 5% by weight in water at 25°C. Accordingly, sodium dodecylbenzene sulfonate is unfavorable for the present invention because of the high solubility in water.
• An aliphatic group in R1 and R2 represents a straight or branched chain or cyclic alkyl, alkenyl or alkynyl group having 8 or more carbons, which may be substituted with a substituent.
• An aromatic group in R1 and R2 may represent either one of a carbon-cyclic aromatic group (e.g., phenyl, naphthyl) and a hetero­cyclic aromatic group (e.g., furyl, thienyl, pyrazolyl, pyridyl, indolyl) having 8 or more carbons, which may have a single or condensed ring structure (e.g., benzo­furyl, phenanthridinyl). Moreover, these aromatic rings may have substituents.
• a heterocyclic group in R1 and R2 preferably represents a 3 to 10 membered ring structure group having 8 or more carbons in total, which consists of carbon, oxygen, nitrogen, sulfur or hydrogen as a hetero atom wherein the heterocyclic ring itself may be saturated or unsaturated, and further which may be substituted with a substituent (e.g., coumanyl, pyrorid­yl, pyrolinyl, morpholinyl).
• a substituent e.g., coumanyl, pyrorid­yl, pyrolinyl, morpholinyl.
• substituent reprevers alkyl, halogen, alkoxy, aryloxy, hydroxy, cyano, nitro, alkylthio, arylthio, acyloxy, sulfonyloxy, alkoxycarbonyloxy, acylamino, sulfonamido, imido, amino, anilino, ureido, alkoxycarbonylamino, aryloxycarbonylamino, a nitrogen heterocyclic group (e.g., N-pyrazolyl, N-imidazolyl, N-triazolyl, N-­pyroridinyl), alkoxycarbonyl, acyl, aryloxy-carbonyl, carbamoyl, sulfamoyl, sulfamoylamino, alkylsulfonyl, arylsulfonyl, and a heterocyclic thio group.
• An atom or atomic group to form an inorganic or organic salt in M1 and M2 represents an inorganic cation, for example, Li, Na, K, Ca, or Mg, or an organic cation, for example, triethyl ammonium, methyl ammonium, tetra­butyl ammonium, ammonium, or trimethylbenzyl ammonium.
• a preferable protective group to be hydrolyzed with alkali in M1 represents a group to be hydrolyzed in a pH value of 7.5 or more which is represented by the following formula: wherein each of R3 and R3′ represents a hydrogen atom, an acyl group (e.g., acetyl, benzoyl); or a sulfonyl group (e.g., methanesulfonyl, benzenesulfonyl); each of R4 and R5 represents a hydrogen atom, an alkyl group (e.g., methyl, butyl, dodecyl, ethoxyethyl) or an aryl group (e.g., phenyl, ⁇ -naphthyl, ⁇ -naphthyl); and R4 and R5 may form a 4 to 7 membered ring structure (e.g., cyclo­butane, cyclopentane, cy
• the compounds represented by said general formula (I) and (II) have preferably a solubility of no more than 5% by weight in water at 25°C, more preferively, no more than 1% by weight.
• the preferable group represented by R1 or R2 of the compounds of formulae (I) and (II) is an aromatic group having 10 or more carbons.
• R1 of formula (I) and R2 of formula (II) may be different from each other but preferably are the same.
• R10, R11, R12, R13 and R14 may be the same or different, and each thereof represents a hydrogen atom, an aliphatic group (e.g., methyl, isopropyl, t-butyl, vinyl, benzyl, octadecyl, cyclohexyl), an aromatic group (e.g., phenyl, pyridyl, naphthyl), a heterocyclic group (e.g., piperidyl, pyranyl, furanyl, chromanyl), a halogen atom (e.g., chlorine, bromine), -SR15-, -OR15, an aliphatic acyl group or an aromatic acyl group (e.g., acetyl, benzoyl), an alkoxycarbonyl group (e.
• R10, R11, R12, R13 and R14 may be the same or different, and each thereof represents a hydrogen atom, an aliphatic
• the amount of the sulfinic acid compounds of formula (I) is preferably 1 to 50 mol%, more preferably 2 to 20 mol% on the basis of the amount of the couplers included in the same layer. In case where they are not existed in the same layer, the amount is based on the amount of the magenta coupler.
• the amount of the sulfonic acid compounds of formula (II) is preferably over 2% by weight, more preferably 10 to 200% by weight on the basis of that of the sulfinic acid compounds of formula (I).
