Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • 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
  • G03C1/37—Antiseptic agents
• • 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
  • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper

Definitions

• the present invention relates to a method of forming an image with use of a silver halide color photographic light-sensitive material, and more particularly to an image forming method capable of simply easily providing color prints having excellent sharpness and gloss.
• a silver halide photographic light-sensitive material (hereinafter may be merely called 'light-sensitive material'), provides an excellent image quality and has a high sensitivity, but it is demanded that the image quality be still further improved.
• Important factors determining the image quality include sharpness, which causes a print image to look clear and solid, and gloss, which is effective to cause the print image to look fine and high-grade.
• the support of a photographic paper for color pint-making use is a reflective support having on each of both sides thereof a polyolefin-coat layer, which has a large influence upon the above-mentioned sharpness and gloss.
• a light-sensitive material manufacturer is proceeding with various measures for higher production efficiency, but among these measures, increasing the rate of coating photographic component layers such as silver halide emulsion layers and the like on a support contributes directly to its productivity improvement, so that the use of a highly-increased-speed coating is urgently needed.
• the light-sensitive material comprises a paper support for photographic paper having polyolefin layers each provided on both sides of the support and a photographic layer comprising at least one silver halide emulsion layer provided on a surface of the support.
• the polyolefin layer provided on the surface of the support on which the emulsion layer to be provided contains titanium oxide particles in an amount of not less than 14% by weight of the polyolefin in the layer, and the surface of this polyolefin layer has a roughness expressed by arithmetical mean deviation of the profile SR A calculated by the following equation of not more than 1.0 am.
• the photographic layer contains gelatin in an amount of not more than 7.5 g /m2.
• Lx is the length of measured area in the direction of X axis
• Ly is the length of measured area in the direction of Y axis
• S A is the measured area
• S A Lx X Ly
• S A 25mm 2
• the central surface roughness (SRa) of a support can be measured and determined by using, e.g., a surface roughness analyser SE-3AK, manufactured by Kosaka Research Institute.
• the material usable as the paper support according to the invention is one selected from among materials generally used; those produced from natural pulps such as sulfite-bleached soft wood pulp (NBKP), sulfite-bleached hard wood pulp (LBKP), alkali sulfite bleached soft wood pulp (NBSP) and alkali sulfite bleached hard wood pulp (LBSP), which may be used in combination.
• natural pulps such as sulfite-bleached soft wood pulp (NBKP), sulfite-bleached hard wood pulp (LBKP), alkali sulfite bleached soft wood pulp (NBSP) and alkali sulfite bleached hard wood pulp (LBSP)
• the preferred proportion of broadleaf tree pulp/needle-leaf tree pulp is from 95/5 to 60/40.
• the above natural pulp may be used in combination with straw pulp, esparto pulp or bamboo pulp, and also, if necessary, with synthetic fibers.
• the paper preferably has its strength such as waterproofness increased by adding thereto various additives, e.g., sizing agents such as an alkylketene dimer fatty acid salt, rosin, maleated rosin, an alkenylsuccinate, an alkylsuccinate and a polysuccharide, which each may be used in an amount of 0.2 to 2% of that of the pulp used.
• sizing agents such as an alkylketene dimer fatty acid salt, rosin, maleated rosin, an alkenylsuccinate, an alkylsuccinate and a polysuccharide, which each may be used in an amount of 0.2 to 2% of that of the pulp used.
• a dry paper strength-increasing agent there may be used cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified vinyl alcohol and the like.
• melamine resin As a wet paper strength-increasing agent there may be used melamine resin, urea resin, epoxidized polyamide resin, and the like.
• a fixing agent there may be used polyvalent metal salts such as aluminum sulfate and aluminum chloride, and a cationic polymer such as cationized starch.
• the paper may, if necessary, contain a white pigment, such as clay, talc, calcium carbonate, titanium oxide or barium sulfate.
• a white pigment such as clay, talc, calcium carbonate, titanium oxide or barium sulfate.
• the pulp has its surface tub sized or press sized by using a liquid containing various water-soluble polymer additives.
• water-soluble polymer additive there may be used cationized starch, polyvinyl alcohol, carboxymodified polyvinyl alcohol, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide or gelatin.
• An inorganic electrolyte such as Sodium chloride or sodium sulfate; a hygroscopic material such as glycerol or polyethylene glycol; a pH adjusting agent such as hydrochloric acid, sodium hydroxide or sodium carbonate; and other additives such as dyes, a brightening agent, an antistatic agent, a defoaming agent, and the like, may be used in combination.
• the pulp after being appropriately beaten and adding as needed the above additives thereto, becomes a pulp slurry, which, by means of a paper machine such as Fourdrinier machine, is formed into a paper layer and the layer is then dried and subjected to super calender treatment. Before or after this drying process, the surface of the paper is subjected to sizing treatment.
• the support according to the invention is one obtained by coating a polyolefin resin on both sides of the paper obtained in the above manner.
