EP0305926B1 - Farbempfindliche Silberhalogenidmaterialien - Google Patents

Farbempfindliche Silberhalogenidmaterialien Download PDF

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Publication number
EP0305926B1
EP0305926B1 EP88113968A EP88113968A EP0305926B1 EP 0305926 B1 EP0305926 B1 EP 0305926B1 EP 88113968 A EP88113968 A EP 88113968A EP 88113968 A EP88113968 A EP 88113968A EP 0305926 B1 EP0305926 B1 EP 0305926B1
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Prior art keywords
group
compounds
silver halide
aromatic
acid
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EP88113968A
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French (fr)
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EP0305926A1 (de
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Osamu Takahashi
Nobuo Furutacho
Masakazu Morigaki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • 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 high color density and an improved 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 a better sharpness than 5-pyrazolone type magenta couplers both in the shorter wavelength side and the longer wavelength side, and so the former is preferable in respect of color reproduction but has the disadvantage that the magenta color stain due to the above-mentioned source (2) easily occurs.
  • the developing bath is seldom newly prepared in every development processing.
  • a developing solution is supplied again according to the amount used for development.
  • the solution composition is not maintained by adding only water used in development.
  • 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 alkyl- hydroquinones (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 quaternary nitrogen 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 or the photosensitive materials before development.
  • the objects thereof are essentially different from that of the present invention as stated hereinafter.
  • Jp-A-62-143048 (corresponding to EP-A -0 228 655) discloses that sulfinic acid compounds containing oil-soluble groups are effective against the above-mentioned stains. It is certain that said sulfinic acid compounds are effective, but have the following problems:
  • the object of the present invention is to provide silver halide color photosensitive materials which result in color photographs having a high color image density, little stains in the non-colored part (white ground), a good color-reproducibility and high image quality, the silver halide color photosensitive materials containing a highly stable emulsion.
  • a silver halide color photosensitive material which comprises a lipophilic fine grain dispersed in at least one hydrophilic colloidal layer formed on a support containing at least one compound represented by formula (I) wherein R 1 and represents an aliphatic, aromatic or heterocyclic group having 8 or more carbon atoms; M 1 represents a hydrogen atom or an inorganic or organic salt-forming cation; a protective group to be hydrolyzed with alkali represented by the following formulae: wherein each of R 3 and R3,, which may be the same or different, represents a hydrogen atom, an acyl group or a sulfonyl group each of R 4 and R 5 which may be the same or different represents a hydrogen atom, an alkyl group or an aryl group or R 4 and R 5 may form a 4 to 7 ring structure; characterized in that said grain further contains at least one compound represented by formula (II) wherein R 2 represents an aliphatic, aromatic or heterocyclic group having 8 or more carbon atoms;
  • 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 allphatic group in R 1 and R 2 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 R 1 and R 2 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 R 1 and R 2 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., coumaryl, pyroridyl, pyrolinyl, morpholinyl).
  • a substituent e.g., coumaryl, pyroridyl, pyrolinyl, morpholinyl.
  • substituent represents alkyl, halogen, alkoxy, aryloxy, hydroxy, cyano, nitro, alkylthio, arylthio, acyloxy, sulfonyloxy, alkoxycarbonyloxy, acylamino, sulfonamido, imido, amino, anlino, 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.
  • N-pyrazolyl N-imidazolyl, N-tri
  • An atom or atomic group to form an inorganic or organic salt in M 1 and M 2 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.
