EP0930534A1 - Procédé de formation d'une image, noir et blanc - Google Patents

Procédé de formation d'une image, noir et blanc Download PDF

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Publication number
EP0930534A1
EP0930534A1 EP99300370A EP99300370A EP0930534A1 EP 0930534 A1 EP0930534 A1 EP 0930534A1 EP 99300370 A EP99300370 A EP 99300370A EP 99300370 A EP99300370 A EP 99300370A EP 0930534 A1 EP0930534 A1 EP 0930534A1
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EP
European Patent Office
Prior art keywords
processing
silver halide
solution
sensitive material
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP99300370A
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German (de)
English (en)
Inventor
Hirohide Ito
Sachiko Hirano
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP744298A external-priority patent/JPH11202455A/ja
Priority claimed from JP1125098A external-priority patent/JPH11212220A/ja
Priority claimed from JP10014192A external-priority patent/JPH11212224A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0930534A1 publication Critical patent/EP0930534A1/fr
Withdrawn legal-status Critical Current

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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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/42—Developers or their precursors
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/02—Sensitometric processes, e.g. determining sensitivity, colour sensitivity, gradation, graininess, density; Making sensitometric wedges
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/261—Non-bath processes, e.g. using pastes, webs, viscous compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/061—Hydrazine compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/067—Additives for high contrast images, other than hydrazine compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
    • G03C1/83—Organic dyestuffs therefor
    • G03C1/832—Methine or polymethine dyes
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C2005/3007—Ascorbic acid
    • 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
    • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
    • G03C2007/3025—Silver content
    • 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
    • G03C2200/00—Details
    • G03C2200/26—Gamma
    • 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
    • G03C2200/00—Details
    • G03C2200/39—Laser exposure
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/04—Photo-taking processes
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • 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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

  • This invention relates to a processing method of a black-white silver halide photographic light-sensitive material.
  • the silver halide photographic light-sensitive material is processed by immersing it in processing solution which is accumulated in processing tank in a predetermined time.
  • processing in processing tank there have been problems such that the activity of a fresh processing solution is deferent from that of a running processing solution or change of composition of processing solution occurs by distillation and air-oxidation during accumulating processing solution in processing tank.
  • it is widely employed to replenish a replenishing solution.
  • the purpose of replenishing a replenishing solution is to dilute a compound which leach out of the light-sensitive material, adjust an amount of distillation and compensate a consumed component.
  • Another method is so-called monobath process by which development and fix is performed in a processing solution.
  • the monobath processing has advantages to diminish a solution, compact an automatic processor and lessen preparing the processing solution, on the other hand, in forming black-white image with monobath processing, reproducibility of fine dot which is required in the light-sensitive for the graphic art is remarkably inferior and lowering of sensitivity is significant. Therefore, since there exist big problems in monobath processing as mentioned above to be solved.
  • an replenishment amount of the processing solution was not more than 350 ml per 1 m 2 of the light-sensitive material, however, recently it is necessary to process the light-sensitive material with the replenishment amount of the processing solution was not more than 250 ml per 1 m 2 of the light-sensitive material
  • the first object of the invention is to provide the image forming method for the silver halide photographic light-sensitive material, wherein the problems such that the activity of a fresh processing solution is deferent from that of a running processing solution and change of composition of processing solution occurs by distillation and air-oxidation during accumulating processing solution in processing tank never occur.
  • the second object of the invention is to provide the processing method for the silver halide photographic light-sensitive material, wherein in the light-sensitive photographic material having high contrast image whose ⁇ is not less than 10, the problem of non-uniformity of processed light-sensitive material never occurs.
  • the third object of the invention is to provide the developer for the silver halide photographic light-sensitive material which is used in said image forming method.
  • the fourth object of the invention is to provide the processing way in which the processed image has an excellent discrimination between high density and minimum density and an excellent image stability with desirable sharpness in a short time.
  • the fifth object of the invention is to provide the processing method which is excellent from the viewpoint of working environment.
  • the sixth object of the invention is to provide the image forming method by which the processed silver halide photographic material with high sensitivity, high ⁇ and no black spot is obtained.
  • the silver halide emulsion layer preferably contains at least one compound selected from transition metals of VI group to X group in a periodic table.
  • sexidentate metal complex represented by the following formula is preferred.
  • M represents a transition metal selected from the elements of VI group to X group in a periodic table
  • L represents a ligand
  • m is 0, -1, -2, or -3.
  • the ligand represented by L are nitrosyl, thionitorosyl, halogen (fluoride, chloride, bromide and iodide), cyanide, cyanate, thicyanate, selenocyanate, tellurocyanate azido and aquo.
  • the aquo preferably occupies one or two ligand(s).
  • L may be the same or different.
  • M are rhodium (Rh), ruthenium (Ru), rhenium (Re), osmium (Os) and iridium (Ir).
  • the added amount of these metal complexes is 10 -8 to 10 -3 mol per a mol of silver halide, preferably 10 -8 to 10 -6 mol.
  • the exemplified compounds are cited hydrazine derivatives, 5 or 6-membered nitrogen containing heterocyclic compounds, and tetrazolium compounds, and these compounds are preferably used in combination with nucleation accelerating compounds.
  • the organic contrast accelerating agents are preferably contained in an adjacent layer to a silver halide emulsion layer.
  • A represents an aryl group or a heterocycle containing therein a sulfur atom or oxygen atom
  • a 1 or A 2 both represent hydrogen atoms, or one of A 1 and A 2 represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group
  • R represents a hydrogen atom, or an alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group or oxycarbonyl group, each of which may be substituted; and
  • the compound represented by the above-mentioned general formula (H) is preferable and the compound represented by the following general formula (Ha) is particularly preferable.
  • R 1 represents a substituted or unsubstituted aliphatic group, for example, octyl group, decyl group, etc.; a substituted or unsubstituted aromatic group, for example, phenyl group, 2-hydroxylphenyl group, chlorophenyl group, etc.; or a substituted or unsubstituted heterocyclic group, for example, a pyridyl group, a thienyl group, a furyl group, etc.; and these groups may be substituted by an appropriate substituent. Further, it is also preferable that R 1 contains at least one ballast group or a silver halide adsorption-accelerating group.
  • ballast groups which are commonly used in the immobile photographic additives such as couplers are preferable, and for such ballast groups, for example, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, a phenyl group, a phenoxy group, an alkylphenoxy group, etc., which are relatively photographically inert consisting of carbon atoms of not less than 8, are cited.
  • the silver halide adsorption-accelerating agent includes, for example, a thiourea group, a thiourethane group, a mercapto group, a thioether group, a thione group, a heterocyclic group, a thioamide heterocyclic group, mercapto heterocyclic group, or those adsorbing groups disclosed in Japanese Patent O.P.I. Publication No.64-90439(1989), etc.
  • X represents a group which is capable of being a substituent on a phenyl group
  • m represents an integer of zero through four, provided when m is two or more, X may be the same or different.
  • a 3 and A 4 independently have the same definition as A 1 and A 2 in the formula (H) respectively, it is preferable that both A 3 and A 4 are hydrogen.
  • G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and carbonyl group is preferable as G.
  • R 2 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkoxy group, a hydroxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group and a substituted or unsubstituted oxy carbonyl group.
  • R 2 s are -COOR 1 and - CON(R 4 )(R 5 ) group.
  • R 3 represents an alkinyl group or a saturated heterocyclic group;
  • R 4 represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
  • R 5 represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted saturated heterocyclic group, a hydroxy group or a substituted or unsubstituted alkoxy group.
  • the hydrazine derivatives used in the present invention can be synthesized according to the conventionally known methods in the art. For example, they may be synthesized according to the method disclosed on column 59 through 80 in the United States Patent No.5,229,248.
  • the hydrazine derivatives used in the present invention can be added in any layer of photographic composition layers of the silver halide emulsion layer side. Preferably, it is added in at least two layers of an emulsion layer and/or it's adjoining hydrophilic colloidal layer.
  • the adding amount of the hydrazine derivative is usually within the range of 10 -6 to 10 -1 moles, preferably 10 -5 to 10 -2 moles, per mole of silver halide even though the optimum amount is varied depending on the diameter of the silver halide grain, halide composition, and the degree of chemical sensitization of silver halide grain, and the kind of stabilizing agent.
  • a molar ratio of the total amount of the hydrazine compound contained in the first silver halide emulsion layer and/or hydrophilic colloidal layer(s) closer to the support than the first emulsion layer to that contained in the second silver halide emulsion layer and/or hydrophilic colloidal layer(s) farther from the support than the first emulsion layer is 0.2 - 0.8, preferably, 0.4 to 0.6.
  • the hydrazine derivative can be used singly or in combination of two kinds or more.
  • the hydrazine derivatives according to the invention is preferably contained in the silver halide emulsion in the form of solid dispersion particle from the viewpoint of the stability of the light-sensitive material.
  • dispersion methods the following two methods are recommended,
  • the average particle diameter of the hydrazine derivative dispersion obtained by the above mentioned methods is generally 0.05 to 1.5 ⁇ m, preferably 0.1 to 1.0 ⁇ m.
  • a stabilizer or an auxiliary dispersion agent is used.
  • a surfactant or a hydrophilic colloid is cited.
  • anionic surfactant known anionic surfactant, cationic surfactant, nonionic surfactant, betainoic surfactant and fluoride containing surfactant can be used.
  • anionic surfactants are cited alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfuric ester, alkyl phosphoric ester, N-acyl-N-alkyl taurine, sulfosuccinic acid ester, sulfoalkylpolyoxyethylene alkylphenyl ether and polyoxyethylenealkyl phosphoric ester.
  • All these compounds mentioned above include acid groups such as carboxy group, sulfo group, phospho group, sulfuric ester group and phosphoric ester group.
  • cation surfactants are cited alkylamine salt derivative, aliphatic or aromatic quaternary ammonium salt derivative, heterocyclic quaternary ammonium derivatives such as pyridinium and imidazolium and phosphonium or sulfonium salt containing aliphatic group or heterocyclic ring.
  • the examples of non-ionic surfactants are cited steroid saponin, alkyleneoxide derivative, glycidol derivative, ester derived from polyhydric alcohol and fatty acid, and alkyl ester of sugar derivative.
  • hydrophilic colloids known water soluble polymer, for example, polyethylene glycohol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacryl amide, polystyrene sulfonate, gelatin, gelatin derivatives (phthalated gelatin, phenylcarbamoylated gelatin), cellulose derivatives(cellulose ether, cellulose ester), starch, gum arabi, pluran, dextran, dextrin or natural high molecular compound etc.
  • water soluble polymer for example, polyethylene glycohol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacryl amide, polystyrene sulfonate, gelatin, gelatin derivatives (phthalated gelatin, phenylcarbamoylated gelatin), cellulose derivatives(cellulose ether, cellulose ester), starch, gum arabi, pluran, dextran, dextrin or natural high molecular compound etc.
  • An emulsified dispersion of the hydrazine derivative in a high boiling solvent is preferably used from the viewpoint of the stability of the light-sensitive material.
  • the similar method for dispersing an oil soluble coupler or an oil soluble ultra violet absorbing agent etc. can be employed.
  • the hydrazine derivative is dissolved in the high boiling solvent optionally together with a low boiling solvent, thereafter thus obtained solution is mixed with a gelatin aqueous solution containing surfactant, then the mixture is dispersed by colloid mill etc.
  • the examples of the high boiling solvents are carboxylic acid ester, phosphoric acid ester, carboxylic acid amide and hydrocarbon etc. The exemplified high boiling solvents are shown below.
  • the surface pH of the silver halide light-sensitive material is preferably not more than 6.
  • the surface pH is measured by dropping 0.5 ml of the aqueous solution whose concentration and composition are each the same as those of the comparative electrode interior solution (in the case of GS-5013F, KCl of 3.3 mol/l) onto 1 cm 2 of the surface of the light-sensitive material, then after leaving it for 5 min. under 80% RH, the pH is measured using silver chloride electrode(AgCl/KCl) as a standard electrode, and contacting a unit of plate-like glass electrode (plate-like complex electrode) with the surface to be measured after 5 min.
  • An example of the plate-like complex electrode is GS-5013F produced Toadenpakogyo Co., Ltd.
  • a method by adding acid a method by applying volatile alkali while drying the film, and a method by applying the compound which can release acid by reaction after drying the film, can be employed.
  • the hydrazine derivative according to the invention may be contained in an optional layer of the silver halide light-sensitive material, from the viewpoint of the stability of the light-sensitive material, it is preferable that it is contained in a layer other than a silver halide emulsion layer.
  • a 1 , A 2 , A 3 , A 4 or A 5 represent non-metal atoms to complete 5 to 6 membered nitrogen containing heterocyclic ring, and said heterocyclic ring may contain oxygen atom, nitrogen atom and sulfur atom, and said heterocyclic ring may be condensed with benzene ring.
  • the 5 to 6 membered nitrogen containing heterocyclic ring composed of A 1 , A 2 , A 3 , A 4 or A 5 may be substituted by substituents.
  • the examples of substituents are an alkyl group, an aryl group, an aralkyl group.
  • pyridine As the 5 to 6 membered nitrogen containing heterocyclic ring composed of A 1 , A 2 , A 3 , A 4 or A 5 is cited pyridine, imidazole, thiazole, oxazole, pyrazine and pyrimidine, and preferable one is pyridine.
  • Bp represents divalent linking group.
  • the divalent linking group is cited alkylene, arylene, alkenylene, -SO 2 -, -SO-, -O-, -S-, -CO-, and -N(R 6 )-(R 6 represent an alkyl group, an aryl group and a hydrogen atom), and these divalent linking group can be used singly or in combination of these groups arbitrarily selected.
  • Preferable Bp are alkylene, alkenylene and alkyleneoxy. m is 0 or 1.