• polystyrene resin examples include a-olefin homopolymers such as polyethylene, polypropylene, etc., and mixtures of such various polymers; the particularly preferred polyolefin is a high-density polyethylene, a low-density polyethylene or a mixture thereof. These polyolefins are not restricted in the molecular weight, but those having a molecular weight of 20,000 to 200,000 may be generally used.
• the thickness of the polyolefin resin coat layer is not limited either, but is normally about 15 to 50 ⁇ rn.
• the titanium oxide used in the polyolefin coat layer of the invention may or may not undergo surface treatment with aluminum hydroxide, alcohol or surfactant.
• the above white pigment is used in an amount of not less than 14% by weight, preferably 15 to 18% by weight of the polyolefin resin of the polyolefin resin coat layer on the photographic emulsion-coating side of the reflective support.
• the SRa of the support of the invention is not more than 1.0 ⁇ m, preferably 0.05 to 0.09tim.
• Preparation of a support having a SRa of not more than 1.0 ⁇ m is carried out by single or combined use of methods for (1) increasing the thickness of the resin coat layer, (2) increasing compression pressure at the time of resin coating, (3) increasing the machine calender pressure in order to improve the surface flatness of the paper support, (4) adjusting the pulp fiber length, void rate, average fiber width and average fiber thickness which form the paper, and (5) application of a single sided glossed paper obtained by bringing one side of a wet- state paper into close contact with a heated mirror surface dryer.
• the silver halide grain contained in the emulsion layer in the invention preferably has a silver chloride content of not less than 90 mol%, a silver bromide content of not more than 10 mol%, and a silver iodide content of not more than 0.5 mol%, and more preferably is a silver chloride having a silver bromide content of 0.1 to 1 mol%.
• the silver halide grains of the invention may be used alone or used in a mixture with other silver halide grains different in the composition; may also be mixed with silver halide grains having a silver chloride content of less than 90 mol%.
• the silver halide grains having a silver chloride content of not less than 90 mol% accounts for preferably not less than 60% by weight and more preferably not less than 80% by weight of the whole silver halide grains contained in the emulsion layer.
• the silver halide grain may be of either a uniform structure with the same composition from the inside through the outside or a not-uniform structure with difference in the composition between the inside and the outside of the grain. If the inside and the outside of the grain are different in the composition, the composition may change continuously or discontinuously.
• the grain diameter of the silver halide grain is preferably 0.2 to 1.6 ⁇ rn and more preferably 0.25 to 1.2 ⁇ m in consideration of rapid processing, sensitivity and other photographic characteristics.
• the grain diamter can be determined according to one of various methods well-known to those skilled in the art.
• the grain diameter distribution of the silver halide grains of the invention may be either of the polydisperse type or monodisperse type.
• the silver halide grains are monodisperse silver halide grains whose grain diameter distribution's coefficient of variation is not more than 0.22, and more preferably not more than 0.15, wherein the coefficient of variation is a coefficient showing the broadness of a grain diameter distribution, which is defined by
• the silver halide grains of the invention may be prepared according to any one of an acidic method, neutral method or ammoniacal method.
• the grains may be grown at a time or grown after preparing seed grains.
• the reaction between a water-soluble silver salt and a water-soluble halide may take place in any one of the normal precipitation process, reverse precipitation process and double-jet process or a process in combination thereof, but the silver halide is preferably one obtained in the double-jet process.
• the double-jet process there may be used the pAg-controlled double-jet process described in JP O.P.I. No. 48521/1979.
• a solvent for silver halide such as thioether, may be used if necessary.
• the silver halide grain used may be in any arbitrary form.
• a preferred example of the grain form is a cubic grain having ⁇ 100 ⁇ planes as its crystal surfaces.
• the grain may also be in a octahedral, tetradecahedral or dodecahetral crystal form, and further may be a grain having twin planes.
• the silver halide used may be either of grains in a single crystal form or a mixture of grains in various crystal forms.
• the silver halide grain may have metallic ions incorporated into its inside and/or its surface by adding thereto a cadmium salt, zinc salt, lead salt, thalium salt, iridium salt including its complex salt, rhodium salt including its complex salt or ion salt including its complex salt in the grain forming process and/or the grain growing process, and also may have a reduction sensitization nucleus provided to its inside and/or its surface by being placed in an appropriate reductive atmosphere.
• the silver halide emulsion to be used in the invention after completion of the growth of the silver halide, may have its useless water-soluble salts either removed therefrom or allowed to remain thereinside.
• the silver halide grain may be of either the type of forming a latent image mainly on its surface or the type of forming a latent image thereinside; preferably it is of the type of forming a latent image mainly on its surface.
• the silver halide emulsion is chemically sensitized in the usual manner: a sulfur sensitization method, which uses an active gelatin or a compound containing sulfur, capable of reacting with silver ions; a selenium sensitization method, which uses a selenium compound: a reduction sensitization method, which uses a reductive material; and a noble-metallic sensitization method, which uses a gold compound or other noble-metallic compound, may be used alone or in combination.
• a chemical sensitizer there may be used, for example, a chalcogen sensitizer, a general term for sulfur sensitizers, selenium sensitizers and tellurium sensitizers.
• sulfur sensitizers and selenium sensitizers are suitable.