  • M 1 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 R 3 and R 3 ' represents a hydrogen atom, an acyl group (e.g., acetyl, benzoyl); or a sulfonyl group (e.g., methanesulfonyl, benzenesulfonyl); each of R 4 and R 5 represents a hydrogen atom, an alkyl group (e.g., methyl, butyl, dodecyl, ethoxyethyl) or an aryl group (e.g., phenyl, a-naphthyl, ⁇ -naphthyl); and R 4 and R 5 may form a 4 to 7 membered ring structure (e.g., cyclobutane, cyclopentane, cylohexane, or cycloheptane ring
  • 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 preferably, no more than 1 % by weight.
  • the preferable group represented by R 1 or R 2 of the compounds of formulae (I) and (II) is an aromatic group having 10 or more carbons.
  • R 1 of formula (I) and R 2 of formula (II) may be different from each other but preferably are the same.
  • the most preferable of the compounds of formulae (I) and (II) are those represented by the following general formulae (III) and (III'), respectively: wherein Rio, R 11 , R 12 , R 13 and R 14 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), -SR 15 -, -OR 15 , an aliphatic acyl group or an aromatic acyl group (e.g., acetyl, benzoyl), an alkoxycarbonyl
  • JP-A-62-143048 The compounds of formula (I) are disclosed in JP-A-62-173470 (corresponding to EP-A-0288655 and EP-A -0 235 913, respectively.)
  • 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. When they do not exist 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 so on), more preferably to the same silver halide emulsion layer, and particularly most preferably to the same lipophilic fine grains.
  • the most preferable compounds to be used with the compounds of formulae (I) and (II) are compounds represented by the following general formulae (A-I) or (A-II) which chemically combine with aromatic amine developing agents remaining after color development processing to form chemically inert and substantially colorless compounds:
  • 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 K 2 with p-anisidine (in trioctyl phosphate at 80°C) ranges from 1.0 liter/mols•s to 1x10- 5 liter/mol•s.
  • the amount of the compounds represented by formulae (A-I) and (A-II) is 1x10 -1 to 10 mol, preferably 3x10 -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 form of a polymer or oligomer. Moreover, the couplers may be used independently or as a combination of two or more.
  • the preferable couplers to be used in the present invention are represented by the following formulae: wherein each of R 31 , R 34 , and R 35 represents an aliphatic group, an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group; R 32 represents an aliphatic group; each of R 33 and R 36 represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group; R 35 ' represents a hydrogen atom or has the same definition as given in R 35 ; each of R 37 and R 39 represents a substituted or unsubstituted phenyl group; R 38 represents 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; each of Y i , Y 2 , Y 3 ,
  • R 31 , R 32 , R 33 or Y 1 ; R 34 , R 35 , R 36 or Y 2 ; R 37 , R 38 , R 39 or Y 3 ; R 4o , Z 21 , Z 22 or Y 4 ; Q or Y 5 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 Z 21 -Z 22 is a carbon-carbon double bond, the bonding may be a part of the aromatic ring.
  • R 40 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, a ureido group, an imido group, a sulfamoylamino group, a carbamoylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonamido group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl
  • 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 (e.g.
  • a halogen atom e.g., chlorine, bro
  • the coupling-off groups represented by Y 1 to Y 5 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, toluenesul- fonyloxy), an amido group (e.g.,
  • 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 the sharpness and the 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 an intramolecular nucleophilic reaction caused in the groups eliminated by the coupling reaction, intramolecular electron-transfer reaction and so on (which are called timing DIR couplers and timing DIR compounds).
  • Inhibitors having good diffusibility and those having little diffusibility can be used independently or in combinations 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.
  • R 40 and Y 4 have the same definition as given in formula (VI)
  • R 41 has the same definition as R 40 ;
  • R 40 and R 41 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 1x10 -3 to 1 mol, more preferably 1x10 -2 to 8x10 -1 mol per mol of silver halide.
  • the compounds represented by formulae (I) and (II) 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.