  • R 1 , R 2 and R 5 each represents a saturated or an unsaturated alkyl group or aryl group having 1 to 20 carbon atoms, and these groups may be substituted by the same substituents as cited for A 1 , A 2 , A 3 , A 4 or A 5 .
  • R 1 , R 2 and R 5 are the alkyl group having 4 to 10 carbon atoms or the substituted or unsubstituted aryl group, and more preferable ones are the substituted or unsubstituted phenyl group, the unsaturated alkyl group or the alkyl group substituted by phenyl group.
  • X p - represents a counter ion necessary to neutralize whole electric charge of the molecules, for example, chloride ion, bromide ion, iodide ion, nitric ion, sulfuric ion, p-toluenesulfonate and oxalate
  • n p represents number of counter ion necessary to neutralize whole electric charge of the molecules.
  • n p is 0.
  • Added amount of the compound represented by the formula (Pa), (Pb) or (Pc) is 1 x 10 -6 mol to 1 x 10 -1 mol per a mol silver, preferably 1 x 10 -5 mol to 5 x 10 -2 mol.
  • the compound represented by the formulae (Pa), (Pb) or (Pc) according to the invention can be used by dissolving them in an appropriate solvent, for example, alcohol (methyl alcohol, ethyl alcohol, propyl alcohol, alcohol containing fluorine atom in it's molecule), ketone (acetone, methylethylketone), dimethylformamide, dimethyl sulfoxide and methyl cellosolve.
  • an appropriate solvent for example, alcohol (methyl alcohol, ethyl alcohol, propyl alcohol, alcohol containing fluorine atom in it's molecule), ketone (acetone, methylethylketone), dimethylformamide, dimethyl sulfoxide and methyl cellosolve.
  • the compound represented by the formulae (Pa), (Pb) or (Pc) can be used by known emulsification dispersion method, in which these compounds are dissolved in oil such as dibutylphthalate, tricresylphosphate, glyceryltriacetate or diethylphthalate together with auxiliary solvent such as ethylacetate and cyclohexanone, thereafter the mixture is mechanically dispersed to obtain the emulsified dispersion.
  • the compound represented by the formulae (Pa), (Pb) or (Pc) can be also used by known solid dispersion method, in which powder of these compounds are dispersed by ball mill, colloid mill or ultrasonic homogenizer.
  • nucleation accelerating agent such as hydrazine derivative, amine derivative, onium derivative, disulfido derivative and hydroxyl amine derivative in combination with the compound represented by the formula (Pa), (Pb) or (Pc).
  • nucleation accelerating agents the exemplified compounds (2-1) - (2-20) and (3-1) - (3-6) described in JP-A No. 8-314066 and JP-A No. 6-258751, the compound represented by the formula I described in JP-A No. 7-104420, the compound described in JP-A No. 2-103536, page 17 - 18, and thiosulfonic acid described in JP-A No. 1-237538, are preferably used. More preferable one is the compound described in JP-A No. 8-314066.
  • nucleation accelerating agent For the purpose of accelerating the high contrast by means of hydrazine compound or 5,6 membered nitrogen containing heterocyclic derivative effectively, it is preferable to use a nucleation accelerating agent.
  • the nucleation accelerating agent represented by the following formula (Na) or (Nb) is preferably used.
  • R 31 , R 32 and R 33 represent a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkinyl group, an aryl group and a substituted aryl group, R 31 , R 32 and R 33 may form a ring.
  • one is an aliphatic tertiary amine compound.
  • the compound having a nondiffusing group or an adsorption group onto silver halide in a molecule are preferable. In order to have a nondiffusing property, a compound having molecular weight of not less than 100 is preferable, and one having molecular weight of not less than 300 is more preferable.
  • adsorption-promoting group there are given a heterocyclic ring, a mercapto group, a thioether group, a thion group and a thiourea group.
  • An especially preferable one as the formula (Na) is a compound having at least one thioether group in a molecule as a adsorption-promoting group onto silver halide.
  • nucleation accelerating agent Na
  • Ar represents a substituted or unsubstituted aromatic group or heterocyclic group.
  • R 34 represents a hydrogen atom, an alkyl group, an alkinyl group or an aryl group, and Ar and R 34 may be coupled with a coupling group to form a ring.
  • These compounds are preferable when they contain a nondiffusing group or a silver halide adsorption group in a molecule.
  • a preferable molecular weight to cause a preferable nondiffusing property to be contained is 120 or more, and 300 or more is especially preferable.
  • As a silver halide adsorption group is cited similar silver halide adsorption group cited for the compound represented by the formula (H).
  • Exemplary examples of other preferable nucleation accelerating compound are those of (2-1) - (2-20) described in JP-A No. 6-258751, and those of (3-1) - (3-6) described in JP-A No. 6-258751, the onium salt compound described in JP-A No. 7-270957, the compound represented by the formula I described in 7-104420, the compound described in JP-A No. 2-103536, page 17 - 18, and thiosulfonic acid described in JP-A No. 1-237538, are preferably used.
  • a nucleation accelerating agent used in the invention can be used for any layer provided that the layer is a photographic component layer provided on the silver halide emulsion layer side, and it is preferable to use it for a silver halide emulsion layer or for a layer adjoining the silver halide emulsion layer.
  • an added amount though an optimum amount varies depending on a grain size of a silver halide grain, halogen composition, a degree of chemical sensitization and a kind of an inhibiting agent, an amount ranging from 10 -6 to 10 -1 mol per mol of silver halide is generally preferable, and a range of 10 -5 to 10 -2 mol is especially preferable.
  • a tetrazolium compound as an organic high contrast accelerating agent, as a tetrazolium compound the compound represented by the following general formula (T) is preferable.
  • Each of R 1 , R 2 and R 3 substituted on the phenyl groups of the compound represented by the general formula (T) preferably represents a hydrogen atom or a group, of which Hammett's ⁇ -value showing degree of electron withdrawal is in the negative.
  • ⁇ values of the phenyl substituents are disclosed in lots of reference books. For example, a report by C.Hansch in "The Journal of Medical Chemistry", vol.20, on page 304(1977), etc. can be mentioned.
  • n 1 or 2
  • anions represented by X n- T for example, halide ions such as chloride ion, bromide ion, iodide ion, etc.; acid radicals of inorganic acids such as nitric acid, sulfric acid, perchloric acid, etc.; acid radicals of organic acids such as sulfonic acid, carboxylic acid, etc.; anionic surface active agents, specifically including lower alkyl benzenesulfonic acid anions such as p-toluenesulfonic anion, etc.; higher alkylbenzene sulfonic acid anions such as p-dodecyl benzenesulfonic acid anion, etc.; higher alkyl sulfate anions such as lauryl sulfate anion, etc.; boric acid-type anions such as tetraphenyl borone, etc.; dialkylsulfo succinate anions such as
  • the tetrazolium compound represented by the formula (T) may be used singly or in combination of not less than two kinds of them in any ratio.
  • a and A' may be either the same with or different from each other, and each of them represents an acidic nucleus
  • B represents a basic nucleus
  • Q represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group
  • B' represents a substituted or unsubstituted heterocyclic group
  • X and Y may be either the same with or different from each other and each of them represents an electron withdrawing group
  • each of L 1 , L 2 and L 3 represents a substituted or unsubstituted methine group.
  • the symbol m represents 0 or 1
  • n represents 0, 1 or 2
  • p represents 0 or 1.
  • each of dyes represented by the formulae (1) - (6) preferably contains in a molecule at least one group selected from the group of a carboxy group, a sulfonamide group and a sulfamoyl group.
  • Acidic nuclei represented by A and A' in the formulae (1), (2) and (3) preferably include 5-pyrazolone, barbituric acid, thiobarbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isooxazolone, indanedione, pyrazolidinedione, oxazolidinedione, hydroxypyridone and pyrazolopyridone.
  • Basic nucleuses represented by B in Formulas (3) and (5) preferably include pyridine, quinolin, oxazole, benzoxazole, naphthoxazole, thiazole, benzthiazole, naphthothiazole, indolenin, pyrole and indole.
  • aryl group represented by Q in the above-mentioned formulae (1) - (4) there may be given a phenyl group and a naphthyl group or the like, for example.
  • a heterocyclic group represented by Q there may be given pyridine, quinoline, isoquinoline, pyrole, pyrazole, imidazole, indole, furyl and thienyl residues.
  • Aforesaid aryl group and heterocyclic group include those having substituents which are represented by, for example, an alkyl group, a cycloalkyl group, an aryl group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a cyano group, a hydroxy group, a mercapto group, an amino group, an alkoxy group, an aryloxy group, an acyl group, a carbamoyl group, an acylamino group, an ureido group, a sulfamoyl group and a sulfonamide group, and two or more kinds of these substituents may be combined.
  • Preferable one include an alkyl group having 1-6 carbon atoms (e.g., a methyl group, an ethyl group, a butyl group, a 2-hydroxyethyl group, etc.), a hydroxyl group, a halogen atom (e.g., a fluorine atom, a chlorine atom, etc.), an alkoxy group (e.g., a methoxy group, an ethoxy group, a methylenedioxy group, a 2-hydroxyethoxy group, an n-buthoxy group, etc.), a substituted amino group (e.g., a dimethylamino group, a diethylamino group, a di(n-butyl)amino group, an N-ethyl-N-hydroxyethylamino group, an N-ethyl-N-methanesulfonamido-ethylamino group, a morpholino group, a pipe
  • Electron withdrawing groups represented by X and Y in the formulae (4) and (5) may be either the same with or different from each other.
  • the preferable groups include a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group.
  • Heterocyclic rings represented by B' in the formula (6) include, for example, pyridine, pyridazine, quinolin, pyrole, pyrazole, imidazole and indole.
  • Methine groups represented by L 1 , L 2 and L 3 in Formulas (1) - (5) include those having a substituent, and the substituent includes, for example, an alkyl group having 1-6 carbon atoms (e.g., methyl, ethyl, propyl, isobutyl, etc.), an aryl group (e.g., phenyl, p-tolyl, p-chlorophenyl, etc.), an alkoxy group having 1-4 carbon atoms (e.g., a methoxy group, an ethoxy group, etc.), an aryloxy group (e.g., a phenyl group, etc.), an aralkyl group (e.g., a benzyl group, a phenethyl group, etc.), a heterocyclic group (e.g., pyridyl, furyl, thienyl, etc.), a substituted amino group (e.g., dimethyla
  • dyes represented by the formulas (1) - (6) those having at least one carboxyl group in a molecule are preferably used, and dyes represented by the formula (1) are more preferable, in which the dyes represented by the formula (1) wherein Q is a furyl group are especially preferable.
  • Solid fine particle dispersion of the invention can be used either singly or in combination of two kinds or more, and they can further be used together with solid fine particle dispersion other than that of the invention. When using in combination of two kinds or more, they can be mixed after being dispersed independently, or they may be dispersed simultaneously.
  • Such surfactant to be used includes an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant, and preferable ones are anionic surfactants such as, for example, alkyl sulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkyl sulfonates, sulfosuccinate, sulfoalkylpolyoxyethylenealkylphenyl ethers, and N-acyl-N-alkyltaurine, and nonionic surfactant such as, for example, saponin, alkylene oxide derivative and alkylester of sugar. Aforesaid anionic surfactants are especially preferable.
  • Exemplary examples of the surfactant are
  • An amount of anionic surfactants and/or nonionic surfactants varies depending on a kind of surfactant or on dispersion conditions of aforesaid dyes, but 0.1 mg - 2000 mg per 1 g of dye is normally preferable, 0.5 mg - 1000 mg is more preferable, and 1 mg - 500 mg is especially preferable.
  • concentration used in a dye dispersion it is preferable to be used so that 0.01 - 50% by weight may be attained, and 0.1 - 30% by weight is more preferable.
  • timing for adding surfactants it is good to add them before the start of dispersion of dyes, and they can also be added to a dye-dispersed solution after completion of dispersion of the dyes, when it is necessary.
  • anionic surfactants and/or nonionic surfactants can be used either independently or in combination of two or more kinds, and further, both surfactants may be combined.
  • hydrophilic colloid used as a binder for a photographic component layer it is possible to add hydrophilic colloid used as a binder for a photographic component layer to solid fine particle dispersed products used in the invention, before the start of dispersion or after completion of dispersion.
  • hydrophilic colloid it is advantageous to use gelatin.
  • gelatin derivatives such as phenylcarbamated gelatin, acylated gelatin or phthalated gelatin, cellulose derivatives such as graft polymer with monomer having an ethylene group capable of being polymerized with gelatin, carboxymethylcellulose, hydroxymethylcellulose and cellulose sulfate, synthesized hydrophilic polymer such as polyvinyl alcohol, partially oxidized polyvinyl acetate, polyacrylicamide, poly-N,N-dimethylacrylicamide, poly-N-vinylpyrrolidone and polymethacrylic acid, agar, acacia, alginic acid, albumin and casein. These can be used in combination of two or more kinds.
  • As an amount of hydrophilic colloid added to solid fine particle dispersed products it is preferable to add so that a percentage by weight of 0.1% - 12% may be attained, and 0.5% - 8% is more preferable.
  • the average particle diameter of a dye in the form of a solid particle dispersion used in the invention is not more than 0.2 ⁇ m, especially preferably 0.05 - 0.15 ⁇ m. With regard to the distribution of the particle diameter, it is preferred that the particle diameter of not more than 0.3 ⁇ m occupies not less than 70% in the term of scattering strength distribution.
  • a method for measuring the particle diameter and the particle diameter distribution of the dye in the form of the solid particle dispersion is carried out by using ELS-800 produced by Otsuka Denshi Co., Ltd.
  • an added amount of the dye in the form of the solid particle dispersion though an optimum amount varies depending on an absorption coefficient of the dye in the form of the solid particle dispersion, an amount of not more than 200 mg/m 2 is preferred, and an amount ranging 5 to 50 mg/m 2 is especially preferable.