• the sulfur sensitizer include thiosulfates, allylthiocarbazide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonates, rhodanine.
• the adding amount of a sulfur sensitizer depends largely on various conditions such as pH, temperature and silver halide grain size, but as a standard it is preferably 10- 7 to 10- 1 mol per mol of silver halide.
• a selenium sensitizer may be used in place of the sulfur sensitizer.
• the selenium sensitizer include aliphatic isoselenocyanates such as allyisoselenocyanate, selenoureas, selenoamides, selenocar- boxylates and esters thereof, selenophosphates, and selenides such as diethyl selenide, diethyl diselenide.
• a reduction sensitizer may also be used. Any reducing agent may be used without restriction, but preferred examples of the reduction sensitizer include stannous chloride, thiourea dioxide, hydrazine and polyamine, which may be used in combination with a non-gold noble metallic compound such as a palladium compound.
• the silver halide grain used in the invention preferably contains a gold compound.
• the gold compound suitably usable in the invention may be of a gold's oxidation number of either + 1 or +3, and thus a variety of gold compounds may be used, typical examples of which include chloroaurates such as potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold, gold sulfide and gold selenide.
• chloroaurates such as potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichlorogold, gold sulfide and gold selenide.
• the gold compound may be used so as to sensitize the silver halide or so as substantially not to contribute to sensitizing the silver halide.
• the adding amount of the gold compound depends upon various conditions, but as a standard, it is 10- 8 to 10- 1 mol, preferably 10- 7 to 10- 2 mol per mol of silver halide.
• the compound may be added at any point of time, such as during the silver halide grain formation, during the physical ripening, during or after the chemical ripening in the emulsion preparation process.
• the emulsion used in the invention may be spectrally sensitized to desired wavelength regions by using sensitizing dyes known to those skilled in the art. Such sensitizing dyes may be used alone or in combination. Further, in combination with such sensitizing dyes there may be incorporated into an emulsion a supersensitizer which in itself has no spectral sensitization effect or does substantially not absorb visible light, but serves to intensify the sensitization effect of sensitizing dyes.
• gelatin applicable to the invention there may be used lime-treated gelatin, acid-treated gelatin, and the enzyme-treated gelatin described in Bull. Soci. Sci. Phot. Japan, No.16, p.30 (1966). Further, a hydrolyzed product or enzyme-decomposed product of gelatin may also be used.
• the coating weight of gelatin of the photographic layer of the light-sensitive material of the invention is not more than 7.5g/m 2 , more preferably 6.5 to 7.2g/m 2 .
• At least one of the layers of the color light-sensitive material of the invention contains preferably at least one compound selected from among the compounds represented by the following Formulas I, II, III, IV, V and VI
• R 1 represents a hydrogen atom, an alkyl group or an aryl group
• R 2 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxyl group, an alkoxy group or a thiazolyl group
• Z 1 is a group of non-metallic atoms necessary to form a thiazoline ring
• R 3 and R 4 each represent an alkyl group, an aryl group, a -COR group or a -S02N(R')(R") group, wherein R, R' and R" each are an alkyl or aryl group provided that R 3 and R 4 may form a ring together with the nitrogen atom
• Rs, R 6 and R 7 each are a halogen atom or an alkyl group
• R 8 and R 9 each are a hydrogen
• R 1 is an alkylene group or an arylene group.
• R 1 is a lower alkyl group having 1 to 5 carbon atoms, preferably methyl or ethyl.
• the substitutable groups represented by R 1 to R 1 3 in above include those having further substituents.
• Those compounds represented by Formulas I through VI are known compounds, which include the compounds described in JP O.P.I. Nos. 27424/1979, 157244/1982, 84237/1984, 226344/1984, 263938/1985 and 233743/1986.
• any of the above compounds represented by Formulas I to VI may be added to any photographic component layers, but is added preferably to non-light-sensitive layers when taking into account photographic characteristics such as fog and sensitivity.
• the adding point of time of the above compound is during the preparation of a colloid emulsion for photographic component layers, which compound is capable of preventing the emulsion from being decomposed by bacteria, mould, etc., after the addition.
• the adding amount thereof to photographic component layers is preferably 5x10 -7 to 2x10- 3 mol, and more preferably 5x10- 6 to 5x10 -4 mol per m 2 .
• the compound is added preferably in the form of a solution or emulsified liquid after being dissolved in a solvent such as water, methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, ethanolamine, diethanolamine or triethanolamine.
• acylacetanilide couplers are usable as the yellow dye-forming coupler for the invention.
• benzoylacetanilide and pivaloylacetanilide compounds are advantageous; particularly those represented by the following Formula Y-I are suitable for the invention.
• R 21 is a halogen atom or an alkoxy group
• R 22 is a hydrogen atom, a halogen atom or a substitutable alkoxy group
• R 23 is a substitutable acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamido group, an alkylureido group, an arylureido group, a succinimido group, an alkoxy group or an aryloxy group
• Z 2 is a group capable of splitting off upon its coupling reaction with the oxidation product of a color developing agent.