• the sulfinic acid compounds of formula (I) and the sulfonic acid compounds of formula (II) can be added to the silver halide emulsion layers and the other hydrophilic colloidal layers (intermediate layer, ultra­violet ray absorbing layer, protective layer and son on), more preferably to the same silver halide emulsion layer, and particularly most preferably to the same lipophilic fine grains.
• the remaining aromatic amine develop­ing agents can be chemically combined by substitution or addition reaction.
• the preferable compounds represented by formulae (A-I) and (A-II) are those whose secondary reaction rate constant K2 with p-anisidine (in trioctyl phosphate at 80°C) range from 1.0 liter/mol ⁇ sec to 1 ⁇ 10 ⁇ 5 liter/mol ⁇ sec.
• the amount of the compounds represented by formulae (A-I) and (A-II) is 1 ⁇ 10 ⁇ 1 to 10 mol, preferably 3 ⁇ 10 ⁇ 10 mol to 5 mol per mol of the amount of the couplers used in the same layer.
• a yellow coupler a magenta coupler and a cyan coupler which have good dispersion resistance and good oil-solubility.
• couplers may be 4 or 2 equivalents on the basis of silver ion and may be in the state of polymer or oligomer. Moreover, the couplers may be used in­dependently or in the combination of two or more.
• each of R31, R34, and R35 represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group
• R32 represents an aliphatic group
• each of R33 and R36 represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group
• R35′ represents a hydrogen atom or has the same defini­tion as given in R35
• each of R37 and R39 represents a substituted or unsubstituted phenyl group
• R38 repre­ sents a hydrogen atom, an aliphatic group, an aromatic acyl group or an aliphatic or aromatic sulfonyl group
• Q represents a substituted or unsubstituted N-phenyl­carbamoyl group
• R31, R32, R33 or Y1; R34, R35, R36 or Y2; R37, R38, R39 or Y3; R40, Z21, Z22 or Y4; Q or Y5 may form a dimer or higher polymeric form.
• the above-mentioned aliphatic group represents a straight, branched or cyclic alkyl, alkenyl, or alkynyl group.
• the bonding of Z21-Z22 is a carbon-carbon double bond, the bonding may be a part of the aromatic ring.
• R40 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 sulf
• R40 represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, propyl, iso-propyl, t-­butyl, trifluoromethyl, tridecyl, 3-(2,4-di-t-amyl­phenoxy)propyl, allyl, 2-dodecyloxyethyl, 3-phenoxy­propyl, 2-hexylsulfonyl-ethyl, 3-(2-butoxy-5-t-hexyl­phenylsulfonayl)propyl, cyclopentyl, benzyl), an aryl group (e.g., phenyl, 4-t-butylphenyl, 2,4-di-t-amyl­phenyl, 4-tetradecanamidophenyl), a heterocyclic group
• a halogen atom e.g., chlorine, bro
• the coupling-off groups represented by Y1 to Y5 include a halogen atom (e.g., fluorine, chlorine, bromine), an alkoxy group (e.g., dedecyloxy, dodecyloxy­carbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyl­oxy, methanesulfonyloxy), an aryloxy group (e.g., 4-­methylphenoxy, 4-tert-butylphenoxy, 4-methoxyphenoxy, 4-­methanesulfonylphenoxy, 4-(4-benzyloxyphenylsulfonyl)­phenoxy), an acyloxy group (e.g., acetoxy, tetradecano­yloxy, benzoyloxy), a sulfonyloxy group (e.g., methanesulfonyloxy, toluenesulfonyloxy), an amido group (e
• the couplers having photographically useful groups include couplers which release photographically useful fragments such as development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardening agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers by coupling with oxidation products of color developing agents, colored couplers which have the effect of color correction, and DIR couplers which release development inhibitors along with the process of development to improve sharpness and graininess of image.
• DIR couplers may be replaced with DIR compounds which cause the coupling reaction with said couplers and oxidation products of developing agents to form colorless compounds and simultaneously release development inhibitors.
• DIR couplers include the couplers having inhibitors which are directly bonded to the coupling position and the couplers having inhibitors which are bonded to the coupling position through divalent groups so that the inhibitors are released by intramolecular nucleophilic reaction caused in the groups eliminated by coupling reaction, intramolecular electron-transfer reaction and so on (which are called timing DIR couplers and timing DIR compounds). Also, the inhibitors having good diffusibility and those having little diffusibility can be used independently or in combinations thereof after the elimination.
