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
  • 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
  • G03C5/267—Packaging; Storage

Definitions

• the present invention relates to a processing chemical kit for light-sensitive silver halide photographic materials (hereinafter often "photographic processing chemical kit”), and a method for its dissolution. More particularly, the present invention relates to a photographic processing chemical kit that can completely prevent its photographic processing chemicals fine powder from flying up, makes use of no plastic bottle, can achieve an improved storage stability, has a superior suitability to its dissolution and also has a suitability to work environment and social environment, and a method for its dissolution.
• Light-sensitive silver halide photographic materials are usually photographically processed using processing solutions such as a black and white developing solution, a fixing solution, a color developing solution, a bleaching solution, a bleach-fixing solution and a stabilizing solution, to give an imagewise reproduction.
• processing solutions such as a black and white developing solution, a fixing solution, a color developing solution, a bleaching solution, a bleach-fixing solution and a stabilizing solution.
• the respective processing solutions used here are each put into a plastic bottle or bottles in the form of a single or plural parts of liquid concentrates, and supplied to users as processing chemical kits. When used, users dilute these processing chemical kits with water to prepare service solutions (starting solutions or replenishing solutions).
• mini-labs In recent years, in the photographic processing business, there is a rapid increase in small-scale photofinishing laboratories called mini-labs. With a wide spread of such mini-labs, the quantity of use of processing chemical kit plastic bottles is rapidly increasing year by year.
• Plastics used therefor are also widely used for articles other than photographic processing chemical kit bottles because of their light and tough properties.
• the production of plastics throughout the world is steadily increasing year by year, and has increased to an amount more than one hundred million in the year 1988.
• waste plastic materials are also in an enormous amount. Taking an example in Japan, about 40 % of the whole production is disposed every year.
• waste plastic materials when thrown away in the ocean, cause a pollution of inhabitation environment for orceanic life.
• waste plastic materials are burnt in incinerators having imperfect exhaust-gas disposal equipment to cause the problem of acid rain or the like.
• Japanese Patent Publication Open to Public Inspections (hereinafter "Japanese Patent O.P.I. Publication(s)") No. 109042/1990 and No. 109043/1990 disclose techniques in which photographic processing chemicals are formed into granules to give a granular mixture. Even such techniques, however, can not be perfect, and have the disadvantage that a considerable part of granular mixtures are unwantedly finely powdered during transportation of the processing chemicals.
• the present inventors have found that the above problems can be settled by packaging photographic processing chemicals with a water-soluble film or by binding or covering the processing chemicals with a water-soluble binder.
• the water-soluble film or binder has the disadvantage that it has so extremely high a moisture vapor permeability that the water-soluble film itself absorbs moisture in the rainy season to become liable to break.
• the water-soluble film or binder has been also found to have the disadvantage that the moisture permeates through the water-soluble film or binder and, as a result, the photographic processing chemicals packaged or covered therein absorb the moisture to undergo changes in properties.
• At least two parts of photographic processing chemicals are each packaged with a water-soluble film or bound or covered with a binder, and the packaged, bound or covered parts are packaged together using a moistureproof packaging material (hereinafter often "combination package of the present invention"). This can bring about good results.
• a first object of the present invention is to provide a photographic processing chemical kit for light-sensitive silver halide photographic materials, that can decrease use of plastic bottles and has a suitability to social environment.
• a second object of the present invention is to provide a processing chemical kit for light-sensitive silver halide photographic materials, that can be free from flying up of fine powder of solid photographic processing chemicals, and has a suitability to work environment.
• a third object of the present invention is to provide a processing chemical kit for light-sensitive silver halide photographic materials, that has been improved in its storage stability and can better prevent occurrence of stain at non-image areas of light-sensitive silver halide photographic materials.
• a fourth object of the present invention is to provide a processing chemical kit for light-sensitive silver halide photographic materials, having photographic processing chemicals separated into at least two parts and having a superior suitability to their dissolution, and a method of dissolving the photographic processing chemical kit.
• a fifth object of the present invention is to provide a processing chemical kit for light-sensitive silver halide photographic materials, that can better prevent crystals from being deposited at portions at which photographic processing solutions come into contact with machine walls or air in an automatic processor.
• a sixth object of the present invention is to provide a processing chemical kit for light-sensitive silver halide photographic materials, that has been made light-weight because of no water content in processing chemicals, promises reduction of transportation cost, and requires no wide space for keeping processing chemical kits in photofinishing laboratories.