• magenta couplers may be used as the magenta coupler for the invention.
• those represented by the following Formula M-1 are suitably used.
• Z 3 is a group of non-metallic atoms necessary to form a nitrogen-containing heterocyclic ring which may have a substituent
• X represents a hydrogen atom or a substituent capable of splitting off upon the reaction with the oxidation product of a color developing agent
• R is a hydrogen atom or a substituent.
• the substituent represented by R is not restricted, but is typically an alkyl group, aryl group, anilino group, acylamino group, sulfonamido group, alkylthio group, arylthio group, alkenyl group, cycloalkyl group, halogen atom, cycloalkenyl group, alkynyl group, heterocyclic group, sulfonyl group, sulfinyl group, phosphonyl group, acyl group, carbamoyl group, sulfamoyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, alkylamino group, imido group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbaonylamino group, alk
• the preferred scope and examples of the substituent represented by R, the group represented by X, capable of splitting off upon the reaction with the oxidation product of a color developing agent, the nitrogen-containing heterocyclic ring formed by Z, and the substituent which the ring formed by Z may have, and the preferred extent of the magenta couplers represented by Formula (M-I) are the same as those described in European Patent Publication No. A-0327272, pp 23 to 52.
• Examples of the above compound include the exemplified compounds M-1 to M-61 described in European Patent Publication No. A-0273712, pp.6 to 21 and Compounds Nos. 1 to 223 described in European Patent Publication No. A-0235913. pp.36 to 92.
• the above couplers may be used in combination with different other magenta couplers. They may be used in an amount of normally 1x10- 3 mol to 1 mol, and preferably 1x10- 2 mol to 8x10-' mol per mol of silver halide.
• cyan dye-forming coupler for the invention are phenol or naphthol four- equivalent or two-equivalent-type cyan dye-forming couplers, and the most preferred among them are 2- acylamino-5-alkylphenol and 2,5-diacylaminophenol couplers.
• UV absorbents such as benzophenon and benzotriazole compounds
• antistain agents such as hydroquinone derivatives
• surfactants such as sodium alkylnaphthalenesulfonate, sodium alkylbenzenesulfonate, sodium alkylsuccinatesulfonate and polyalkylene glycol
• water-soluble antiir- radiation dyes such as azo, styryl, triphenylmethane, oxonol and anthraquinone compounds
• hardeners such as halogeno-s-triazine.
• vinylsulfone, acryloyl, ethyleneimine, N-methylol and epoxy compounds and water-soluble aluminum salts physical property-improving agents for coated layers such as glycerol, aliphatic polyhydric alcohols, polymer dispersions (latex), solid or liquid paraffin and colloidal silica; and brightening agents such as diaminostilbene compounds, and various oil-soluble coating materials.
• the photographic layers of the light-sensitive material of the invention comprise emulsion layers and, if necessary, other layers such as a subbing layer, intermediate layer, yellow filter layer, UV absorbent layer, protective layer and antihalation layer.
• incorporación of photographically useful hydrophobic compounds such as dye-forming compounds and image stabilizers into the light-sensitive material can be carried out in accordance with various methods such as the solid dispersing method, latex dispersing method and oil-in-water emulsification dispersing method; an appropriate one of the methods may be selected according to the chemical structure of a hydrophobic compound to be used.
• the oil-in-water-type emulsification dispersing method includes various ways for dispersing hydrophobic compounds; normally, a hydrophobic compound is dissolved in a high-boiling organic solvent having a boiling point of higher than 150°C, if necessary, in combination with a low-boiling and/or water-soluble organic solvent, and the solution is emulsifiedly dispersed with the aid of a surfactant in a hydrophilic binder such as an aqueous gelatin solution by a dispersing means such as a stirrer, homogenizer, colloid mill, flow-jet mixer, supersonic device or the like, and then the obtained dispersion is added to a hydrophilic colloid layer.
• a process for removing the low-boiling solvent at the time of dispersing may be inserted.
• the color developing agent used in a color developer includes those known compounds widely used in various color photographic processes, such as aminophenol and p-phenylenediamine derivatives. These compounds are used generally in the form of salts such as hydrochlorides or sulfates because they, when in such the salt form, are more stable than in the free state. Any of these compounds is used in a concentration of preferably about 0.1 g to about 30g, more preferably about 1 g to about 15g per liter of a color developer solution.
• aminophenol developing agent examples include o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene and 2-hydroxy-3-amino-1,4-dimethylbenzene.
• the most useful aromatic primary amine color developing agents are N,N-dialkyl-p-phenylenediamine compounds, in which the alkyl group and phenyl group may be substituted by arbitrary substituents.
• Those particularly useful among the compounds are N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenyl-enediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-#-methansulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl- ⁇ -hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, and 4-amino-N-(2-methoxyethyl)-N
• the developer that applies to processing the color light-sensitive material of the invention may contain known developer component compounds, including alkali agents such as sodium hydroxide or sodium carbonate, alkali metal thiocyanate, alkali metal halide, benzylalcohol, water softener, and thickener.