• magenta couplers are preferable and 5-­pyrazolone series couplers and pyrazoloazole series couplers, particularly, represented by formulae (V) and (VI), are more preferable. Moreover, the couplers represented by formula (VI) are the most preferable.
• the compounds represented by formula (VI) are preferable, and particularly, the two-equivalent couplers are more preferable.
• R40 and Y4 have the same definition as given in formula (VI)
• R41 has the same definition as R40; R40 and R41 may be the same or different.
• formula (VIII) is more preferable than formula (VII).
• the amount of the compounds represented by the formulae (III) to (VIII) is preferably 1 ⁇ 10 ⁇ 3 to 1 mol, more preferably 1 ⁇ 10 ⁇ 2 to 8 ⁇ 10 ⁇ 1 mol per mol of silver halide.
• the compounds represented by formulae (I) and (II) of the present invention are dissolved in high boiling point coupler solvents being immiscible with water and then can be dispersed in hydrophilic colloids as lipophilic fine grains (oil droplets).
• Auxiliary solvents may be used, if desired, when dissolved.
• water-insoluble and organic solvent-soluble polymer compounds may be present in the lipophilic fine grains.
• the compounds of formulae (I) and (II) can also be impregnated in polymer latex grains.
• the high boiling point coupler solvents there can be used compounds which have a melting point of 100°C or less and a boiling point of 140°C or more, being immiscible with water and acting as good solvents for the couplers.
• the melting point of the high boiling point coupler solvents is preferably 80°C or less.
• the boiling point of the high boiling point coupler solvents is preferably 160°C or more, more preferably 170°C or more.
• high boiling point coupler solvents include, for example, phthalic acid alkyl esters (e.g., dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, dimethoxyethyl phthal­ate), phosphates (e.g., diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trioctyl phosphate, trinonyl phosphate, dioctyl butyl phosphate, monophenyl-­p-t-butyl phenyl phosphate), citrates (e.g., tributyl acetyl citrate), benzoates (e.g., octyl benzoate), alkylamides (e.g., diethyl lauryl amide, dibutyl lauryl amide), fatty acid esters (e.g., dibutoxy ethyl succinate,
• auxiliary solvents are organic solvents having low boiling points of about 30 to 140°C under atmospheric pressure, for example, lower alkyl acetate 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, dimethyl­sulfoxide, chloroform, cyclohexane and so on.
• lower alkyl acetate such as ethyl acetate, isopropyl acetate and butyl acetate
• ethyl propionate methanol, ethanol, secondary butyl alcohol, cyclohexanol
• fluorinated alcohol
• the dispersion method by polymer latex is, for example, the low double polymer latex dispersing method described in U.S. Patent 4,203,716.
• the hydrophilic colloidal layer preferably contains ultraviolet ray absorbing agents, such as benzotriazole compounds substituted with aryl group (e.g., disclosed in U.S. Patent 3,533,794), 4-­thiazolidone compounds (e.g., disclosed in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (e.g., disclosed in JP-A-46-2784), cinnamic acid ester compounds (e.g., disclosed in U.S. Patents 3,705,805 and 3,707,357), butadiene compounds (e.g., disclosed in U.S.
• ultraviolet ray absorbing agents such as benzotriazole compounds substituted with aryl group (e.g., disclosed in U.S. Patent 3,533,794), 4-­thiazolidone compounds (e.g., disclosed in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (e.g., disclosed in JP-A-46-2
• Patent 4,045,229) and bisphenol derivatives e.g., disclosed in U.S. Patent 3,700,455
• ultraviolet ray absorbing couplers e.g., ⁇ -naphthol series cyan dye forming couplers
• ultraviolet ray absorbing polymers e.g., ⁇ -naphthol series cyan dye forming couplers
• These ultraviolet ray absorbing agents may be mordanted in a specific layer.
• the preferable ultraviolet ray absorbing agents are represented by the general formulae (U-I) and (U-­II): wherein each of R51, R52, and R53 represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkyl group, an alkoxyl group, an aryl group, an aryloxy group or an acylamino group; wherein each of R54 and R55 represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group or an acyl group; X is -CO- or -COO-; and n is an integer of 1 to 4.