  • a preferable density of the dye in the form of the solid particle dispersion is preferably associated with a preferable particle diameter range of the dye in the form of the solid particle dispersion.
  • An absorption optical density of the dye in the form of the solid particle dispersion is 0.05 to 1.0 at the maximum absorption wave length of the silver halide emulsion, preferably 0.1 to 1.0, especially preferably 0.3 to 1.0.
  • hydrophilic colloid layer which is a layer of the dye in the form of the solid particle dispersion and located at the farther position than the silver halide emulsion layer on the silver halide emulsion layer side to a support
  • a hydrophilic colloid layer consisting of gelatin, polyacrylamide, and synthetic polymer such as hydrophilic high molecular compound and latex.
  • a solid fine particle dispersion product of the dye stuff used in the invention is preferably added in a layer locating between a support and an emulsion layer.
  • a maximum density of the dye in a hydrophilic layer coated on the support opposite to the emulsion layer is preferably not more than 0.5, more preferably not more than 0.1, and it is especially preferable that said hydrophilic layer does not substantially contain any dye.
  • Developing agent incorporated in the light-sensitive material is optionally selected from known ones.
  • the developing agent includes a developing agent precursor which releases a developing agent during development.
  • p-phenylenediamines, p-aminophenols, phosphoramidephenols and sulfonamideanilines described in U.S. Patent No. 3,351,286, 3,761,270, 3,764,328, 3,342,599, 3,719,492, Research Disclosure (hereinafter referred to as RD) 12146, 15108, 15127, and JP-A 56-27132, 53-135628, 57-79035, and hydrazones, phenols, sulfonamidephenols, polyhydroxybenzenes, naphthols, hydroxy bisnaphthyls, methylenebisphenols, ascorbic acid derivatives, 1-aryl-3-pyrazolidones and hydrazones, and precursors of these developing agents.
  • RD Research Disclosure
  • Number of carbon atom of the developing agent incorporated in the light-sensitive material of the invention is not more than 20, preferably not more than 15 so that an amount of developing agent is effectively added and it develops the light-sensitive material effectively.
  • These developing agents can be used in combination of two kinds or more, especially combined usage of 1-aryl-3-pyrazolidone derivatives and hydroquinone derivatives is preferable.
  • the incorporate amount of the developing agent is an amount with which not less than 15% silver halide contributing to forming an image is developable, preferably not less than 50% silver halide is developable, especially preferably not less than 100%.
  • the incorporated amount of the developing agent with which the silver halide is developable means that the developing agent theoretically reduces the silver halide with the incorporated amount of the developing agent.
  • These developing agents can be incorporated in the silver halide emulsion layer and other hydrophilic colloidal layers. These developing agents are preferably incorporated in the layers which are coated on the same side as the silver halide emulsion layer to the support, more preferably they are incorporated in the hydrophilic colloidal layers other than the silver halide emulsion layer. They can be incorporated in the optional layers between the support and the silver halide emulsion layer. In cases where the silver halide photographic light-sensitive material contains the developing agent, adding amount of the developing agent is preferably 0.3 to 5.0 g/m 2 .
  • the developing agents according to the invention is preferably contained in the light-sensitive material in solid dispersion form from the viewpoint of the stability of the light-sensitive material.
  • the following two methods are recommended, (i) a method that the developing agents is mixed with an aqueous solution which does not contain substantially an organic solvent such as ethylacetate, methyl alcohol and methylethylketone etc., but contains one or more kinds of stabilizer(s) or pulverizing agent(s), thereafter the organic solvent is removed by evaporation under a reduced pressure, (ii) a method that solid developing agent is crashed with an inorganic pulverizing medium repeatedly in an aqueous solution containing one or more kinds of stabilizer(s) or pulverizing agent(s).
  • bead such as sand, silica ball, stainless steel, silicon carbide, glass, zirconium, zirconium oxide, alumina and titanium.
  • the bead size of these mediums is in the range of 0.25 to 3.0 mm.
  • ball mill media mill, attriter mill, jet mill and vibration mill etc.
  • the average particle diameter of the dispersed product of developing agent obtained by the above mentioned methods is generally 0.05 to 1.5 ⁇ m, preferably 0.1 to 1.0 ⁇ m.
  • a stabilizer or an auxiliary dispersion agent is used.
  • a surfactant or a hydrophilic colloid is cited.
  • the light-sensitive material according to the invention comprises the light-sensitive silver halide.
  • the light-sensitive silver halide known one is available, such as silver chloride, silver bromide, silver iodobromide and silver chloroiodobromide. It is preferable to use the light-sensitive material containing the silver halide containing 60 mol% or more silver chloride. Concretely, silver chlorobromide or silver chloroiodobromide containing 60 mol% or more silver chloride is preferably used.
  • a silver halide grain may either be uniform in terms of halogen composition from its core to surface or be composed of plural layers, each being different in terms of halogen composition from its core to surface. Such silver grain forms a core/shell form or a grain of which halide composition is stepwise or continuously changed.
  • the average grain size of the silver halide is preferably 0.6 ⁇ m or less, and, more preferably 0.5 to 0.05 ⁇ m.
  • the silver halide grain may be mono-dispersed grain of relatively uniform grain distribution or poly-dispersed grain of relatively wide grain distribution.
  • grain size usually refers to as average diameter of the grain, when the grain is of spherical shape or in the form close thereto. In the case when the grain is a cubic shape, it means as average diameter of a sphere when the cube is converted into a sphere having the equivalent volume.
  • method of obtaining the average diameter one can refer to the disclosure on pages 36 - 43, third edition of "The theory of the photographic process" edited by C.E. Mees and T.H.James and published by Mcmillan Co. in 1966.
  • the shape of the silver halide grain there is no limitation as to the shape of the silver halide grain, and any one of tabular, cubic, spheric, tetradeca hedral or octahedral shape can optionally be used.
  • Concerning grain size distribution the narrower, the more preferable.
  • so-called mono-dispersed emulsion in which more than 90% (preferably 95%) of the total number of grains fall in the range ⁇ 40% around the average grain size, is preferable.
  • An emulsion composed of a tabular silver halide grain with ratio of not less than about 5 of a diameter to a thickness is preferred and an emulsion composed of a tabular grain with not less than 90% of silver chloride having (100) face as the major face is preferred.
  • Such the emulsion can be prepared by referring U.S. Patent Nos. 5,264,337, 5,314,798 and 5,320,958.
  • a method for mixing soluble silver halide and soluble halogen salt in the invention may include any of a single-sided mixing method, a simultaneous mixing method a combination thereof. It is also possible to use a method (so-called reverse precipitation method) in which grains are formed under the condition of excessive silver ions. As a type of double-jet methods, it is possible to use a method to keep the pAg constant in a liquid phase in which silver halides are produced, namely the so-called controlled double jet method. Owing to this method, it is possible to obtain a silver halide emulsion in which crystal shapes are regular and grain diameters are almost uniform.
  • the light-sensitive silver halide and the light-sensitive silver halide forming composition used in the light-sensitive material is used in an amount of 0.3 to 3.4 g, preferably 0.9 to 3.0 g per m 2 of the light-sensitive material in term of silver.
  • the silver halide emulsion is preferably subjected to a chemical sensitization.
  • chemical sensitization sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization are known commonly and can also be used singly or in combination of two kinds or more.
  • sulfur sensitizing agent various sulfur compounds such as, for example, thiosulfate, thiourea, rhodanine and polysulfide compounds can be used in addition to sulfur compounds contained in gelatin.
  • selenium sensitizing agent known selenium sensitizing agent is used.
  • These chemical sensitizing agents can be added optionally in course of preparing the silver halide emulsion, and preferably during chemical sensitization.
  • An added amount of these chemical sensitizing agents is 10 -9 to 10 -3 per mol of silver halide, preferably 5 x 10 -6 to 5 x 10 -4 , more preferably 1 x 10 -5 to 2 x 10 -4 .
  • light-sensitive materials used in the invention it is possible to cause light-sensitive materials used in the invention to contain various compounds for the purpose of preventing fog in the course of manufacturing the light-sensitive materials or during storage of photographic processing or stabilizing photographic performances.
  • antifoggant or stabilizer such as azoles, for example, benzthiazolium salt, nitroindazole, nitrobenzimidazole, chlorobenzimdazole, bromobenzimidazole, mercaptothiazole, mercaptobenzthiazole, mercaptobenzimidazole, mercaptothiadiazole, aminotriazole, benztriazole, nitrobenztriazole, mercaptotetrazole (1-phenyl-5-nercaptotetrazole in particular); mercaptopyrimidine, mercaptotriazine; thioketo compound such as, for example, oxazolinethion; azaindene, for example, triazaindene, tetrazainden
  • Gelatin is advantageously used as a binder of a photographic emulsion, but another hydrophilic colloid can be used.
  • the examples of the hydrophilic colloid include gelatin derivatives, grafted gelatins with another polymer, proteins such as albumin or casein, cellulose derivatives such as hydroxycellulose, carboxymethylcellulose or cellulose sulfate, starch, agar, acacia, saccharides such as sodium alginate or starch derivatives and synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyethyleneglycol (molecular weight of not less than 2000) polyacryl amide, polyvinyl imidazole or polyvinyl pyrazole.
  • Gelatin includes limed gelatin, acid processed gelatin, gelatin hydrolysate or enzyme decomposed gelatin.
  • An amount of a binder used in each composing layer is usually preferably 0.05 to 8 g per m 2 of a support, more preferably 0.2 to 5 g, especially preferably 0.2 to 1.5 g.
  • a total amount of a binder used in thermal development light-sensitive material is preferably 1 to 30 g per m 2 of a support, more preferably 2 to 15 g.
  • the photographic emulsion may contain water insoluble or sparingly soluble synthetic polymer in order to improve dimensional stability.
  • the synthetic polymer includes polymers obtained by polymerization of alkyl-(meth)acrylate, alkoxyacryl(meth)acrylate, glycidyl (meth)acrylate, (meth)acryl amide, vinylester such as vinyl acetate, acrylonitrile, olefin, styrene or a combination thereof, or its combination with acrylic acid, methacrylic acid, ⁇ , ⁇ -unsaturated dicarboxylic acid, hydroxyalkyl-(meth) acrylate, sulfoalkyl(meth)acrylate or styrene sulfonic acid.
  • the photographic emulsion or non-light sensitive hydrophilic colloid in the invention may contain inorganic or organic hardeners.
  • the hardeners include chromium salts (chrome alum, chromium acetate), aldehydes (formaldehyde, glyoxal, glutaraldehyde), a N-methylol compound (dimethylolurea, methyloldimethylhydantoin), dioxane derivatives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacroyl-hexahydro-s-triazine, bis(vinylsulfonyl)methylether, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine), mucohalogen acids (mucochloric acid, phenoxymucochloric acid), isooxazoles, starch dialdehyde, 2-chloro-6-hydroxy-triazinyl
  • the plastic supports include polyethylene compound (e.g., polyethylene terephthalate, polyethylene naphthalate), triacetatecompound (e.g., triacetylcellulose), polystyrene (e.g., syndiotacticspolystyrene).
  • polyethylene compound e.g., polyethylene terephthalate, polyethylene naphthalate
  • triacetatecompound e.g., triacetylcellulose
  • polystyrene e.g., syndiotacticspolystyrene
  • Preferable thickness of a support is 50 to 250 ⁇ m, especially preferably 70 to 200 ⁇ m.
  • a hydrophobic binder preferably used in the invention is transparent or semitransparent, generally coloress, and a synthesized resin derived from natural polymer, polymer, copolymer and a medium which can form film, for example, gelatin, acacia, polyvinylalcohol, hydroxyethylcellulose, celluloseacetate, celluloseacetatebutylate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, poly methylmethacrylic acid, polyvinylchloride, polymethacrylic acid, styrene-maleic acid anhydride copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, polyvinylacetal derivative (polyvinylformal, poly vinylbutyral etc.), polyester, polyurethane, phenoxy resin, polychlorovinylidene, polyepoxide derivative, polycarbonate derivative, polyvinylacetate,
  • An organic silver salt can be used in the invention.
  • the organic silver salt is relatively stable to light and can form a silver image in the presence of an exposed light catalyst (photographic silver salt etc.) and a reducing agent at 80 °C or more.
  • the organic silver salt is derived from any organic compound which forms reducible silver salt, especially a silver salt of an organic acid having 10 to 30 carbon atoms, preferably 15 to 28 carbon atoms is preferable.
  • a silver complex of an organic or an inorganic salt of which ligands have total stable constant ranging 4.0 to 10.0 is preferably used.
  • a tungsten lamp, a halogen lamp, a xenon lamp, a mercury lamp, CRT light source, FO-CRT light source, an emission diode and a laser beam (e.g., a gas laser, dye laser, YAG laser and semi-conductor laser etc.) is used either singly or in combination of two kinds or more. Furthermore, combined usage of a semi-conductor laser and SHG element (second high frequent wave emission element) is also employed. Among them a laser beam source is preferably used, and the laser beam source ranging 600 - 850 nm is preferable, 600 - 700 nm is more preferable.
  • the processing process according to the invention wherein a processing solution is supplied on the surface of the silver halide photographic light-sensitive material which is transferred in a gas phase, may be applicable to not only developing process but also optionally fixing process, stabilizing process and washing process.
  • various kinds of coating methods can be employed.
  • a method by supplying the processing solution directly or forming beads from the processing solution supplying outlet such as slit or porous outlet onto the light-sensitive photographic material, and a method by supplying the processing solution onto the light-sensitive photographic material through a gas phase are preferably used.
  • the diameter of pore is preferably 0.03 to 1.0 mm, more preferably 0.05 to 0.5 mm.
  • the interval between pores is preferably 0.1 to 1.0 mm, more preferably 0.15 to 0.5 mm.
  • the slit width is preferably 0.03 to 1.0 mm. Too narrow slit width is not preferable for uniformity of coating the processing solution and too wide slit width is not preferable because of the occurrence of solution dripping.