• Development of the light-sensitive material is made at a temperature of preferably not lower than 15°C, and more preferably 30 ° C to 45 ° C, and at a pH of not less than 7, and generally about 10 to about 13.
• Developing time is preferably not longer than 3 minutes.
• the effect of the invention comes even more excellent in the case of processing in a short time, the so-called rapid processing; a great effect can be obtained where processing time is 90 seconds or less, particularly in the case of 30 seconds or less.
• the light-sensitive material of the invention when containing in its hydrophilic colloid layers a color developing agent as it is or in the form of a precursor thereof, can be processed in an alkaline activator bath.
• the color developing agent precursor is a compound capable of producing a color developing agent under an alkaline condition, and examples of the precursor include aromatic aldehyde derivative-Schiff's base-type precursors, multivalent metallic ion complex precursors, phthalic acid imide derivative precursors, phosphoric acid amide derivative precursors, sugar-amine reaction product precursors and urethane-type precursors.
• the aromatic primary amine color developing agent or its precursor when used in an activator solution, needs to be added thereto in so much an amount that alone can carry out sufficient color formation.
• the amount depends largely upon the kind of the light-sensitive material used, but is preferably 0.1 to 5 mols, and more preferably 0.5 to 3 mols per mol of silver halide. These color developing agents or precursors thereof may be used alone or in combination.
• the color developing agent or its precursor in order to be incorporated into the light-sensitive material, may be added in the form of a solution of it dissolved in an appropriate solvent such as water, methanol, ethanol or acetone; in the form of an emulsified dispersion made from a solution of it dissolved in a high-boiling solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate; or in the form of being impregnated in a latex polymer as described in Research Disclosure No. 14850.
• the color light-sensitive material is subjected to color developing, followed by bleaching and fixation.
• a ferric complex salt of an organic acid represented by Formula A or B is used as a bleaching agent for the bleaching solution.
• a 1 to A4 may be either the same or different and each represent -CH 2 0H, -COOM or -P0 3 M l M 2 ; wherein M, M 1 and M 2 each are a hydrogen atom, an alkali metal such as sodium or potassium, or an ammonium group; and X is a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms, such as propylene, butylene or pentamethylene, wherein the substituent thereto includes a hydroxyl group, an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl or propyl.
• a 1 to A4 are as defined in Formula A; n is an integer of 1 to 8; and B 1 and B 2 may be either the same or different and each represent a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, such as ethylene, propylene, butylene or pentamethylene, in which the substituent thereto includes the same groups as those defined for X in Formula A.
• ferric complex salts of these compounds of A-1 through A-12 and B-1 to B-7 there may be arbitrarily used sodium salts, potassium salts or ammonium salts of these ferric complex salts. From the invention's object and solubility point of view, the ammonium and potassium salts of these ferric complex salts are preferably used.
• the most preferably usable in the invention are compounds A-1, A-3, A-4, A-5, A-9, B-1, B-2 and B-7.
• the ferric complex salt of the organic acid represented by Formula A or B is preferably contained in a concentration of not less than 0.1 mol, more preferably not less than 0.2 mol and most preferably 0.2 to 1.5 mols per liter of a bleaching solution.
• an additional bleaching agent may be used in combination with the above compound represented by Formula A or B.
• Examples of the combinedly usable bleaching agent include ferric complex salts with ammonium, sodium, potassium and triethanolamine salts of the following acids:
• An organic acid ferric complex salt may be used as it is, i.e., in the complex salt form, or in a solution a ferric ion complex salt may be formed by using a ferric salt such as ferric sulfate, ferric chloride, ferric acetate, ferric-ammonium sulfate, ferric phosphate, and aminopolycarboxylic acid or a salt thereof.
• a ferric salt such as ferric sulfate, ferric chloride, ferric acetate, ferric-ammonium sulfate, ferric phosphate, and aminopolycarboxylic acid or a salt thereof.
• a ferric salt such as ferric sulfate, ferric chloride, ferric acetate, ferric-ammonium sulfate, ferric phosphate, and aminopolycarboxylic acid or a salt thereof.
• ferric salt such as ferric sulfate, ferric chloride, ferric acetate, ferric
• the above ferric salt ion complex salt-containing bleaching bath may contain additional complex salts of non-ferric metal ions such as of cobalt, copper, nickel and zinc.
• the bleaching solution when containing the imidazole and its derivative described in JP O.P.I. No. 295258/1989 or at least one of the exemplified compounds represented by the Formulas [I] to [IX] in the same publication, can exhibit its effect for rapid processing.
• those which may also be used in the invention are the exemplified compounds described in pp.14 to 30 of JP O.P.I. No. 123459/1987 the exemplified compounds described in pp.22 to 25 of JP O.P.I. No. 17445/1988 and the exemplified compounds described in JP O.P.I. Nos. 95630/1978 and 28426/1978.
• the above bleaching accelerators may be used alone or in combination; the adding amount thereof is preferably about 0.01 to 100g, more preferably 0.05 to 50g and most preferably 0.05 to 15g per liter of a bleaching bath.
• the bleaching accelerator may be added as it is, but is generally in advance dissolved in water, an alkali or organic acid, if necessary, with an organic solvent such as methanol, ethoanol or acetone, to be added in the form of a solution.