• the silver halides used in the silver halide emulsions of the present invention include any silver halides used in ordinary silver halide emulsions such as silver chloride, silver iodobromide, silver bromide, silver chlorobromide and silver chloroiodobromide. These silver halide grains may be coarse or fine in any arbitrary wide or narrow range of grain size but it is desirable that a monodispersed emulsion can be used preferably in a variable rate of 15% or less, more preferably 10% or less.
• these silver halide grains may be in the form of regular crystals or irregular crystals such as spherical, tabular and twin crystals and also in any ratio of [100] and [111] crystal faces.
• the crystalline structures of these silver halide grains may be uniform in the inside and in the outside or in the state of layers having different qualities in the inside and in the outside.
• these silver halides may be the type of forming latent images mainly on the surface or the other type of forming internal latent images mainly inside the grains. The type of forming internal latent images inside grains is particularly advantageously used to form direct positive images.
• these silver halides may be produced by any of a neutral method, an ammonia method and an acid method and also by any of a single jet method, a double jet method, a reverse mixing method and a conversion method.
• a mixture of two or more kinds of silver halide emulsions prepared independently can be used.
• Silver halide photographic emulsions prepared by dispersing silver halide grains in binder liquids can be sensitized by chemical sensitizers.
• the chemical sensitizers advantageously used together in the present invention include noble metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.
• the noble metal sensitizers include gold compounds, ruthenium compounds, rhodium compounds, palladium compounds, iridium compounds and platinum compounds.
• ammonium thio­cyanate and sodium thiocyanate can also be used together.
• the sulfur sensitizers include active gelatin and sulfur compounds.
• the selenium sensitizers include active or inert selenium compounds.
• the reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethane sulfinic acid, hydrazinium salts, and hydrazine derivatives.
• the photosensitive materials of the present invention preferably may have the other auxiliary layers than the silver halide emulsion layers such as a protective layer, an intermediate layer, a filter layer, an antihalation layer and a back layer.
• gelatin is advantageous and also the other hydrophilic colloids are employable.
• proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; and various synthetic hydrophilic high molecular weight substances such as homopolymers or copolymers of polyvinyl alcohols, polyvinyl alcohol partial acetal, poly-N-­vinylpyrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.
• proteins such as gelatin derivatives, graft polymers of gelatin and other polymers, albumin, and casein
• cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfates
• sugar derivatives such as sodium alginate and starch derivatives
• various synthetic hydrophilic high molecular weight substances such as homopoly
• gelatin there can be used lime-treated gelatin, and enzyme-treated gelatin described in Bull. Soc. Sci. Phot. Japan , No. 16, page 30 (1966). Furthermore, hydrolysis decomposition product or enzyme decomposition product of gelatin can be used.
• the emulsion layers and the auxiliary layers of the photosensitive materials of the present invention can contain other various additives for photography, for example, antifoggants, dye image discoloration-prevent­ing agents, color stain preventing agents, brightening agents, antistatic agents, hardening agents, surface active agents, plasticizers, wetting agents and ultra­violet ray absorbing agents, as disclosed in Research Disclosure , Vol. 176, No. 17643.
• the silver halide photosensitive materials of the present invention are produced by applying the emulsion and auxiliary layers containing said various photographic additives, if desired, onto supports treated with corona discharge, flame or ultraviolet radiation directly or through an undercoating or intermediate layer.
• the supports used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, and transparent supports having a reflecting layer or using a reflector such as glass plates, polyester films such as cellulose acetate, cellulose nitrate or polyethylene terephthal­ate, polyamide films, polycarbonate films, polystyrene films and vinyl chloride resins. These supports are properly selected according to the use objects of the photosensitive materials.
• the emulsion layers and the other layers used in the present invention are coated by various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating. Moreover, two or more layers can be coated at the same time by the methods described in U.S. Patents 2,761,791 and 2,941,898.
• the emulsion layers of the present invention can be arbitrarily coated, for example, in an order of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer or another order of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer successively arranged from the support side.
• an ultraviolet ray absorbing layer is prepared next to the layer being farthest apart from the support to be faced to the support side and, if desired, also on the reverse side of the support. Particularly in the latter case, it is desirable that a protective layer consisting of substantially only gelatin is formed on the most upper layer.
• the color developing solution used for the development of the photosensitive materials of the present invention is preferably an alkaline aqueous solution consisting principally of an aromatic primary amine series color developing agent.