  • the slit width is preferably 0.05 to 0.5 mm, more preferably 0.10 to 0.3 mm.
  • the interval between the solution supplying outlet and the light-sensitive photographic material is 0.03 to 10 mm, preferably 0.05 to 5 mm, more preferably 0.1 to 3 mm from the viewpoint of coating uniformity.
  • a method by supplying the processing solution through a gas phase is cited a method by coating the processing solution onto the light-sensitive photographic material through a gas phase such as curtain coater.
  • the processing solution supplying method by spraying through a gaseous phase.
  • a method by spraying the solution actively by generating a pressure like the similar structure to ink-jet head portion of ink-jet printer this is called ink-jet method in the invention
  • a method by spraying the solution utilizing a liquid pressure like a spray bar are cited.
  • spraying the solution actively a method by spraying the solution utilizing the vibration of piezo electricity element or a method by spraying the solution utilizing bumping.
  • the method by supplying the processing solution by spraying the solution actively utilizing the similar structure to ink-jet head portion of ink-jet printer is especially preferably used, because it is easy to control the supplied amount of the processing solution and to select the processing position of the light-sensitive photographic material.
  • the processing solution supplying means a method by supplying the processing solution through a gaseous phase onto the light-sensitive photographic material from a stripe-like head, or a plane-like head, or a dot-like head etc. is employed.
  • the processing solution through a gaseous phase onto the light-sensitive photographic material is employed on condition that the position relation between the light-sensitive photographic material and the supplying head being fixed. Shifting the position relation between the light-sensitive photographic material and the supplying head, a method by supplying the processing solution through a gaseous phase onto the light-sensitive photographic material is preferable because it is possible to supply sufficient amount of the processing solution onto the light-sensitive photographic material using the small supplying head. In case of using the stripe-like supplying head, the supplying head may move.
  • moving the light-sensitive photographic material in the direction other than parallel to the stripe-like supplying head is preferable.
  • moving the light-sensitive photographic material in the vertical direction to the stripe-like supplying head is preferable to maintain the processing time constant.
  • spraying means shifting the position relation between the light-sensitive photographic material and the supplying head, spraying the processing solution through a gaseous phase onto the light-sensitive photographic material from the supplying head will be explained in detail below.
  • the number of times per sec. of spraying the processing solution through a gaseous phase onto the light-sensitive photographic material is preferably not less than 1, especially preferably not less than 10.
  • the number of times per sec. of spraying the processing solution through a gaseous phase onto the light-sensitive photographic material is preferably not more than 1 x 10 6 , especially preferably not more than 1 x 10 5 .
  • the form of the supplying outlet takes any of circle, square, ellipse etc.
  • the area of each form of the supplying outlet is preferably 1 x 10 -11 m 2 . especially preferably 1 x 10 -10 m 2 to avoid choking caused by drying up. Further, the area of each form of the supplying outlet is preferably 1 x 10 -11 m 2 .
  • the average interval between the margin of the outlet and the margin of the nearest outlet is preferably not less than 5 x 10 -6 m from the viewpoint of strength, and to supply sufficient amount of the processing solution, the average interval between the margin of the outlet and the margin of the nearest outlet is preferably not more than 1 x 10 -3 m.
  • the interval between the solution supplying outlet and the emulsion surface of the light-sensitive photographic material is preferably not less than 50 ⁇ m (more preferably not less than 1 mm) to control this interval easily, especially preferably not more than 10 mm (more preferably not more than 5 mm).
  • an used amount of the processing solution is preferably less provided from the viewpoint of waste and handling of the processing solution.
  • 1 to 200 ml per m 2 of the light-sensitive material is preferable, 10 to 150 ml is more preferable, further 15 to 110 ml is more preferable, especially 20 to 80 ml is most preferable.
  • UV and visible density are each not more than 0.3, preferably not more than 0.2, more preferably not more than 0.1.
  • the visible spectra absorption does no have preferably specified color. That the UV and visible density of whole layers on the second surface side is not more than 0.3 does not mean the density of each layer on the second surface side, but means that the total UV and visible density of throughout whole layers on the second surface side is not more than 0.3.
  • water is preferably supplied from the viewpoint of rapidity of the processing.
  • water and processing solution cab be contacted with both surface of the light-sensitive photographic material.
  • water tank may be provided or may be not provided.
  • any of known method and technique is employed.
  • the amount of supplied water is preferably 0.5 to 100 g per m 2 of the light-sensitive photographic material, more preferably 1 to 40 g.
  • the supplied water can be heated to optional temperature. In this case, absorbed amount of water in the opposite layer to the layer comprising the light-sensitive silver halide emulsion is less than that in the layer comprising the light-sensitive silver halide emulsion.
  • the absorbed amount of water in the opposite layer to the layer comprising the light-sensitive silver halide emulsion is preferably not more than 2 g per m 2 of the light-sensitive photographic material, more preferably not more than 1 g.
  • the absorbed amount of water mentioned above can be attained by the technique described in JP-A No. 9-90584 and other technique known to the art. That the absorbed amount of water in whole layers on the second surface side is not more than 2 g does not mean the absorbed amount of water of each layer on the second surface side, but means that the total absorbed amount of water of throughout whole layers on the second surface side is not more than 2 g.
  • the light-sensitive photographic material supplied and coated with the processing solution is preferably heated. Heating may begin, before the processing solution being supplied, at the same time the processing solution being supplied, and after the processing solution being supplied, but heating preferably begins before the processing solution being supplied. Heating may be carried out at constant temperature continuously during processing or at variable temperature with the passage of time.
  • the temperature of the light-sensitive material is 25 °C to 150 °C, preferably 25 °C to 50 °C, more preferably 35 °C to 46 °C. Heating is carried out so that the temperature before 30% of total processing time after beginning of processing is not more than 40 °C and the temperature after 70% of total processing time is not less than 40 °C.
  • heating is carried out so that the temperature before 40% of total processing time after processing begins is not more than 40 °C and the temperature after 60% of total processing time is not less than 40 °C.
  • beginning of processing means the time when the processing solution (except water supplied prior to the development) was supplied and the term “total processing time” in the invention means time of throughout whole processes after the beginning of processing until completion of drying.
  • heating means to heat the light-sensitive photographic material is cited a conductive heating method for contacting the light-sensitive photographic material with heat dram and heat belt, a convective heating method for heating the light-sensitive photographic material by heat convection generated by dryer etc., and a emissive heating method for heating the light-sensitive photographic material by emission of infra redray and high frequent electromagnetic waves.
  • Heating means is used in combination with transfer means for the silver halide photographic light-sensitive material and detecting means for the silver halide photographic light-sensitive material.
  • the light-sensitive photographic material is transferred by the transfer means and the existence of the light-sensitive photographic material is detected by the detecting means.
  • the existence of the light-sensitive photographic material is detected by the detecting means, heating the light-sensitive photographic material begins and the light-sensitive photographic material is heated in predetermined time.
  • the surface tension of the solution is preferably 40 dyn/cm, especially preferably 30 dyn/cm.
  • various kinds of surfactants were used.
  • the surfactant containing fluorine atom(s) in it's molecule is more preferable.
  • the method according to the present invention is especially effective in forming high contrast image whose ⁇ is 10 to 100 using later mentioned high contrast increasing agent.
  • the light-sensitive material prior to processing the light-sensitive material, it is preferable to maintain the light-sensitive material temporarily on a carrier having gum-containing layer from the viewpoint of planeness, dimensional stability and stability.
  • the gum-containing layer has a gum and is a slippage preventing layer utilizing the effect of preventing slippage by gum.
  • a natural gum is available, but a synthetic gum is preferable.
  • the synthetic gum are cited styrene-butadiene gum, butadiene gum, isoprene gum, chloroprene gum, urethane gum, polysulfide gum, tetrafluoroethylene-propylene gum, acryl gum, epichlorohydrin gum, ethylene-vinylacetate gum, 1,2-polybutadiene gum, heat plasticity elastomer (styrene derivative, olefin derivative, urethane derivative, polyester derivative, polyamide derivative, fluorine derivative etc.), ethylene-propylene copolymer, ethylene-propylene-diene copolymer, nitrile-butadiene gum, butyl gum, fluoride gum, chlorosulfonatedpolyethylene gum, propyleneoxide gum, ethylene-acryl gum, norbonane gum and silicon gum. Especially silicon gum is preferable.
  • a slippage preventing layer In a slippage preventing layer, (a) pasting resin such as rosin, polyterpene, phenol resin, xylene resin, petroleum hydrogencarbonate, (b) plasticizer such as phthalic acid ester, phosphoric ester, chloride parafine, (c) oil such as animal oil, mineral oil can be added to adjust contact with sheet. Further, age resister, stabilizer, filler, coloring agent can be added.
  • resin such as rosin, polyterpene, phenol resin, xylene resin, petroleum hydrogencarbonate
  • plasticizer such as phthalic acid ester, phosphoric ester, chloride parafine
  • oil such as animal oil, mineral oil can be added to adjust contact with sheet. Further, age resister, stabilizer, filler, coloring agent can be added.
  • n is an integer of not less than 2
  • R represents an alkyl group having 1 to 10 carbon atoms, a halogenated alkyl group, a vinyl group or an aryl group.
  • R which consists of methyl group of not less than 60% of R is preferable.
  • Silicon gum usable in the invention is obtained by condensation reaction of silicon based polymer with the following silicon cross-linking agent.
  • R is a synonym of the aforementioned R
  • R' represents an alkylgroup such as methyl group, ethyl group
  • Ac is an acetyl group.
  • R is a synonym of the aforementioned R
  • m is an integer of not less than 2
  • n is 0 or 1.
  • catalysts such as organic carboxylic acid metal salts comprising tin, zinc, cobalt, lead, calcium and manganese, for example, tin dibutyllaurate, tin (II) octoate, cobaltnaphthenate or chloroplatinic acid are added.
  • a filler can be mixed.
  • the silicon gum mixed with a filler in advance is available in the market as a silicon gum stop or a silicon gum dispersion. If coating a slippage invention layer on silicon gum is preferred, RTV or LTV silicon gum dispersion is preferably used.
  • RTV or LTV silicon gum dispersion is preferably used.
  • paper coating silicon gum dispersions such as Syl Off-23, SRX-257 and SH-237 produced by Toray Silicon Co., Ltd.
  • silane coupling agent it is preferable to use a silane coupling agent to improve the contact between the silicon gum layer and a support.
  • silane coupling agent is cited as follows.
  • a slippage preventing layer may be singly piled on a dram or completely sticked together (for example, laminating method) with a stick or a primer.
  • a material containing a gum composing the slippage preventing layer is dissolved and dispersed in a solvent, and thus obtained solution may be coated on the dram and dried.
  • the dram is made of metal and has stiffness so that the light-sensitive material carried on it is not easily disfigured, and flatness of it's surface is macroscopically maintained.
  • a cylindrical dram, other optional forms (an ellipse form, an equilateral form etc.) of rotational body can be employed.
  • a circulating endless belt can be also employed. Further, a straight moving belt can be also employed.
  • the thickness of the slippage preventing layer is not limited thereto, as far as the light-sensitive material can be carried, but from the viewpoint of keeping flatness of the light-sensitive material, it is preferable 0.1 to 500 ⁇ m.
  • the slippage preventing layer can be provided on heat dram, but to avoid preventing heat conducdtance, it is preferably 0.1 to 300 ⁇ m.
  • dihydroxybenzene e.g., hydroquinone, hydroquinonemonosulfate
  • 3-pyrazolidone e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone
  • aminophenol e.g., o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol
  • ascorbic acid derivative e.g., ascorbic acid sodium arcorbate, erysorbic acid
  • metal complex e.g., EDTA-Fe salt, DTPA-Fe salt, DPTA-Ni salt
  • the ascorbic acid and it's derivatives are preferable.
  • the known ascorbic acid are described in U.S. Patent Nos., 2,688,548, 2,688, 549, 3,022,168, 3,512,981, 4,975,354, 5,326,816, and can be used.
  • the combined usage of the developing agent consisting of the ascorbic acid and it's derivative together with the developing agent consisting of 3-pyrazolidone derivative e.g., 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone
  • aminophenol derivative e.g., o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol
  • dihydroxybenzene derivative e.g., hydroquinone, hydroquinonemonosulfate, sodium hydroquinonemonosulfate, potassium 2,5-hydroquinonedisulfate
  • hydroquinone hydroquinonemonosulfate, sodium hydroquinonemonosulfate, potassium 2,5-hydro
  • the added amount of the developing agent consisting of 3-pyrazolidone derivative, aminophenol derivative or dihydroxybenzene is usually 0.01 to 0.2 moles per a liter of developing solution.
  • the combination of the ascorbic acid and it's derivative with 3-pyrazolidone derivative, and the combination of the ascorbic acid and it's derivative with 3-pyrazolidone derivative and dihydroxybenzene derivative is preferably used.
  • an alkali agent sodium hydroxide and potassium hydroxide,
  • a pH buffer agent e.g., carbonate, phosphate, borate, acetic acid, citric acid and alkanolamine
  • carbonate is preferable, and an added amount of it is preferably 0.5 to 2.5 moles per a liter, more preferably 0.75 to 1.5 moles.
  • a dissolving aid e.g., polyethyleneglycol and its ester, alkanolamine
  • a sensitizing agent e.g., nonionic surfactant including polyoxyethylene and quaternary ammonium compound
  • a surfactant, anti-foaming agent and antifoggant e.g., halogenide such as potassium bromide or sodium bromide, nitrobenzindazole, nitrobenzimidazole, benztriazole, benzthiazole, tetrazole and thiazole
  • a chelating agent e.g., ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate and polyphosphate
  • a development accelerating agent e.g., compounds described in U.S.