• the bleach solution has a pH of preferably not more than 5.5, more preferably 2.5 to 5.5, wherein the pH is of the bleaching solution at the time of processing a light-sensitive material, which can be definitely distinguished from that of a bleacher replenisher.
• the bleaching solution is used at a temperature of preferably 20 ° C to 50 °C, and more preferably 25 ° C to 45 ° C.
• the bleaching time for color photographic paper is preferably not longer than 40 seconds, more preferably not longer than 30 seconds, and most preferably not longer than 25 seconds, which makes the effect of the invention conspicuous also in rapid processing.
• the bleaching time herein means the duration between the moment when the leading end of a light-sensitive material begins to dip into the bleaching solution and the moment when the leading end gets out of the same solution.
• the bleaching solution usually contains a halide such as ammonium bromide, potassium bromide or sodium bromide, and may also contain a brightening agent, defoaming agent and surfactant.
• a halide such as ammonium bromide, potassium bromide or sodium bromide
• the replenisher to the bleaching solution is preferably comprised partially or wholly of an overflow of a bleaching solution that was once used in processing a different-type color light-sensitive material. That is, where bleaching baths A and B are used for two processing systems, respectively, a bleaching solution overflow from the bleaching bath A is utilized as a replenisher to the bleaching bath B.
• Light-sensitive materials to be processed in the bleaching baths A and B needs to be of types different from each other; for example, color negative film and color paper; color negative film or color paper and color reversal film or paper; color negative films different in the silver chloride concentration, silver bromide concentration or sensitivity; color papers different in the silver chloride concentration, silver bromide concentration or sensitivity, and the like; thus various combinations can be considered, but the combination of color negative film with color paper is particularly preferred in the embodiment of the invention.
• the preferred replenishing amount to the bleaching solution is preferably not more than 50 ml/m 2 , more preferably not more than 30 ml/m 2 for color photographic paper, and preferably not more than 180 ml/m 2 , more preferably not more than 140 ml/m 2 for color negative film; the less the replenishing amount, the more conspicuous does the effect of the invention appear.
• air- or oxygen-blow-in may be made inside the processing bath or inside the replenisher storage tank therefor, or else an appropriate oxidation agent such as hydrogen peroxide, a bromate or a persulfate may be discretionarily added thereto.
• thiosulfates and/or thiocyanates Suitably usable as the fixing agent for the fixing solution in the fixing process that follows the bleaching process are thiosulfates and/or thiocyanates.
• the adding amount of the thiosulfate is preferably not less than 0.4 mol/liter, and that of the thiocyanate is preferably not less than 0.5 mol/liter.
• the fixation bath may also contain a pH buffer comprised of a single salt or two or more salts such as boric acid, borax, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, acetic acid, sodium acetate, ammonium hydroxide.
• a pH buffer comprised of a single salt or two or more salts such as boric acid, borax, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, acetic acid, sodium acetate, ammonium hydroxide.
• the solution further contain a large amount of an alkali halide or ammonium halide, e.g., rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide.
• the solution may also contain discretionary amounts of compounds known as additives for ordinary fixer solutions.
• the ammonium ion should account for preferably not more than 50 mol%, more preferably not more than 20 mol%, and most preferably 0 to 20 mol% of the whole cations, which is considered a preferred embodiment because it enables to prevent possible stain that appears when fixation is made directly after bleaching, and also because it uses a reduced amount of ammonium ions to thereby meet low-pollution requirements.
• a thiocyanate in a concentration of 0.5 mol to 3.0 mols per liter or a thiosulfate in a concentration of preferably 0.4 mol or more, more preferably 1.0 mol or more, and most preferably 1.2 to 2.5 mols per liter of the solution.
• the replenishing amount to the fixing bath is preferably 120 ml or less, more preferably 20 to 1000 ml, and most preferably 50 to 800 ml per m 2 of a light-sensitive material.
• the pH range of the fixing solution is preferably 4 to 8.
• the fixing solution may be added a compound represented by the formula [FA] or one of the exemplified compounds thereof described in JP O.P.I. No. 295258/1989, p.15; the use of that fixing bath provides an additional effect that it significantly curbs a sludge possibly produced when processing a small quantity of light-sensitive materials over a long period of time.
• the adding amount of the compound having the formula [FA] is preferably 0.1 to 200g per liter of a fixing solution.
• the fixing solution there may be used a sulfite or a sulfite-releasing compound, examples of which include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogensulfite, potassium hydrogensulfite, sodium hydrogensulfite, potassium metabisulfite, sodium metabisulfite and ammonium metabisulfite.
• the fixing solution may also contain a compound represented by the formula [B-1] or [B-2] described in JP O.P.I. No.295258/1989, p.16.
• the concentration of the sulfite or sulfite-releasing compound in the fixing solution is preferably at least 0.05 mol, more preferably 0.08 to 0.65 mol, further preferably 0.10 to 0.50, and most preferably 0.12 to 0.40 mol per liter of the fixing bath.