• an aromatic primary amine series color developing agent As the color developing agents, aminophenol series compounds are also useful, but p-phenylenediamine series compounds are preferably used.
• color developing solutions contain pH buffers such as carbonate of alkali metal, borate and phosphate, development retarders or antifoggants such as bromide, iodide, benzimidazoles, benzothiazole, and mercapto compounds.
• pH buffers such as carbonate of alkali metal, borate and phosphate
• development retarders or antifoggants such as bromide, iodide, benzimidazoles, benzothiazole, and mercapto compounds.
• various preservatives such as hydroxyl amine, diethyl­hydroxyl amine, hydrazine sulfites and the like, phenyl­semicarbazide and the like, triethanol amine, catechol sulfonic acid and the like, triethylene diamine(1,4-­diazabicyclo[2,2,2]octane) and the like; organic solvents such as ethylene glycol and diethylene glycol; developing accelerators such as benzyl alcohol, poly­ethylene glycol, quaternary ammonium salt and amines; dye-forming couplers; competing couplers; fogging agents such as sodium boronhydride; auxiliary develop­ing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting agents; and various chelating agents such as aminopolycarboxylic acid, aminopolyphsphonic acid, alky­lphosphonic acid, phosphonocarboxylic acid (e.g., ethy
• the amount of benzyl alcohol is preferably restricted to the lower level in view of the protection of environment and the prevention of poor recoloring, and most preferably, benzyl alcohol is not used.
• black and white development is usually carried out as the first step and then followed by the step of color development.
• the black and white developing solutions can employ the well-known black and white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-­pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol alone or in combinations thereof.
• the use of the above-mentioned internal latent-image type silver halide emulsions can directly provide positive images without conducting any reversal process.
• fogging treatment is carried out by light or a nucleating agent when or before the color development is achieved.
• These color developing and black and white developing solutions generally have a pH value of 9 to 12.
• the replenishment of these solutions is generally supplied in an amount of 3 liters or less per 1 m2 of photosensitive materials though depending on the sorts of color photosensitive materials to be treated and the amount can be decreased to 500 ml or less by lowering the concentration of bromide ions contained in the solution to be supplied.
• the replenish amount of the developing solution is decreased, it is desirable to diminish the area made in contact with the air in a treating tank to prevent the evaporation and air oxidation of the solution. Further, the replenish amount of the developing solution can be lowered by means of restricting the accumulation of bromide ions in the developing solution.
• the photosensitive emulsion layers are usually bleached after color-development.
• the bleaching treatment may be carried out simultaneously with the fixing treatment (bleach-fix treatment) or each treat­ment may be conducted independently.
• the bleach-fix treatment may be conducted after the bleaching treatment.
• the bleaching agents used in the present invention include multivalent metal compounds such as iron (III) compound, cobalt (III) compound, chrome (VI) compound and copper (II) compound; peracids, quinones and nitro compounds.
• the typical bleaching agents to be used in the present invention include ferricyanide; dichromates; organic complex salts of iron (III) or cobalt (III) such as complex salts of amino­polycarboxylic acids (e.g., ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane­diaminetetraacetic acid, methyliminodiacetic acid, 1,3-­diaminopropanetetraacetic acid, and glycoletherdiamine­tetraacetic acid); citric acid, tartaric acid or malic acid; persulfates; bromates; permanganates; and nitrobenzenes.
• amino­polycarboxylic acids e.g.,
• aminopoly­carboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and persulfates are preferable in view of the quick treatment and the prevention of environmental pollution.
• aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and in a bleach-fix bath.
• the bleaching solutions or bleach-fix baths using these aminopolycarboxylic acid iron (III) complex salts have a pH of 5.5 to 8, which can be lowered for the purpose of accelerating the process of treatment.
• bleaching solutions, bleach-fix baths and prebaths thereof can employ bleach-accelerators, if desired.
• the examples of useful bleach-accelerators are disclosed in the following specifications: namely, the compounds having a mercapto group or a disulfide disclosed in U.S.
• Patent 3,893,858 West German Patents 1,290,812 and 2,059,988, JP-A-53-32736, JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-­95631, JP-A-53-10423, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, Research Disclosure No.
• JP-B 17129 (July, 1978); thiazolidine derivatives disclosed in JP-A-50-­140129; thiourea derivatives disclosed in JP-B-45-8506 (the term "JP-B” as used herein means an "examined Japanese patent publication"), JP-A-52-20832, JP-A-53-­32735 and U.S.