  • Patent No. 2,304,025 and Japanese Patent Examined Publication No. 45541/1972 a hardening agent (e.g., glutaraldehyde or addition product of its metabisulfite), or an anti-foaming agent.
  • a hardening agent e.g., glutaraldehyde or addition product of its metabisulfite
  • an anti-foaming agent e.g., anti-foaming agent
  • the pH of the developing solution is preferably adjusted to 9.0 to 12.0 with alkaline agents, more preferably 9.0 to 11.0.
  • the developing solution according to the invention preferably contains the compound presented by the following formula (A). Next, the compound represented by the above mentioned formula (A) used in the present invention will be explained.
  • R 1 and R 2 each independently represents a subsituted or an unsubsituted alkyl group, a subsituted or an unsubsituted amino group, a subsituted or an unsubsituted alkoxy group, and a subsituted or an unsubsituted alkylthio group, and R 1 and R 2 may be linked with together to form ring, k is 0 or 1, and X is -CO- or -CS- when k is 1, and M 1 and M 2 are each a hydrogen atom or an alkali metal atom.
  • R 3 represents a hydrogen atom, a substituted or an unsubstituted alkyl group, a substituted or an unsubstituted aryl group, a substituted or an unsubstituted amino group, a substituted or an unsubstituted alkoxy group, a sulfo group, a carboxyl group, an amide group and a sulfonamide group, Y 1 represents O, S or NR 4 , R 4 represents a substituted or an unsubstituted alkyl group, and a substituted or an unsubstituted aryl group, and M 1 and M 2 are each a hydrogen atom or an alkali metal atom.
  • an alkyl group in Formula (A) or Formula (A-a) is preferably cited a lower alkyl group having 1 to 5 carbon atoms, as an amino group is preferably cited an unsubstituted amino group or an amino group substituted by a lower alkyl group, as an alkoxy group is preferably cited a lower alkoxy group, as an aryl group is preferably cited a phenyl group or a naphthyl group which may possess substituents such as a hydroxyl group, a hologen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group and a sulfonamide group.
  • These compounds are representatively ascorbic acid and erythorbic acid, and their salts, or derivatives derived from ascorbic acid and erythorbic acid, and they are commercially available or easily synthesized according to known synthetic method.
  • the developer according to the invention is preferably used under the alkaline condition of pH of not less than 9.
  • alkaline agent and the developer containing the compound represented by the formula (A) are separately supplied.
  • the pH of the developer containing the compound represented by the formula (A) is preferably not more than 8, and it is preferable to supply separately an alkaline solution whose pH is not less than 9 to maintain alkaline condition.
  • simultaneous coating or separate coating is available, it is preferable to coat the alkaline solution after coating the developer containing the compound represented by the formula (A).
  • water and processing solution are contacted with both surface of the light-sensitive photographic material.
  • water is preferably supplied from the viewpoint of rapidity of the processing.
  • water tank may be provided or may be not provided.
  • the amount of supplied water is preferably 0.5 to 100 g per m 2 of the light-sensitive photographic material, more preferably 1 to 40 g.
  • the supplied water can be heated to optional temperature.
  • absorbed amount of water in the opposite layer to the layer comprising the light-sensitive silver halide emulsion is less than that in the layer comprising the light-sensitive silver halide emulsion.
  • the absorbed amount of water in the opposite layer to the layer comprising the light-sensitive silver halide emulsion is preferably not more than 2 g per m 2 of the light-sensitive photographic material, more preferably not more than 1 g.
  • the absorbed amount of water mentioned above can be attained by the technique described in JP-A No. 9-90584 and other technique known to the art.
  • the developing solution preferably contains a silver halide solvent.
  • a silver halide solvent is cited the compound represented by the formula (I) to (IV) in Japanese Examined Patent Publication No. 7-120023.
  • thiosulfate salt e.g., sodium thiosulfate, ammonium thiosulfate
  • imide compound e.g., uracil, 5-methyluracil, 6-methyluracil, 6-butylthiouracil
  • 4-substituted thiourea compound organic thioethr compound.
  • thione compound, active methylene compound and mesoion compound are preferably used.
  • the silver halide solvent added in the developing solution can be used singly or in combination of two kinds or more and combined usage of plural kinds of the silver halide solvents is preferable. Combined usage of an organic silver halide solvent is more preferable.
  • the pH of the fixing solution is usually between 3.0 and 8.0.
  • thiosulfates such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, and thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate and other organic sulfur compounds which are capable of producing a stable silver complex salts and are known in the art as a fixing agent
  • thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate and other organic sulfur compounds which are capable of producing a stable silver complex salts and are known in the art as a fixing agent
  • the aforesaid fixing agents are preferably used in monobath processing solution, in which is also preferably used uracil or hydantoin described in JP-A 8-179458.
  • a compound which functions as a hardening agent including, for example, water-soluble aluminium salts such as aluminium chloride, aluminium sulfate, potassium alum, aldehyde compounds (such as glutal aldehyde or its sulfite adduct, etc.) may be added.
  • water-soluble aluminium salts such as aluminium chloride, aluminium sulfate, potassium alum, aldehyde compounds (such as glutal aldehyde or its sulfite adduct, etc.) may be added.
  • the fixing solution may contain, if necessary, preservatives such as sulfites or metasulfites; pH buffers such as acetic acid, citric acid, etc.; pH adjuster such as sulfuric acid, or chelating agents capable of softening hard water, etc.
  • preservatives such as sulfites or metasulfites
  • pH buffers such as acetic acid, citric acid, etc.
  • pH adjuster such as sulfuric acid, or chelating agents capable of softening hard water, etc.
  • the fixing agent contains a salt of citric acid, tartaric acid, malic acid, succinic acid or an optical isomer thereof.
  • a salt of citric acid, tartaric acid, malic acid, succinic acid lithium salt, potassium salt, sodium salt, ammonium salt, etc. can be mentioned.
  • lithium hydrogen salt, potassium hydrogen salt, sodium hydrogen salt, or ammonium hydrogen salt of the tartaric acid; ammonium potassium tartarate; or sodium potassium tartarate, etc. may also be used.
  • Developing solution and/or fixing solution may employ a solution which contains a solid processing composition such as a tablet agent or a granule agent which is dissolved in a solvent such as water.
  • a solid processing composition such as a tablet agent or a granule agent which is dissolved in a solvent such as water.
  • Each part of granule of developer and fixer used as solid processing composition according to the invention is preferably covered.
  • sugars and water soluble high molecular compounds to cover the granule are cited sugar alcohol, monosaccharide (e.g., glucose, galactose), disaccharide (e.g., maltose, sucrose, lactose), polysaccharide, polyalkyleneglycol, polyvinylalcohol, polyvinylpyrrolidone, polyvinylacetal, polyvinylacetate, aminoalkylmethacrylate copolymer, methacrylacid-methacrylacidester copolymer, methacrylacid-acrylacidester copolymer and vinylpolymer containing bataine structure.
  • sugar alcohol, polysaccharide and polyalkyleneglycol are preferable.
  • sugar alcohol Preferable examples of sugar alcohol are threitol, erythritol, arabitol, ribitol, xylitol, sorbitol, mannitol, iditol, talitol, galactitol and allodulcitol.
  • polysaccharide are pulran, methylcellulose, ethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, acetic acid phthalic acid cellulose, hydroxypropylmethylcellulosephthalate, hydroxypropylmethylcellulosesuccinate, carboxymethylethylcellulose, dextrin derivative, cyclodextrin derivative and starch decompositions.
  • starch decompositions are pineflow (produced by Matsugaya Chemical Co., Ltd.) and pine-dex.
  • polyalkyleneglycol Preferable examples of polyalkyleneglycol are polyethyleneglycol #2000, #4000 and #6000 etc.
  • a tumbling granulation method for the granulating method in the invention, a tumbling granulation method, a extrusion granulation method, a jet-layer granulation method, a fluidized layer granulation method, a crush granulation method, a stirring granulation method and a compression granulation method are usable.
  • the sugar or water-soluble high molecular weight compound can be coated on the granule prepared by an optional method by a coating method such as a pan coating method, a tumbling coating method, a fluidized layer coating method.
  • the granulation and coating can be continuously performed in the same vessel by using a fluidized layer granulation apparatus or a tumbling layer granulation apparatus. Such the method shows a high production efficiency and is preferable from the viewpoint of the effect of the invention.
  • a fluid layer granulation apparatus available on the market such as Multiprex series, GPCG series and WST/WSG series manufactured by Pawrex Co., Ltd., New Marumerizer series manufactured by Fuji Powdal Co., Ltd., Mixgrard series manufactured by Ookahara Seisakusyo Co., Ltd., and Spira flow series and Flow coater series manufactured by Freund Co., Ltd., is useful.
  • the silver halide light-sensitive photographic material according to the present is usually subjected to process in a washing(or rinsing) bath or in a stabilizing bath.
  • the stabilizing solution usually contains, for the purpose of stabilizing an produced image, an inorganic or organic acid or salt thereof for adjusting pH of the membrane (at pH 3 - 8 after processing), or an alkaline agent or a salt thereof, including, for example, boric acid, metaboric acid, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, ammonia water, mono-carboxylic acids, dicarboxylic acids polycarboxylic acids, citric acid, oxalic acid, malic acid acetic acid, etc.; aldehydes such as formalin, glyoxal, glutalalhehyde, etc.; chelating agents such as ethylenediamintetraacetic acid, or an alkali metal salt thereof, nitrilotriacetic acid, polyphosphates, etc
  • the light-sensitive materials according to the invention are processed while being replenished with a given amount of developing solution in proportion to the processed area of the light-sensitive material.
  • the replenishing amount of the fixing solution is not more than 300 ml per square meter of the light-sensitive material. Preferably, it is between 30 to 250 ml.
  • the replenishing amount of the developing solution is not more than 250 ml per square meter of the light-sensitive material, preferably, it is between 20 to 200 ml.
  • the temperature of the fixing bath, washing bath and/or stabilizing bath is preferably 30 to 45 °C and the temperature of each bath may be separately controlled.
  • the replenishing amount of the fixing solution and developing solution used herein means the amount replenished.
  • the overall processing time (Dry-to-Dry) from the time when the front end of a film is put into the automatic processing machine to the time when it comes out of the drying zone is between 10 to 60 seconds.
  • the total processing time mentioned here includes a time period for all steps necessary for processing a black and white light-sensitive material, and it means the time including concretely all time periods for steps of developing, fixing, bleaching, washing, stabilizing and drying, for example, necessary for processing, namely the time of Dry to Dry.
  • More preferable overall processing time is 15 to 50 sec.
  • the developing time is preferably not more than 18 sec. and not less than 2 sec.
  • a heat conductive member e.g., a heat roller heated at 60 to 130 °C
  • a radiation body by directly applying electricity to a tungsten, carbon, Nicrome, a mixture of zirconium oxide, yttrium oxide or thorium oxide to heat and emit radiation, or by conducting thermal energy from a resistance pyrogeneous substance to a radiation emissive substance such as copper, stainless, nickel and various types of ceramics to generate heat or radiative infrared rays
  • a radiation emissive substance such as copper, stainless, nickel and various types of ceramics to generate heat or radiative infrared rays
  • a heat roller As the heat conductive substance of 60 °C or higher, a heat roller can be mentioned as an example.
  • the heat roller is preferably made of hollow aluminum cylinder and the peripheral surface thereof is coated with a resin such as silicon rubber, polyurethane or Teflon. Both end portions of this heat roller is preferably arranged inside the drying section in the vicinity of the in-let transport mouth of the processor with shaft bearings made of a heat resistant resin such as "Luron"(trade name) and rotationally supported against side walls of the section.
  • one end portion of the heat roller is fixed with a gear, and is rotated in the direction of transport.
  • a halogen heater has been inserted, and the halogen heater is preferably connected to a heat regulator arranged in the automatic processing machine.
  • a thermister which is arranged in contact with the peripheral surface of the heat roller, is connected to the heat regulator, and the heat regulator has preferably been set up so as to change the switch of the halogen heater, when detected temperature by the thermister is between 60 and 150 °C and more preferably, between 70 and 130 °C.
  • the following substances can be mentioned: tungsten, carbon, tantalum, Nichrome, a mixture of zirconium oxide, yttrium oxide and thorium oxide, carbon silicate, molybdenum disilicate.
  • a radiating element such as tungsten, carbon, Nicrome, a mixture of zirconium oxide, yttrium oxide and thorium oxide to heat and emit radiation, or conducting thermal energy from a resistance pyrogeneous substance to a radiation emissive substance such as copper, stainless steel, nickel and various types of ceramics, to generate heat or radiate infrared rays may also be used.
  • the combined usage of the heat conductive substance of 60 °C or higher with the substances capable of emitting radiations with temperature higher than 150 °C can be employed.
  • warm wind of 60 °C or lower is also used in combination.
  • the automatic processor having the method and structure as described below can be preferably used.
  • a solution A To a solution A, were simultaneously added a solution B 1 shown below and an aqueous soluble halide solution C 1 for 15 min. with constant added amount of each solution B 1 and C 1 while keeping at pH 3.0, at the temperature of 35 °C.
  • the resulting emulsion was proved to be an emulsion comprising cubic type silver halide grains having an average diameter of 0.11 ⁇ m (comprised of 70 mol% of silver chloride and 30 mol% of silver bromide).
  • pAg was 160 mV before adding and 100 mV when the adding was finished.
  • the pH of the emulsion was raised to pH 5.6 by 1N-NaOH aqueous solution, and ripened at 50 °C for 10 min. Thereafter, by ultrafiltration unnecessary salts were removed, then to the resulting solution 15 g of gelatin per mol of silver was added and the pH of the solution was adjusted at pH 5.7 and thus obtained solution was dispersed for 30 min. After dispersion, 4 x 10 -4 mol of chloramine T per mol of silver was added. The pAg of thus obtained emulsion was 190 mV (40 °C).