  • 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., dietnyl lauryl amide, dibutyl lauryl amide), fatty acid esters (e.g., dibutoxy ethyl succinate, diethoxy e
  • 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, ; 8-ethoxyethy!acetate, 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-46-2784)
  • Patent 4,045,229) and bisphenol derivatives e.g., disclosed in U.S. Patent 3,700,455
  • ultraviolet ray absorbing couplers e.g., a-naphthol series cyan dye forming couplers
  • ultraviolet ray absorbing polymers e.g., a-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 R 51 , R 52 , and R 53 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 R 54 and R 55 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 according to 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 is 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 the layers may have different qualities in the inside and in the outside.
  • these silver halides may be of the type forming latent images mainly on the surface or of the type forming internal latent images mainly inside the grains. The type 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 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, can be used.
  • gelatin lime-treated gelatin, and enzyme-treated gelatin described in Bull. Soc. Sci. Phot. Japan, No. 16, page 30 (1966), can be used. Furthermore, the hydrolysis decomposition product or the 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 according to the present invention can be arbitrarily coated, for example, in the order of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer or the 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, aminopolyph- sphonic acid, alkylphosphonic acid, phosphonocarboxylic acid (e.g., ethylenediaminetetraace
  • 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 combination.
  • 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 m 2 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 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. Moreover, in order to speed up the treatment, the bleach-fix treatment may be conducted after the bleaching treatment. Furthermore, according to the object of the present invention, there can be arbitrarily conducted the continuous two-tank bleach-fix bath treatment, the fix treatment after bleach-fix treatment or the bleach treatment after bleach-fix 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 glycolether- diaminetetraacetic acid); citric acid, tartaric acid or malic acid; persulfates; bromates; permanganates; and nitrobenzenes.
  • aminopolycarboxylic acids e.g., ethylenediaminetetra
  • 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.
  • Suitable fixing agents are thiosulfates, thiocyanates, thioether series compounds, thioureas, and various iodides.
  • Thiosulfates are generally used, and particularly, ammonium thiosulfate can most widely be used.
  • As preservatives, 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 Sokin Bobai Gakkai (“Japan Bactericide and Fungicide Society”).
  • chlorine sterilizers such as isothiazolone compounds, thiabendazoles and chlorinated isocyanuric acid sodium
  • other benzotriazole and also the bactericides disclosed
  • 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.
  • Processing using cobalt or hydrogen peroxide intensification disclosed in West German Patent 2,226,770 or U.S. Patent 3,674,499 may also be carried out so as to curtail the amount of silver of the photosensitive materials.
  • a coupler (M-35) according to the present invention 10 g of a coupler (M-35) according to the present invention, 20 g of a high boiling point coupler solvent (S-1) and 40 ml 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 ml 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 ⁇ m.
  • 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 of the compositions of the layers.
  • the numerical figures show the amounts of solutions coated (g/m 2 ).
  • Silver halide emulsions are given in the conversion amounts of silver.
  • Polyethylene-laminated paper (polyethylene on the first layer side contained a white pigment (Ti0 2 ) and a bluish dye.)
  • 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.
  • the above-mentioned photosensitive materials were exposed to light through an optical wedge and then processed by the following steps.
  • blue-sensitive layer and the red-sensitive layer can obtain the same effect as 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.
  • composition of each processing salt is given as follows:

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (3)

1. Farbfotographisches Silberhalogenidmaterial, welches ein lipophiles Feinkorn umfaßt, das in mindestens einer hydrophilen Kolloidschicht dispergiert ist, die auf einem Träger gebildet ist, enthaltend mindestens eine Verbindung, dargestellt durch die Formel (I)
Figure imgb0223
worin R1 eine aliphatische, aromatische oder heterocyclische Gruppe mit 8 oder mehr Kohlenstoffatomen darstellt; M1 ein Wasserstoffatom oder ein anorganisches oder organisches salzbildendes Kation; eine Schutzgruppe, die mit Alkali hydrolysiert wird, dargestellt durch die folgenden Formeln
Figure imgb0224
darstellt, worin jedes R3 und R3', die gleich oder verschieden sein können, ein Wasserstoffatom, eine Acylgruppe oder eine Sulfonylgruppe darstellt, jedes R4 und R5, die gleich oder verschieden sein können, ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe darstellt oder R4 und R5 eine 4- bis 7-gliedrige Ringstruktur bilden können;
dadurch gekennzeichnet, daß das Korn weiterhin mindestens eine Verbindung, dargestellt durch die Formel (11)
Figure imgb0225
enthält, worin R2 eine aliphatische, aromatische oder heterocyclische Gruppe mit 8 oder mehr Kohlenstoffatomen darstellt und M2 ein Wasserstoffatom oder ein anorganisches oder organisches salzbildendes Kation darstellt;
mit der Maßgabe, daß die Verbindung der Formel (II) nicht Natriumdodecylbenzolsulfonat ist.
2. Farbfotographisches Silberhalogenidmaterial nach Anspruch 1, worin jedes R1 und R2 in den Formeln (I) und (II) eine aromatische Gruppe mit 10 oder mehr Kohlenstoffatomen darstellt.
3. Farbfotographisches Silberhalogenidmaterial nach Anspruch 1 oder 2, worin R1 und R2 in den Formeln (I) und (II) gleich sind.
EP88113968A 1987-08-28 1988-08-26 Farbempfindliche Silberhalogenidmaterialien Expired - Lifetime EP0305926B1 (de)

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JP214681/87 1987-08-28
JP62214681A JPH07109500B2 (ja) 1987-08-28 1987-08-28 ハロゲン化銀カラ−写真感光材料

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US5043256A (en) * 1988-09-27 1991-08-27 Fuji Photo Film Co., Ltd. Color photographic material
US5089380A (en) * 1989-10-02 1992-02-18 Eastman Kodak Company Methods of preparation of precipitated coupler dispersions with increased photographic activity
DE69300583T2 (de) * 1992-05-29 1996-05-15 Eastman Kodak Co Farbphotographische Materialien und Verfahren mit stabilisierten Silberchloridemulsionen.
US5443947A (en) * 1993-11-30 1995-08-22 Eastman Kodak Company Heat stabilized silver chloride photographic emulsions containing thiosulfonate/sulfinate compounds
EP0655643A1 (de) * 1993-11-30 1995-05-31 Eastman Kodak Company Wärmestabilisierte photographische Silberchloridemulsionen, enthaltend Schwefeldonotoren und Sulfinatverbindungen
US5601970A (en) * 1995-01-03 1997-02-11 Eastman Kodak Company Photographic elements exhibiting improved stability
WO2024035712A1 (en) * 2022-08-08 2024-02-15 Ohio State Innovation Foundation Jigs and related methods for guiding a cutting instrument for controlled surgical cutting of a body portion of a patient

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FR1524760A (fr) 1967-05-29 1968-05-10 Wolfen Filmfab Veb Matériel multicouche pour photographie en couleurs et son procédé de fabrication
BE705617A (de) * 1966-11-30 1968-03-01
DE1572264A1 (de) 1966-12-06 1970-03-05 Wolfen Filmfab Veb Farbenfotografisches Mehrschichtenmaterial und Verfahren zu seiner Herstellung
JPS5936733B2 (ja) * 1976-08-11 1984-09-05 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPS6045413B2 (ja) * 1976-08-11 1985-10-09 富士写真フイルム株式会社 熱現像感光材料
JPS5817946B2 (ja) * 1979-11-06 1983-04-11 コニカ株式会社 ハロゲン化銀写真感光材料
JPS5975249A (ja) * 1982-10-22 1984-04-27 Fuji Photo Film Co Ltd ハロゲン化銀カラ−写真感光材料
JPS6142652A (ja) * 1984-08-07 1986-03-01 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS6289038A (ja) * 1985-10-15 1987-04-23 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤
JPH0625861B2 (ja) * 1985-12-17 1994-04-06 富士写真フイルム株式会社 ハロゲン化銀カラ−写真感光材料

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DE3879816D1 (de) 1993-05-06

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