• the compounds having a mercapto group or a disulfide group are preferable in view of the effect of acceleration, and the compounds disclosed in U.S.
• Patent 3,893,858, West German Patent 1,290,812, and JP-A-53-95630 are particularly preferable.
• the compounds disclosed in U.S. Patent 4,552,834 are also preferable. These bleach-accelerators may be added into the photosensitive materials.
• thio­sulfates As the fixing agents, there are given thio­sulfates, thiocyanates, thioether series compounds, thioureas, and various iodides. Thiosulfates are generally used, and particularly, ammonium thiosulfate can most widely be used.
• sulfites, bisulfites or carbonyl bisulfite addition compounds are preferable.
• the silver halide color photosensitive materials of the present invention are generally treated by the steps of washing and,/or stabilizing after the desilver­ing step.
• the amount of water in the step of washing is widely determined according to various conditions such as the specific properties of photosensitive materials (raw materials such as couplers), uses, washing water temperature, number of washing tanks (number of steps), replenishing system such as the down-flow current and the countercurrent and so on.
• the amount of washing water can exceedingly be decreased, but the longer stay of water in the tank causes problems such as the propagation of bacteria and the attachment of the grown floating creatures to the photosensitive materials.
• the treatment of the color photosensitive materials of the present invention can utilize quite effectively the method of decreasing calcium ions and magnesium ions disclosed in JP-A-62-288838.
• the present invention can use chlorine sterilizers such as iso­thiazolone compounds, thiabendazoles and chlorinated isocyanuric acid sodium, other benzotriazole and also the bactericides disclosed in Bokin Bobai no Kagaku ("Chemistry of Bactericides and Fungicides") written by Hiroshi Horiguchi, Biseibutsu no Mekkin, Sakkin, Bobai Gijutsu ("Techniques of Sterilization, Pasteurization, and Fungicides of Microorganisms”) edited by Eisei Gijutsu-kai ("Sanitary Technology Society"), Bokin Bobaizai Jiten (“Dictionary of Bactericides and Fungicides”) edited by Nippon Bokin Bobai Gakkai (“Japan Bactericide and Fungicide Society”).
• Chemistry of Bactericides and Fungicides written by Hiroshi Horiguchi
• Biseibutsu no Mekkin Sakkin
• the pH value of washing water ranges from 4 to 9, preferably from 5 to 8.
• the washing temperature and time are generally selected from the range of 15 to 45°C for 20 seconds to 10 minutes, preferably at 25 to 40°C for 30 seconds to 5 minutes.
• the photosensitive materials of the present invention can be treated directly with a stabilizing solution instead of said water washing.
• Such stabilizing treatment can employ all the known methods disclosed in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.
• said water washing treatment may be followed by the stabilizing treatment.
• the overflow solution by replenishment of said washing and/or stabilizing solution can be utilized again in the other steps such as a desilvering step etc.
• the silver halide color photosensitive materials of the present invention may include color developing agents for the purpose of simplifying and accelerating the processing.
• color developing agents for example, indoaniline compounds disclosed in U.S. Patent 3,342,597; Schiff base type compounds disclosed in U.S. Patent 3,342,599, Research Disclosure Vol. 148, No. 14850 and Vol. 151, No. 15159; aldol compounds disclosed in Research Disclosure No. 13924; metal salt complex disclosed in U.S. Patent 3,719,492; and urethane compounds disclosed in JP-A-53-135628.
• the silver halide color photosensitive materials of the present invention may include various 1-phenyl-3-­pyrazolidones for the purpose of accelerating the color development, if desired.
• the typical compounds thereof are disclosed in JP-A-56-64339, JP-A-57-14454 and JP-A-­58-115438.
• various processing solutions are used at a temperature of 10 to 50°C, normally in the range of 33 to 38°C.
• the temperature may be raised to accelerate the processing and shorten the processing time or may be lowered to improve the image quality and the stability of the processing solutions.
• the processing using cobalt or hydrogen peroxide intensification disclosed in West German Patent 2,226,770 or U.S. Patent 3,674,499 may be carried out so as to curtail the amount of silver of photosensitive materials.