  • a 1 Ossein gelatin 25 g Nitric acid (5%) 6.5 ml Ion-exchanged water 700 ml
  • B 1 Silver nitrate 6.5 g Nitric acid (5%) 4.5 ml
  • C 1 NaCl 47.5 g KBr 51.3 g Ossein gelatin 6 g Transition metal of VI to X groups in a periodic table) shown in Table 1 Ion-exchanged water 200 ml
  • Emulsion Organic contrast accelerationg agent Added amount mg/m 2 Dye in solid dispersion (1-25), added amount mg/m 2 101 A-1 H-7 15 50 102 A-1 H-25 20 50 103 A-1 P-23 15 50 104 A-1 P-27 12 50 105 A-1 T-7 40 50 106 A-2 H-25 20 50 107 A-3 H-25 20 50 108 A-4 H-25 20 50 109 A-5 H-25 20 50 110 A-1 H-7 15 -
  • Samples thus obtained were subjected to wedge exposure using He-Ne laser of 633 nm, and then processed using the developing solution and fixing solution prescribed in the following process 1, 2.
  • the samples were processed by using an automatic processor LD-T1100 (produced by Dainihon Screen Co., Ltd.) under the following condition. Process Temperature (°C) Time (sec.) Development 35 30 Fixation 35 30 Washing Ordinary temp. 30 Squeeze, drying 45 30
  • the replenishing amount of developer and fixer is each 40 ml/m 2 and 40 ml/m 2 respectively.
  • the light-sensitive material was immersed and processed in developing solution and fixing solution.
  • whole processes including development, washing and fixation are carried out by immersing the light-sensitive material in processing solutions.
  • the development was carried out using developing solution supplying portion and development apparatus illustrated in Fig. 1 and 2, and the processes after development, namely, fix, washing and drying were carried out in the same way as used in process 1.
  • Temperature of heat roller (4) 50 °C Time after contacting with heat roller until supplying developing solution 2 sec. Interval between developing solution supplying outlet and the light-sensitive material (L1) 3 mm Slit width of extreme point of developing solution supplying outlet 0.01 mm Time after supplying developing solution until fixation 10 sec. Temperature after supplying developing solution until fixation 45 °C Replenishing amount of developer 40 ml/m 2 Replenishing amount of fixer 40 ml/m 2
  • Fig.1 is a outline of a cross-sectional view of developing process for forming image according to the invention.
  • the silver halide light-sensitive photographic material is transferred on a transferring track 3 by plural transferring rollers 2, and this transferring track 3 is equipped horizontally.
  • the silver halide photographic light-sensitive material is cut in sheet form before transferred into the developing process and transferred by keeping the image forming side (emulsion layer side) P1 upside.
  • a preheat portion, a coating portion and sneeze portion are equipped in this order in the transferring direction.
  • the transferring roller 2 is equipped on the transferring track 3, the heat roller 4 facing the transferring roller 2 is equipped under the transferring track 3.
  • a heater 5 is incorporated in the heat roller 4 which comprises heat means giving heat required to process the silver halide photographic light-sensitive material.
  • the silver halide light-sensitive photographic material P is heated by the heat roller 4 up to 35 to 90 °C, preferably 40 to 60 °C, thereby developing is accelerated.
  • a processing solution supplying means equipped on the transferring track 3 in a coating portion possesses a developing solution supplying portion 8, and the roller 2 facing this developing solution supplying portion 8 is equipped under the transferring track 3.
  • the axis direction of the solution supplying portion 8 is arranged along by the width direction of the silver halide photographic light-sensitive material.
  • the solution supplying portion 8 is equipped at the hind part of the heating means in the transferring direction of the light-sensitive material.
  • a developing solution supplying outlet 9 facing the image forming side P1 of the silver halide light-sensitive photographic material P along by the axis direction is formed in the developing solution supplying portion 8. From this supplying outlet 9, the processing solution was coated on the image forming side P1 of the silver halide light-sensitive photographic material P.
  • squeeze roller 12 is equipped on the transferring track 3. At least upside portion of roller which contacts with the image forming side P1 of the silver halide light-sensitive photographic material P is to be the squeeze roller, wherein underside portion is to be the transferring roller 2.
  • the squeeze roller 12 equipped at the hind part of the developing solution supplying portion 8 in the transferring direction of the light-sensitive material, and squeeze the developing solution supplied on the silver halide photographic light-sensitive material P so that the developing solution is coated uniformly.
  • the squeeze roller is preferably one which absorbs less water.
  • metal roller such as SUS, plastic roller, gum roller, woven fiber roller, non-woven fiber roller and sintered roller.
  • metal roller stainless steel (SUS316L, SUS316, SUS304, SUS303), titan (Ti) and brass (Bs) are preferred.
  • PET polyethyleneterephthalate
  • FE polyethylene
  • PFA tetrafluoroethylene perfluoroalkoxyethylene copolymer
  • POM polyacetal
  • POM polypropylene
  • PTFE polytetrafluoroethylene
  • PVC polyvinylchloride
  • PF phenol resin
  • PPE modified polyphenyleneether
  • PPO polyphenyleneoxide
  • PU polycarbonate
  • PPS polyphenylenesulfide
  • PVDF polyfluorovinylidene
  • FEP tetrafluoroethylene hexafluoropropylene copolymer
  • ETFE tetrafluoroethylene ethylene copolymer
  • ethylenepropylene gum EPDM, EPM
  • silicon gum Si
  • nitryl gum NBR
  • chloroprene gum CR
  • material quality of the woven fiber roller and the non-woven fiber roller polyolefin fiber, polyester fiber, polyacrylnitryl fiber, aliphaticpolyamide fiber, aromatic polyamide fiber and polyphenylenesulfide fiber etc. are preferable.
  • a teflon-coated roller is more preferable.
  • heating means 6, 7 which heat the silver halide photographic light-sensitive material P.
  • an interval L1 between an extreme point 10 of the developing solution supplying outlet 9 formed in the developing solution supplying portion 8 and the silver halide photographic light-sensitive material P is set to be 0.03 to 10 mm.
  • the processing solution supplied from the developing solution supplying portion 8 is coated uniformly on the image forming side P1 of the silver halide light-sensitive photographic material P in the way in which the processing solution is supplied in curtain-like flow.
  • the interval L1 between an extreme point 10 of the developing solution supplying outlet and the silver halide photographic light-sensitive material P is shorter than predetermined interval, because of the fluctuation of the thickness of the silver halide photographic light-sensitive material P and swelling, the surface of the silver halide photographic light-sensitive material P is easily contact with the developing solution supplying portion 8, thereby transferring the silver halide photographic light-sensitive material P does not work well.
  • the interval L1 is larger than predetermined interval, bubble and coating non-uniformity occur easily.
  • the interval of 0.03 mm to 10 mm these problems are solved.
  • Black density of thus developed samples was measured by PDA-65 (Degital densitometer, produced by Konica Co., Ltd.).
  • the sensitivity was defined as a reciprocal of exposure necessary to give a black density of 1.0, wherein sample No. 101 gave black density of 1.0 with an given exposure and a reciprocal of this given exposure was assumed 100.
  • Other sample's sensitivity is a relative value to the reciprocal of exposure of sample 101 (100).
  • Non-image portion of the processed light-sensitive material was observed under a 40-power magnifier for evaluating black spot.
  • the highest quality without any black spot is evaluated as rank 5.
  • the lowest level available for actual use is evaluated as rank 3 by visual observation under a 40-power magnifier.
  • Process 1 and 2 were carried out for all seven days, during these period 30 m 2 per a day was processed, thereafter evaluation of sensitivity, gamma ( ⁇ ) and black spot was done in the same way as mentioned above.
  • the pH of the emulsion was raised to pH 5.6 by 1N-NaOH aqueous solution, and ripened at 50 °C for 10 min.
  • a 2 Silver nitrate 16 g Nitric acid (5%) 5.3 ml Ion-exchanged water 48 ml B 2 : NaCl 3.8 g KBr 3.5 g Ossein gelatin 1.7 g Ion-exchanged water 48 ml C 2 : NaCl 1.4 g Ossein gelatin 7 g Nitric acid (5%) 6.5 ml K 2 RhCl 5 (H 2 O) 0.06 mg Ion-exchanged water 700 ml D 2 : Silver nitrate 154 g Nitric acid (5%) 4.5 ml Ion-exchanged water 200 ml E 2 : NaCl 37 g KBr 33 g Ossein gelatin 6 g K 2 RhCl 5 (H 2 O) 0.04 mg Ion-exchanged water 200 ml
  • a solution A 3 were simultaneously added a silver nitrate solution B 3 and a halide solution C 3 containing NaCl and KBr for 15 min. with constant added amount of each solution B 3 and C 3 while keeping at pH 3.0, at the temperature of 35 °C.
  • the resulting emulsion was proved to be an emulsion comprising cubic type silver halide grains having an average diameter of 0.09 ⁇ m (comprised of 70 mol% of silver chloride and 30 mol% of silver bromide).
  • pAg was 160 mV before adding and 100 mV when the adding was finished.
  • the pH of the emulsion was raised to pH 5.6 by 1N-NaOH aqueous solution, and ripened at 50 °C for 10 min.
  • a 3 Ossein gelatin 25 g Nitric acid (5%) 6.5 ml Ion-exchanged water 700 ml
  • B 3 Silver nitrate 170 g Nitric acid (5%) 4.5 ml
  • C 3 NaCl 47.5 g KBr 51.3 g Ossein gelatin 6 g VI to X transition metal amount shown in Table 2 Ion-exchanged water 200 ml
  • the light-sensitive material thus obtained was subjected to wedge exposure using semi-conductor laser of 780 nm, and then processed using the aforementioned developing solution and fixing solution according to the following process 3.
  • FIG. 3 13 is a transferring roller, 14 is a preheat dram heating in advance, 15 is a dried wind blowing off nozzle, 16 is a washing water puffing out nozzle, 17 is a developing solution puffing out nozzle, 18 is a fixing solution puffing out nozzle.
  • FIG. 19 illustrates an outline of a cross sectional view of a puffing out nozzle of each 17 and 18.
  • Fig. 4 is an outline of a cross sectional view of a structure of solution supplying apparatus.
  • the processing solution is introduced from a chamber 23 through a solution inflow pathway 22 of which flow area is narrowed down, thereafter a vibration panel 25 is changed by a driving element 24, thereby abrupt volume change in a chamber occurs.
  • the orifice is composed of an orifice channel 28 and an orifice panel 29.
  • a wall above the chamber 23 is composed of the vibration panel 25, and through the vibration panel 25, a change of the driving element 24 is conveyed.
  • An upside of the chamber is preferably composed of the vibration panel 25 so that the driving element 24 and the processing solution do not contact directly.
  • Material quality of the wall of the chamber is preferably composed of vinylidene chloride and the channel of the orifice is preferably also composed of vinylidene chloride.
  • Material quality of the orifice panel is composed of nickel.
  • Fig. 5 is an outline of a plane figure of the processing solution supplying apparatus of Fig. 4.
  • a contacting angle of the processing solution on the orifice panel 29 is 20 degrees and the contacting angle of the processing solution on the wall of the chamber is 45 degrees.
  • the vibration panel 25 is, for example, equipped to an exterior material 26 of the processing solution supplying means with epoxy resin stick.
  • the vibration panel is composed of vinylidene chloride resin.
  • the driving element is a piezo electricity element.
  • the piezo electricity element vibrates up and down by stretching and shrinking horizontally, so that it gives the processing solution a pressure.
  • the piezo electricity element is connected by lead lines 31, 32 with an electron pulse emission apparatus which can emit an external pulse voltage.
  • a droplet of the processing solution 30 is sprayed from the orifice 27.
  • An extreme point of the orifice channel 28 is to be a fine diameter circle orifice 27 and the diameter of the droplet of the processing solution sprayed from the solution supplying means is controlled. At this time, a pressure of the processing portion is reduced, thereby the processing solution is inflowed from an external processing tank into the chamber 23 through the solution inflow pathway 22.
  • a driving condition of the processing solution supplying means As a driving condition of the processing solution supplying means, a supplying head of serial type using piezo electricity elements is used. Number of orifice is 64 and zigzag pattern illustrated in Fig. 6 is used. The sprayed volume of the droplet at one time is to be 150 picoliter by adjusting driving voltage, and spraying frequency is set to be 7500 Hz.
  • the used processing condition is as follows. Temperature of preheat dram (14) 40 °C Time until supplying the developing solution after contacting with preheat dram 2 sec. Interval between developing solution supplying portion and light-sensitive material 3 mm Scanning speed of developing solution supplying portion 500 mm/sec. Supplied amount of developing solution 40 ml/m 2 Time until fixation after supplying developing solution 30 sec. Temperature until fixation after supplying developing solution 35 °C Scanning speed of fixing solution supplying portion 500 mm/sec. Supplied amount of fixing solution 40 ml/m 2 Time until washing after supplying fixing solution 15 sec. Temperature until washing after supplying fixing solution 35 °C Time of washing 4 sec. Temperature of washing 40 °C Time of drying 10 sec. Temperature of drying 45 °C
  • process 4 was carried out in the same way in which process 3 was carried out except the used processing condition being changed as follows. Temperature of preheat dram (14) 50 °C Time until fixation after supplying developing solution 10 sec. Temperature until fixation after supplying developing solution 45 °C Time until washing after supplying fixing solution 6 sec. Temperature until washing after supplying fixing solution 45 °C
  • Black density of thus developed samples was measured by PDA-65 (Degital densitometer, produced by Konica Co., Ltd.).
  • the sensitivity was defined as a reciprocal of exposure necessary to give a black density of 1.0, wherein sample No. 201 gave black density of 1.0 with an given exposure and a reciprocal of this given exposure was assumed 100.
  • Other sample's sensitivity is a relative value to the reciprocal of exposure of sample 201 (100).
  • Non-image portion of the processed light-sensitive material was observed under a 40-power magnifier for evaluating black spot.