• the fixing time in the fixing solution is arbitrary, but is preferably not longer than 6 minutes and 30 seconds, more preferably 5 seconds to 4 minutes and 20 seconds, and most preferably 10 seconds to 3 minutes and 20 seconds.
• a forcible stirring or agitation to the bleaching bath and fixing bath because it makes the invention not only more effective but also highly adaptable to rapid processing.
• the forcible stirring or agitation herein unlike the usual circulation of a solution, implies providing an appropriate means for making forced stirring or agitation of the bath.
• the forcible stirring means there may be employed those means described in JP O.P.I. Nos. 206343/1989 and 295258/1989.
• setting the time required for each cross-over run between the color-developing bath and the bleaching bath and between other baths to within 10 seconds, preferably within 7 seconds, although outside the effect of the invention, is effective in reducing the bleaching fog
• the use of a duckhill valve to decrease the amount of the solution carried-in by a light-sensitive material is also a favorable embodiment in practicing the invention.
• the fixing process according to the invention is followed by washing or stabilization treatment, but is preferably by a stabilization treatment in a stabilizing solution.
• the stabilizing solution contains a chelating agent having a chelating stability constant of not less than 8.
• the chelating stability constant herein means the constant generally known by L. G. Sillen and A. E. Martell, 'Stability Constants of Metal-ion Complexes, published from The Chemical Society, London (1964), and by S. Chaberek and A. E. Martell, 'Organic Sequestering Agents, Wiley (1959).
• Examples of chelating agents having a chelating stability of 8 or more to ferric ions (Fe 3+ ) include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents and polyhydroxy compounds.
• the using amount of the chelating agent is preferably 0.01 to 50g, and more preferably 0.05 to 20g per liter of the stabilizing solution.
• Preferred compounds as additives to the stabilizing solution include ammonium compounds, which may be provided in the form of ammonium salts of various inorganic compounds; these may be used alone or in combination.
• the adding amount of the ammonium compound is preferably 0.001 to 1.0 mol, more preferably 0.002 to 2.0 mols per liter of the stabilizing solution.
• the stabilizing solution contains a sulfite.
• a sulfite Any sulfite, organic or inorganic, may be used as long as it releases a sulfite ion, but preferably usable is an inorganic salt, examples of which include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium hydrogensulfite, potassium hydrogensulfite, sodium hydrogensulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite.
• any of these sulfites is added in an amount to make a concentration of preferably at least 1x10- 3 mol, more preferably 5x10- 3 to 10- 1 mol per liter of the stabilizing solution, particularly for antistain effect.
• the sulfite may be added directly to the stabilizing solution, but is preferably added to a replenisher to the stabilizing bath.
• Those generally known as additives except the above compounds to the stabilizing solution include polyvinylpyrrolidones (PVP K-15, K-30, K-90); organic salts such as citrates. acetates, succinates, oxalates and maleates; pH adjusting agents such as phosphates, borates, hydrochloric acid and sulfuric acid; fungicides such as phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, thiabendazole derivatives, organic halide compounds and other fungicides known as the slime-control agent for use in the paper-pulp industry; and further, brightening agents, surface active agents, preservatives and metallic salts such as of Bi, Mg, Zn, Ni, Al, Sn, Ti and Zr. These compounds may be used alone or in combination.
• PVP K-15, K-30, K-90 polyvinylpyrrolidones
• organic salts such as citrates. acetates, succinates,
• a light-sensitive material after being processed in the stabilizing solution, requires no washing treatment at all.
• the light-sensitive material may, if necessary, be discretionarily subjected to a short-time rinse or surface washing with only a slight amount of water.
• a stabilizing solution subjected to ion-exchange resin treatment to have its calcium ion content and magnesium ion content reduced to 5 ppm or less, and further, there may be used a method for incorporating the foregoing fungicide and halogen ion-releasing compound into this stabilizing solution.
• the pH range of the fixing solution of the invention is preferably 5.5 to 10.0.
• the pH adjusting agent to be contained in the stabilizing solution can be any of generally known alkali agents or acidic agents.
• the processing temperature range in the stabilizing bath is preferably 15 to 70 ° C, and more preferably 20 to 55 °C.
• the processing time is preferably not longer than 120 seconds, more preferably 3 to 90 seconds and most preferably 6 to 50 seconds.
• the amount of a replenisher to the stabilizing bath is preferably 0.1 to 50 times, and more preferably 0.5 to 30 times the carry-in amount per unit area of a light-sensitive material from the preceding fixing bath.
• the stabilizing bath is preferred to be comprised of a plurality of baths, preferably not less than 2 baths and not more than 6 baths, more preferably 2 to 3 baths, and most preferably 2 baths in a counter-current system, i.e., a system in which a liquid supply is made to the subsequent bath and overflow is made from the preceding bath.
• a counter-current system i.e., a system in which a liquid supply is made to the subsequent bath and overflow is made from the preceding bath.
• NBSP sulfite bleached soft wood pulp
• LBSP sulfite bleached hard wood pulp
• Additives for paper making were added in the following proportions by weight to the absolute dry weight of the pulp.