• a coupler (M-35) of the present invention 10 g of a coupler (M-35) of the present invention, 20 g of a high boiling point coupler solvent (S-1) and 40 cc of ethyl acetate were dissolved at 60°C to obtain a mixed solution. Then, the solution was added to a 50°C-mixed solution consisting of 125 g of 16% gelatin aqueous solution and 8 cc of 5% dodecylbenzenesulfonic acid with stirring and then emulsified with a high-speed stirrer (homogenizer). Then, water was added to the above emulsified solution to obtain 400 g of a comparative emulsion (A) in total. The emulsion (A) had an average grain size of 0.16 ⁇ .
• the emulsions (A) to (F) were allowed to stand with stirring in the sate of heat-melting (40°C) and the stability thereof was examined after the lapse of time.
• compositions of the layers The following is the description as to the compositions of the layers.
• the numerical figures show the amounts of solutions coated (g/m2). Silver halide emulsions are given in the conversion amounts of silver.
• Polyethylene-laminated paper (polyethylene on the first layer side contained a white pigment (TiO2) and a bluish dye.)
• Second Layer (dye-mix-preventing layer)
• Cpd-12 and Cpd-13 were used as the irradiation-preventing dyes.
• each layer contained emulsification dispersants and coating aids such as Alkanol XC (Du­ Pont), sodium alkylbenzenesulfonate, succinic acid ester and Megafac F-120 (made by Dainippon Ink and Chemicals, Incorporated).
• emulsification dispersants and coating aids such as Alkanol XC (Du­ Pont), sodium alkylbenzenesulfonate, succinic acid ester and Megafac F-120 (made by Dainippon Ink and Chemicals, Incorporated).
• As the stabilizers of silver halide were used Cpd-14, 15, 17.
• the multilayered photographic papers (2) to (8) were prepared in a manner similar to the process of the multilayered photographic paper (1) except the following modified points (green-sensitive layer) shown in Table 2.
• Table 2 modified points added to photographic paper (1)
• Photographic paper Green-sensitive layer Remarks (1) Photographic paper Green-sensitive layer Remarks (1) - Comparison (2) I-2 (30 mg/m2) was further added. Comparison (3) I-2 (30 mg/m2) and II-1 (5 mg/m2) were further added.
• Invention (5) I-2 (30 mg/m2), II-1 (15 mg/m2) and A-12 (20 mg/m2) were further added.
• Invention (6) I-3 (25 mg/m2) was further added. Comparison (7) I-3 (25 mg/m2) and II-8 (20 mg/m2) were further added.
• Invention (8) I-3 (25 mg/m2), II-8 (20 mg/m2) and A-11 (10 mg/m2) were further added.
• Invention (8) I-3 (25
• the above-mentioned photosensitive materials were exposed to light through optical wedge and then processed by the following steps. Processing steps Temperature Time Color development 38°C 100 sec Bleach-fix 30-34°C 60 sec Rinse 1 30-34°C 20 sec Rinse 2 30-34°C 20 sec Rinse 3 30-34°C 20 sec Dry 70-80°C 50 sec (A three-tank countercurrent system from Rinse 3 to Rinse 1 was used.)
• the blue-sensitive layer and the red-­sensitive layer can obtain the same effect as in the case of the green-sensitive layer.
• Photographic papers were prepared in a manner similar to Example 2 except that the following silver halide emulsions EM7 to EM12 were used instead of the silver halide emulsions EM1 to EM6 used in Example 2. These photographic papers were treated by the following steps and tested as to the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer to obtain the results similar to Example 2.
• Variation coefficient *2 EM7 Cube 1.1 1.0 0.10 EM8 " 0.8 1.0 0.10 EM9 " 0.45 1.5 0.09 EM10 " 0.34 1.5 0.09 EM11 " 0.45 1.5 0.09 EM12 " 0.34 1.6 0.10 *1: The same definition as given in Example 2.
• composition of each processing salt is given as follows:
• Ion-exchange solution (the concentrations of calcium and magnesium are 3 ppm or less.)

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• 1987
  • 1987-08-28 JP JP62214681A patent/JPH07109500B2/ja not_active Expired - Lifetime
• 1988
  • 1988-08-26 EP EP88113968A patent/EP0305926B1/de not_active Expired - Lifetime
  • 1988-08-26 DE DE8888113968T patent/DE3879816D1/de not_active Expired - Lifetime
  • 1988-08-29 US US07/237,205 patent/USH706H/en not_active Abandoned

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