  • the highest quality without any black spot is evaluated as rank 5.
  • the lowest level available for actual use is evaluated as rank 3 by visual observation under a 40-power magnifier. Obtained results were shown collectively in Table 5.
  • the silver halide-light photographic light-sensitive material according to the invention comprising the dye stuff in a solid dispersion and having the silver halide emulsion layer containing the transition metals of VI to X groups in a periodic table or the organic high contrast accelerating agents exhibited an excellent photographic characteristics with higher sensitivity, higher gamma and no black spot in the processing way in which the processing solution was supplied by coating it on the silver halide-light photographic light-sensitive material.
  • a solution A were simultaneously added a silver nitrate solution B and a halide solution C containing NaCl and KBr for 15 min. with constant added amount of each solution B and C while keeping at pH 3.0, at the temperature of 35 °C.
  • the resulting emulsion was proved to be an emulsion comprising cubic type silver halide grains having an average diameter of 0.11 ⁇ m (comprised of 70 mol% of silver chloride and 30 mol% of silver bromide).
  • pAg was 160 mV before adding and 100 mV when the adding was finished.
  • the pH of the emulsion was raised to pH 5.6 by 1N-NaOH aqueous solution, and ripened at 50 °C for 10 min. Thereafter, by ultrafiltration unnecessary salts were removed, then to the resulting solution 15 g of gelatin per mol of silver was added and the pH of the solution was adjusted at pH 5.7 and thus obtained solution was dispersed for 30 min. After dispersion, 4 x 10 -4 mol of chloramine T per mol of silver was added. The pAg of thus obtained emulsion was 190 mV (40 °C).
  • Sample thus obtained was subjected to wedge exposure using semi-conductor laser of 780 nm, and then processed as follows using a monobath developer.
  • Developing was carried out using developing solution supplying portion and development apparatus shown in Fig. 1 and 2, thereafter washing and drying were carried out using the automatic processor for graphic art GR960 (produced by Konica Co., Ltd.).
  • Fig.1 is a outline of a cross-sectional view of developing process of automatic developing apparatus.
  • a transferring track 3 which transfers the silver halide light-sensitive photographic material by plural transferring rollers 2 is formed, and this transferring track 3 is equipped horizontally.
  • the silver halide photographic light-sensitive material is cut in sheet form before transferred into the developing process 1 and transferred by keeping the image forming side P1 upside.
  • a preheat portion 100, a coating portion 200 and squeeze portion 300 are equipped in this order in the transferring direction.
  • the transferring roller 2 is equipped on the transferring track 3, the heat roller 4 facing the transferring roller 2 is equipped under the transferring track 3.
  • a heater 5 is incorporated in the heat roller 4 which comprises heat means giving heat required to process the silver halide photographic light-sensitive material.
  • the silver halide light-sensitive photographic material P is heated by the heat roller 4 up to 35 to 90 °C, preferably 40 to 60 °C, thereby developing is accelerated.
  • a processing solution supplying means equipped on the transferring track 3 possesses a solution supplying portion 8, and the roller 2 facing this solution supplying portion 8 is equipped under the transferring track 3.
  • the axis direction of the solution supplying portion 8 is arranged along by the width direction of the silver halide photographic light-sensitive material.
  • the solution supplying portion 8 is equipped at the hind part of the heating means in the transferring direction of the light-sensitive material.
  • a supplying outlet 9 facing the image forming side P1 of the silver halide light-sensitive photographic material P along by the axis direction is formed in the solution supplying portion 8. From this supplying outlet 9, the processing solution was coated on the image forming side P1 of the silver halide light-sensitive photographic material P.
  • squeeze rollers 12 facing each other are equipped on and under the transferring track 3. At least upside portion of roller which contacts with the image forming side P1 of the silver halide light-sensitive photographic material P is to be the squeeze roller, wherein underside portion is to be the transferring roller 2.
  • the squeeze rollers 12 are equipped at the hind part of the solution supplying portion 8 in the transferring direction of the light-sensitive material, and squeeze the developing solution supplied on the silver halide photographic light-sensitive material P so that the developing solution is coated uniformly.
  • the squeeze roller 12 is preferably one which absorbs less water.
  • metal roller such as SUS, plastic roller, gum roller, woven fiber roller, non-woven fiber roller and sintered roller.
  • metal roller stainless steel (SUS316L, SUS316, SUS304, SUS303) titan (Ti) and brass (Bs) are preferred.
  • polyethyleneterephthalate PET
  • PE polyethylene
  • PE polyethylene
  • PFA tetrafluoroalkoxyethylene copolymer
  • POM polyacetal
  • POM polypropylene
  • PP polytetrafluoroethylene
  • PVC polyvinylchloride
  • PF phenol resin
  • PPE modified polyphenyleneether
  • PPO polyphenyleneoxide
  • PU polycarbonate
  • PPS polyphenylenesulfide
  • PVDF polyfluorovinylidene
  • FEP tetrafluoroethylene ⁇ hexafluoropropylene copolymer
  • ETFE tetrafluoroethylene ⁇ ethylene copolymer
  • ethylenepropylene gum EPDM, EPM
  • silicon gum Si
  • nitryl gum NBR
  • chloroprene gum CR
  • material quality of the woven fiber roller and the non-woven fiber roller polyolefin fiber, polyester fiber, polyacrylnitryl fiber, aliphaticpolyamide fiber, aromatic polyamide fiber and polyphenylenesulfide fiber etc. are preferable.
  • a teflon-coated roller is more preferable.
  • An interval L1 between an extreme point 10 of a solution supplying outlet 9 formed in a solution supplying portion 8 and the silver halide photographic light-sensitive material P is set to be 0.03 mm to 10 mm.
  • the processing solution supplied from the solution supplying portion 8 is coated uniformly on the image forming side P1 of the silver halide light-sensitive photographic material P in the way in which the processing solution is supplied in curtain-like flow.
  • the interval L1 between an extreme point 10 of a solution supplying outlet 9 and the silver halide photographic light-sensitive material P is shorter than predetermined interval, because of the fluctuation of the thickness of the silver halide photographic light-sensitive material P and swelling, the surface of the silver halide photographic light-sensitive material P is easily contact with the solution supplying portion 8, thereby transferring the silver halide photographic light-sensitive material P does not work well.
  • the interval L1 is larger than predetermined interval, bubble and coating non-uniformity occur easily.
  • the interval of 0.03 mm to 10 mm these problems are solved.
  • the development was carried out as follows. Temperature of heat roller (11) 50 °C Time until supplying developing solution after contacting with heat roller 2 sec. Interval between developing solution supplying outlet and light-sensitive material (L1) 3 mm Slit width of developing solution supplying outlet (22) 0.10 mm Time until washing after supplying developing solution 15 sec. Temperature of supplying developing solution (for 5 sec. after coating developing solution) 35 °C Before washing after 5 sec. passing after supplying developing solution 45 °C Washing condition 20 °C/9 sec. Drying condition 45 °C/15 sec. Supplying amount: monobath developer 50 ml/m 2 Washing water 5 l/min. Sensitivity, Dmax, Dmin
  • Black density of thus developed samples was measured by PDA-65 (Degital densitometer, produced by Konica Co., Ltd.).
  • the sensitivity was defined as a reciprocal of exposure necessary to give a black density of 1.0, wherein sample No. 101 gave black density of 1.0 with an given exposure and a reciprocal of this given exposure was assumed 100.
  • Other sample's sensitivity is a relative value to the reciprocal of exposure of sample 101 (100).
  • a solution A were simultaneously added a silver nitrate solution B and a halide solution C containing NaCl and KBr for 15 min. with constant added amount of each solution B and C while keeping at pH 3.0, at the temperature of 35 °C.
  • the resulting emulsion was proved to be an emulsion comprising cubic type silver halide grains having an average diameter of 0.09 ⁇ m (comprised of 70 mol% of silver chloride and 30 mol% of silver bromide).
  • pAg was 160 mV before adding and 100 mV when the adding was finished.
  • the pH of the emulsion was raised to pH 5.6 by 1N-NaOH aqueous solution, and ripened at 50 °C for 10 min. Thereafter, by ultrafiltration unnecessary salts were removed, then to the resulting solution 15 g of gelatin per mol of silver was added and the pH of the solution was adjusted at pH 5.7 and thus obtained solution was dispersed for 30 min. at 55 °C. After dispersion, 4 x 10 -4 mol of chloramine T per mol of silver was added. The pAg of thus obtained emulsion was 190 mV (40 °C).
  • Sample thus obtained was subjected to wedge exposure using He-Ne laser of 633 nm, and then processed using the developing solution and fixing solution prescribed in the following process 2, 3, then washed and dried.
  • Biodegradable chelating agent (Ch) 40 g Potassium sulfite 35 g Potassium carbonate 25 g 8-Mercaptoadenine 0.1 g Sanbag-P (produced by Sanai Sekyu Co., Ltd) 20 g
  • a developing processor made on an experimental basis in Fig. 3 evaluation was carried out.
  • the light-sensitive material P with the emulsion layer side upside passed the pathway indicated by an arrow and was developed, fixed, stabilized and dried.
  • 13 is a driving roller which transfer the light-sensitive material
  • 14 is a preheat dram heating in advance
  • 15 is a dried wind blowing off outlet
  • 16 is a stabilizing solution puffing out nozzle
  • 17 is a developing solution puffing out nozzle
  • 18 is a fixing solution puffing out nozzle.
  • 24 is a piezo electricity element
  • 22 is a solution inlet pathway
  • 25 is a vibration panel
  • 23 is a chamber
  • 28 is an orifice channel
  • 27 is an orifice
  • 30 is a droplet.
  • the used processing condition is as follows. Temperature of heat dram 40 °C Time until supplying the developing solution after contacting with heat dram 2 sec. Interval between developing solution supplying portion and light-sensitive material 3 mm Scanning speed of developing solution supplying portion 500 mm/sec. Supplied amount of developing solution 40 ml/m 2 Time until fixation after supplying developing solution 10 sec. Temperature until fixation after supplying developing solution 50 °C Scanning speed of fixing solution supplying portion 500 mm/sec. Supplied amount of fixing solution 40 ml/m 2 Time until washing after supplying fixing solution 10 sec. Temperature until washing after supplying fixing solution 45 °C Time of washing 4 sec. Temperature of washing 40 °C Time of drying 10 sec. Temperature of drying 45 °C
  • the processing solution supplying portions were combined shown in Fig. 7.
  • the same processing way was employed as process 1 except supplying the developing solution A from the portion represented by a and the developing solution B from the portion represented by b.
  • Replenished amount of the developing solution A 20 ml/m 2
  • Replenished amount of the fixing solution B 20 ml/m 2
  • Process 3 was carried out with the developing machine whose developing solution supplying portion illustrated in Fig. 3 was reformed as illustrated in Fig. 8.
  • Process 3 was carried out in the same way as process 1 except supplying the developing solution A from the portion 5c and the developing solution B from the portion 5d.
  • 5c and 5d is each composed of five nozzles illustrated in Fig. 4 tied up in a bundle.
  • Replenished amount of the developing solution B 20 ml/m 2 Supplying time of supplying the developing solution B after supplying the developing solution A 2 sec. Time until supplying the fixing solution after supplying the developing solution B 10 sec.
  • the process 4 was carried out in the same way as process 1 except supplying the developing solution B from the portion 5c and the developing solution A from the portion 5d.
  • Replenished amount of the developing solution B 20 ml/m 2 Supplying time of supplying the developing solution A after supplying the developing solution B 2 sec. Time until supplying the fixing solution after supplying the developing solution A 10 sec.
  • Sensitivity, gamma, development uniformity were evaluated in the same way as in example 1, and black spot was evaluated as follows.
  • Non-image portion of the processed light-sensitive material was observed under a 40-power magnifier for evaluating black spot.
  • the highest quality without any black spot is evaluated as rank 5.
  • the lowest level available for actual use is evaluated as rank 3 by visual observation under a 40-power magnifier. Obtained results were shown collectively in Table 6.
  • Sample No. Process S Black Spot Development unniformity 401 1 100 20 3 4 402 2 120 22 4 5 403 3 120 24 5 5 404 4 100 20 4 5
  • silver bromochloride core grains having an average grain diameter of 0.09 ⁇ m composed of 70 mol% of silver chloride and silver bromide.
  • an aqueous solution of silver nitrate and a water-soluble halide solution were mixed simultaneously in the presence of 7x10 -8 mol of K 3 Rh(NO) 4 (H 2 O) per mol of silver in completion of grain formation and 8x10 -6 mol of K 3 OsCl 6 added. While keeping 40 °C pH 3.0 silver potential (EAg) 165 mV. Then, this core grain was covered with a shell through a double-jet method wherein EAg was lowered to 125 mV by sodium chloride.
  • Silver halide emulsion B 1 was prepared in the same manner as in silver halide emulsion A 1 , except that 6x10 -8 of K 3 RhCl 6 in the shell was used. When chemical sensitization was similarly applied to the emulsion B 1 , its sensitivity is higher than that of the emulsion A 1 by 40%.
  • a gelatin-subbing layer having the following composition 1 was coated so as to have an amount of gelatin of 0.55 g/m 2
  • silver halide emulsion layer 1 having composition 2 was coated on the gelatin-subbing layer so as to have an amount of silver of 1.73 g/m 2 and an amount of gelatin of 0.66 g/m 2
  • silver halide emulsion layer 2 having composition 3 was coated on the silver halide emulsion layer 1 so as to have an amount of silver of 1.5 g/m 2 and an amount of gelatin of 0.65 g/m 2
  • a protective layer coating solution having the following composition 4 was further coated so as to have an amount of gelatin of 1.3 g/m 2 .