• the above additives-containing material was subjected to Fourdrinier-paper-machine treatment, and then to size-press and machine-calender treatments, whereby a paper having a weight of 170g/m 2 , bulk density of 1.0 and a moisture of 8% was produced.
• a press sizing solution agent a 5% sizing liquid prepared by dissolving carboxyl-modified PVA and sodium chloride in a proportion of 2:1 in water was used and coated in a coating weight of 2.2g/m 2 on both sides of the paper.
• Coating liquids for Layers 2 to 7 also were prepared in similar manner to the liquid for Layer 1. As hardeners, H-1 was added to Layers 2 and 4, and H-2 to Layer 7. As coating aids, surfactants SU-2 and SU-3 were added to each coating liquid to adjust its surface tension.
• Solution A and Solution B were simultaneously added spending 30 minutes to 1000 ml of an aqueous 2% gelatin solution kept at a temperature of 40 ° C with pAg and pH controlled to 6.5 and 3.0, respectively, and further the following Solution C and Solution D were simultaneously added spending 180 minutes thereto with pAg and pH controlled to 7.3 and 5.5, respectively, wherein the pAg control was conducted according to the method described in JP O.P.I. No. 45437/1984, and the pH control was made with use of an aqueous solution of sulfuric acid or sodium hydroxide.
• the emulsion was desalted by use of a 5% aqueous solution of Demol N, manufactured by Koa Atlas Co., and a 20% aqueous solution of magnesium sulfate, and mixed with a gelatin solution to obtain a monodisperse cubic emulsion EMP-1, which has an average grain size of 0.85 ⁇ m, a variation coefficient of 0.07 and a silver chloride content of 99.5 mol%.
• the above emulsion EMP-1 was subjected to a 90-minute chemical ripening treatment at 50 ° C with use of the following compounds, whereby a blue-sensitive silver halide emulsion Em-B was obtained.
• a monodisperse cubic grains emulsion EMP-2 having an average grain size of 0.43 ⁇ m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%, was obtained in the same manner as in EMP-1 except that the adding period of time of Solutions A and B and that of Solutions C and D were changed.
• the emulsion EMP-2 was subjected to a 120-minute chemical ripening treatment at 55°C with use of the following compounds, whereby a green-sensitive silver halide emulsion Em-G was obtained.
• a monodisperse cubic grains emulsion EMP-3 having an average grain size of 0.50 ⁇ m, a coefficient of variation of 0.08 and a silver chloride content of 99.5 mol%, was obtained in the same manner as in EMP-1 except that the adding period of time of Solutions A and B and that of Solutions C and D were changed.
• EMP-3 was chemically ripened for 90 minutes at 60°C with use of the following compounds, whereby a red-sensitive silver halide emulsion Em-R was obtained.
• the running tests were carried out by repeating the developing and replenishing procedures, spending 14 days, up to the time when the whole used color developer replenisher amounts to double the volume of the color developer bath.
• Each sample was exposed by being brought into contact with a resolution chart to a white light and subjected to the above running processing to thereby form a chart image on the sample.
• the wedge section of the formed chart image was measured by means of a microphotometer with respect to its yellow, magenta and cyan color components to thereby evaluate the sharpness of the sample.
• the evaluation was made on the basis of the average of the sharpness values of yellow, magenta and cyan images; the larger the average value, the more excellent the sharpness of the sample; 50% or above is excellent.
• Each sample was uniformly exposed through a color separation filter to a white light so that a grey density of about 1.0 can be obtained, then subjected to the running processing, and after that, the processed sample was visually evaluated with respect to the degree of its coating uniformity.
• Each sample was exposed through a color separation filter with an optical wedge to a white light, and subjected to the running processing.
• the processed image was measured with respect to its initial density right after the processing and also with respect to its density after three months of its storage under conditions of 23 ° C/70%RH, and on the basis of the difference between both the densities, the short-term image preservability of each sample was evaluated.
• coating aid SU-4 dispersion assistant SU-1, viscosity adjusting agent, hardeners H-2 and H-3, stabilizer ST-11, antifoggants AF-1 and two kinds of AF-2 having weight average molecular weights of 10,000 and 100,000, respectively, were added to the respective layers.
• the emulsions used in the above sample were prepared in conventional manner similar to that of Example 1. Each emulsion was optimally subjected to gold/sulfur sensitization.
• the average grain size is the length of a side of a cube equivalent in the volume to an averaged grain.
• the thus prepared sample was exposed through an wedge to white light, and processed under the following conditions:
• compositions of the processing baths used in the above steps are as follows:
• the bleaching solution, fixing solution, stabilizing solution and the respective replenishers used in above are the same as those used in the processing condition-B of Example 1.
• Each processing bath has its own replenisher added thereto. All overflows from the bleaching baths in the above processes were employed as the replenisher to the bleaching bath in the process B to thus carry out running processing.

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• 1991
  • 1991-12-11 JP JP32779991A patent/JPH05165163A/ja active Pending
• 1992
  • 1992-11-23 EP EP92310702A patent/EP0546713A1/fr not_active Withdrawn

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