  • a subbing layer on the side of the support opposite to aforesaid layer side was subjected to simultaneous multi-layer coating wherein a backing layer having the following composition 5 was coated so as to have an amount of gelatin of 2.3 g/m 2 , and a backing protective layer having the following composition 6 was coated so as to have an amount of gelatin of 0.7 g/m 2 .
  • Composition 1 Gelatin-subbing layer composition
  • Composition 2 Silicon halide emulsion layer 1 composition
  • Silver halide emulsion A 1 Silver amount 1.45 g/m 2 equivalent Hydrazine derivative (exemplified compound H-15) 2 x 10 -3 mol/Ag mol Compound a 100 mg/m 2 2-pyrydinol 1 mg/m 2 Polymer latex L1 (grain diameter 0.25 ⁇ m) 0.25 g/m 2 Saponin 20 mg/m 2 2-mercapto-6-hydroxypurine 2 mg/m 2 2-mercaptopyrimidine 1 mg/m 2 n-propyl gallate 25 mg/m 2 Ascorbic acid 20 mg/m 2 EDTA 25 mg/m 2 Sodium polystyrenesulfonic acid 15 mg/m 2 Coating solution pH was 5.2.
  • Composition 3 Silicon halide emulsion layer 2 composition
  • Silver halide emulsion B 1 Silver amount 1.45 g/m 2 equivalent Hydrazine derivative (exemplified compound H-15) 4 x 10 -3 mol/Ag mol Amino compound AM-1 7 mg/m 2 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 4 x 10 -3 mol/Ag mol Saponin 20 mg/m 2 2-mercapto-6-hydroxypurine 1 mg/m 2 Nicotinicacidamide 1 mg/m 2 n-propyl gallate 25 mg/m 2 2-mercaptopyrimidine 1 mg/m 2 EDTA 50 mg/m 2 Dye f5 15 mg/m 2 Polymer latex L3 0.25 g/m 2 Colloidal silica (average grain diameter 0.05 ⁇ m) 150 mg/m 2 Reduced dextrin (weight average molecular weight 1000, 0.2% of reduced glucose composition) 0.3 g/m 2 Phthalated gelatin was used as gelatin, and coating solution pH was 4.8.
  • composition 4 Emmulsion-protective layer composition
  • Composition 5 (Backing layer composition)
  • Gelatin 0.5 g/m 2 Sodium iso-amyl-n-decyysulfosuccinate 5 mg/m 2
  • Polymer latex L4 0.4 g/m 2 Colloidal silica (average grain size 0.05 ⁇ m) 100 mg/m 2
  • Sodium polystyrenesulfonate 10 mg/m 2 1-phenyl-5-mercaptotetrazole 10 mg/m 2
  • Hardener h3 100 mg/m 2 Zinc hydroxide 50 mg/m 2
  • Compound D 10 mg/m 2 EDTA 50 mg/m 2
  • Composition 6 (Backing protective layer composition)
  • Gelatin 0.05 g/m 2 Matting agent monodispersed polymethylmethacrylate with average grain size of 5 ⁇ m 400 mg/m 2
  • Polymer latex L4 1 g/m 2
  • Amorphous silica with average grain size of 3 ⁇ m 350 mg/m 2
  • Surfactant S1 18 mg/m 2
  • UV (ultra violet) density and visual density of the backing layer is each 0.09 and 0.06 respectively.
  • the light-sensitive material 1b was prepared in the same way in which the light-sensitive material 1 was prepared except adding dye f1, f2 and f3 in the backing layer each in an amount of 30, 120 and 150 mg/m 2 respectively.
  • the UV density and the visual density of the backing layer is each 0.32 and 0.96 respectively.
  • the developing solution A was prepared as follows.
  • Developing solution B was prepared in the same way in which the developing solution A was prepared except adding uracil in an amount of 0.5 g/l of the working solution.
  • Developing solution C was prepared in the same way in which the developing solution A was prepared except removing sodium thiosulfate.
  • the fixing solution was prepared as follows.
  • Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate ⁇ 3H 2 O 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) 25 ml Sulfuric acid was added so that the pH of the working solution was adjusted to 4.9.
  • step exposure was carried out using a laser sensitometer employing He-Ne laser beam of 633 nm as a light source.
  • a developing processor made on an experimental basis illustrated in Fig. 3 development was carried out.
  • the light-sensitive material P with image forming side upside passed the pathway indicated by an arrow and was developed, fixed, washed and dried.
  • Fig. 3 12 is a squeeze roller, 13 is a transferring roller, 14 is a preheat dram heating in advance, 15 is a dried wind blowing off nozzle, 16 is a washing water puffing out nozzle, 17 is a developing solution puffing out nozzle, 18 is a fixing solution puffing out nozzle. 19, 20 is each a developing portion heater, 21 is a fixing portion heater where panel heaters to heat the light-sensitive material are used. The surface of each roller is coated with YS-3085 (produced by Toshiba Silicon Co., Ltd.) in a shickness of 300 ⁇ m.
  • Fig. 4 is an outline of a cross sectional view of the structure of the processing solution supplying apparatus.
  • the processing solution is introduced from a chamber 23 through a solution inflow pathway 22 of which flow area is narrowed down, thereafter a vibration panel 25 is changed by a driving element 24, thereby abrupt volume change in a chamber occurs.
  • the orifice is composed of an orifice channel 28 and an orifice panel 29.
  • a wall above the chamber 23 is composed of the vibration panel 25, and through the vibration panel 25, a change of the driving element 24 is conveyed.
  • An upside of the chamber is preferably composed of the vibration panel 25 so that the driving element 24 and the processing solution do not contact directly.
  • Material quality of the wall of the chamber is preferably composed of vinylidene chloride and the channel of the orifice is preferably also composed of vinylidene chloride.
  • Material quality of the orifice panel is composed of nickel.
  • Fig. 5 is an outline of a plan view of the processing solution supplying apparatus of Fig. 4.
  • a contacting angle of the processing solution on the orifice panel 29 is 20 degrees and the contacting angle of the processing solution on the wall of the chamber is 45 degrees.
  • the vibration panel 25 is, for example, equipped to an exterior material 26 of the processing solution supplying means with epoxy resin stick.
  • the vibration panel is composed of vinylidene chloride resin.
  • the driving element is a piezo electricity element.
  • the piezo electricity element vibrates up and down by stretching and shrinking horizontally, so that it gives the processing solution a pressure.
  • the piezo electricity element is connected by lead lines 31, 32 with an electron pulse emission apparatus which can emit an external pulse voltage.
  • a droplet of the processing solution 30 is sprayed from the orifice 27.
  • An extreme point of the orifice channel 28 is to be a fine diameter circle orifice 27 and the diameter of the droplet of the processing solution sprayed from the solution supplying means is controlled. At this time, a pressure of the processing portion is reduced, thereby the processing solution is inflowed from an external processing tank into the chamber 23 through the solution inflow pathway 22.
  • a driving condition of the processing solution supplying means As a driving condition of the processing solution supplying means, a supplying head of serial type using piezo electricity elements is used. Number of orifice is 64 and zigzag pattern illustrated in Fig. 6 is used. A sprayed volume of the droplet at one time is to be 150 picoliter by adjusting driving voltage, and spraying frequency is set to be 7500 Hz.
  • the used processing condition is as follows. But a supplied amount of developing solution and, temperature and time of development, fixation, washing and drying are variable. Temperature of heat roller (1) 40 °C Time after contacting with heat roller until supplying developing solution 2 sec. Interval between developing solution supplying outlet and the light-sensitive material 3 mm Scanning speed of developing solution supplying portion 500 mm/sec. Scanning speed of fixing solution supplying portion 500 mm/sec. Supplied amount of fixing solution 60 ml/m 2
  • samples Nos., 501 to 506 were obtained by processing in the way as described in Table 7.
  • a coated amount of the developing solution is 60 ml per m 2 of the light-sensitive material.
  • Sensitivity, Dmax and Dmin of thus developed samples were measured by PDA-65 (Degital densitometer, produced by Konica Co., Ltd.).
  • the sensitivity was defined as a reciprocal of exposure necessary to give a black density of 1.0, wherein sample No. 501 gave black density of 1.0 with an given exposure and a reciprocal of this given exposure was assumed to be 100.
  • Other sample's sensitivity is a relative value to the reciprocal of exposure of sample 501 (100).
  • Sharpness and fixability (clearness) were evaluated by visual observation. The lowest level available for actual use is evaluated as level 3 by visual observation. The highest quality without any problem in quality was evaluated as level 5, therefore level 2 and 1 were not available for actual use.
  • the silver halide photographic light-sensitive material 2 was prepared in the same way as in example 5 except an each amount of silver of silver halide emulsion A 1 and B 1 of silver halide emulsion 1 and 2 to be 1.6 g/m 2 in example 5.
  • the silver halide photographic light-sensitive material 3 was prepared in the same way as in Example 5 except an each amount of silver of silver halide emulsion A 1 and B 1 of silver halide emulsion 1 and 2 to be 1.85 g/m 2 in example 5.
  • samples Nos., 601 to 612 were obtained by using the developing solution B and processing in the way as described in Table 9. Thus obtained samples were evaluated in the same way as in Example 5. The obtained results were shown in table 10.
  • Sample No. Light-sensitive material Coated amount of developing solution (ml/m 2 ) 601 1 180 602 2 180 603 3 180 604 1 120 605 2 120 606 3 120 607 1 90 608 2 90 609 3 90 610 1 60 611 2 60 612 3 60 Sample No.
  • the silver halide photographic light-sensitive material 4 was prepared in the same way as in example 5 except an each amount of gelatin and polymer latex L 4 of the backing layer to be 0.6 g/m 2 and 0.4 g/m 2 respectively in example 5. An absorbing amount of water of the backing layer was 3.5 g/m 2 .
  • samples Nos., 701 to 704 were obtained by using the developing solution B and processing in the way as described in Table 11. Thus obtained samples were evaluated in the same way as in example 5. The obtained results were shown in table 12.
  • Sample No. Light-sensitive material Temperature of water immersion (°C) Time of water immersion (sec.) 701 1 35 2 702 4 35 2 703 1 No water immersion - 704 4 No water immersion - Sample No. S Dmax Dmin Sharpness (Definition) Fixability (Clearness) Drying ability Remarks 701 99 4.4 0.01 4 5 Good Invention 702 99 4.4 0.01 4 5 Not good Invention 703 98 4.3 0.02 4 4 Good Invention 704 98 4.3 0.02 4 4 Not good Invention
  • coated granule was each called a and b respectively.
  • developing solution D was prepared.
  • samples Nos., 801 to 804 were obtained by using the light-sensitive material 1 and processed as described in Table 13. Thus obtained samples were evaluated in the same way as in example 5. The obtained results were shown in table 14.
  • Sample No. Developing Solution Development (Temperature, time after coated) Until 3 sec. Until 6 sec. Until 9 sec. Until 15 sec. 801 B 36°C 38°C 41°C 42°C 802 D 36°C 38°C 41°C 42°C 803 B 38°C 38°C 38°C 38°C 804 D 38°C 38°C 38°C 38°C 38°C 38°C Sample No.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP99300370A 1998-01-19 1999-01-19 Procédé de formation d'une image, noir et blanc Withdrawn EP0930534A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP744298 1998-01-19
JP744298A JPH11202455A (ja) 1998-01-19 1998-01-19 ハロゲン化銀写真感光材料用現像剤及び画像形成方法
JP1125098 1998-01-23
JP1125098A JPH11212220A (ja) 1998-01-23 1998-01-23 画像形成方法
JP10014192A JPH11212224A (ja) 1998-01-27 1998-01-27 ハロゲン化銀写真感光材料の画像形成方法
JP1419298 1998-01-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2624052A1 (fr) * 2012-02-03 2013-08-07 Neroscins, Aleksandrs Révélateur pour le traitement de photographies en noir et blanc et procédé de fabrication de solution de travail de celui-ci

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Publication number Priority date Publication date Assignee Title
US2178896A (en) * 1935-08-07 1939-11-07 Speedtype Inc Process of making photographs
GB1281696A (en) * 1968-12-27 1972-07-12 Douglas Johnson Improvements relating to photography and cinematography
JPH02136850A (ja) * 1988-11-18 1990-05-25 Konica Corp 写真感光材料の処理方法および処理装置
JPH0980720A (ja) * 1995-09-11 1997-03-28 Konica Corp ハロゲン化銀写真感光材料用自動現像機
EP0831367A1 (fr) * 1996-09-18 1998-03-25 Eastman Kodak Company Procédé de développement d'un produit photographique qui contient un agent développateur par application d'un activateur sur sa surface

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Publication number Priority date Publication date Assignee Title
US2178896A (en) * 1935-08-07 1939-11-07 Speedtype Inc Process of making photographs
GB1281696A (en) * 1968-12-27 1972-07-12 Douglas Johnson Improvements relating to photography and cinematography
JPH02136850A (ja) * 1988-11-18 1990-05-25 Konica Corp 写真感光材料の処理方法および処理装置
JPH0980720A (ja) * 1995-09-11 1997-03-28 Konica Corp ハロゲン化銀写真感光材料用自動現像機
EP0831367A1 (fr) * 1996-09-18 1998-03-25 Eastman Kodak Company Procédé de développement d'un produit photographique qui contient un agent développateur par application d'un activateur sur sa surface

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Title
DATABASE WPI Section PQ Week 9723, Derwent World Patents Index; Class P83, AN 97-249438, XP002103280 *
PATENT ABSTRACTS OF JAPAN vol. 14, no. 369 (P - 1090)<4312> 9 August 1990 (1990-08-09) *
R S POMEROY ET AL: "Liquid-sealed gas processing apparatus", RESEARCH DISCLOSURE., no. 122, June 1974 (1974-06-01), HAVANT GB, pages 16, XP002103259 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2624052A1 (fr) * 2012-02-03 2013-08-07 Neroscins, Aleksandrs Révélateur pour le traitement de photographies en noir et blanc et procédé de fabrication de solution de travail de celui-ci

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