• A) a processing chemical kit for light-sensitive silver halide photographic materials comprising preferably at least two parts of photographic processing chemicals, said parts of photographic processing chemicals being each packaged with a water-soluble film, and the whole of said parts being further packaged together using a moistureproof packaging material
• B) a processing chemical kit for light-sensitive silver halide photographic materials comprising preferably at least two parts of photographic processing chemicals, said parts of photographic processing chemicals being each bound and/or covered with a water-soluble binder, and the whole of said parts being further packaged together using a moistureproof packaging material.
• powdered processing chemicals are granulated, and granulated processing chemicals are bound with the water-soluble binder into a mass or block, or granulated processing chemicals are bound into a mass or block and covered with the water-soluble binder as a coating.
• the dissolving method of the present invention that can achieve the above object comprises dissolving photographic processing chemicals separated into at least two parts, one of which is a part comprising a color developing agent and another of which is a part comprising an alkali agent; said part comprising a color developing agent being dissolved in advance of said part comprising an alkali agent when said parts are prepared into a processing solution or supplied as a replenishing solution.
• a) at least one of said parts of photographic processing chemicals is a part comprising a solid photographic processing chemical; b) said solid photographic processing chemical is in the form of a tablet, a granule, a powder, a mass or a paste; c) said solid photographic processing chemical has a bulk density of from 0.40 to 0.95 g/cm 3 ; d) at least one of said parts of photographic processing chemicals contains an organic solvent; e) said moistureproof packaging material comprises a film with a layer thickness of from 10 to 150 ⁇ ; f) said water-soluble film or binder comprises a material of at least one selected from a polyvinyl alcohol type, a methyl cellulose type, a polyethylene oxide type, a starch type, a polyvinyl pyrrolidone type, a hydroxypropyl cellulose type, a polysaccharide type (pullulan), a dextran type and a gum arabic type; g) said water-soluble film or
• the water-soluble film or binder of the present invention that can be preferably used is a film or binder comprising a material of a polyvinyl alcohol type, a methyl cellulose type, a polyethylene oxide type, a starch type, a polyvinyl pyrrolidone type, a hydroxypropyl cellulose, a pullulan type, a dextran type, a gum arabic type, a polyvinyl acetate type, a hydroxyethyl cellulose type, a carboxyethyl cellulose type, a carboxymethylhydroxyethyl cellulose type, a poly(alkyl)oxazoline type or a polyethylene glycol type.
• a material of a polyvinyl alcohol type or a pullulan type is particularly preferably used in view of the effect as aimed in the present invention.
• the polyvinyl alcohol preferably used is a very good film-forming material, and has a good strength and flexibility under almost all conditions.
• Commercially available polyvinyl alcohol compositions that are casted into films have a variety of molecular weight and degree of hydrolysis. They may preferably be those having a molecular weight of from about 10,000 to about 100,000.
• the degree of hydrolysis refers to the percentage in which the ester groups of polyvinyl alcohol are substituted with hydroxyl groups. In order to apply the polyvinyl alcohol to films, it may usually have been hydrolyzed in the rage of from about 70 % to 100 %. What is meant by the term polyvinyl alcohol usually includes polyvinyl acetate compounds.
• These water-soluble films can be prepared by commonly available methods as disclosed, for example, Japanese Patent O.P.I. Publications No. 124945/1990, No. 97348/1986, No. 158245/1985, No. 86638/1990, No. 117867/1982, No. 75650/1990, No. 226018/1984, No. 218741/1988 and No. 13565/1979.
• water-soluble films those commercially available under trade names SOLVLON (Aicello Chemical Co., Ltd.), HICELLON (Nichigo Film Co., Ltd.) and PULLULAN (Hayashibara Company, Ltd.) can also be used.
• Polyvinyl alcohol films available from Mono-Sol Department of Chris Craft Industries Inc. may be particularly preferably used, which dissolve at water temperature of from about 34°F to about 200°F, are harmless and have a high chemical resistance.
• the water-soluble film of the present invention may preferably have a layer thickness of from 10 to 120 ⁇ , more preferably from 15 to 80 ⁇ , and particularly preferably ffrom 20 to 60 ⁇ . This is because a water-soluble film with a thickness smaller than 10 ⁇ may give a poor storage stability of solid processing chemicals and, on the other hand, a water-soluble film with a thickness larger than 120 ⁇ takes an excessively long time to dissolve and also may rather make crystals seriously tend to be deposited at portions at which photographic processing solutions come into contact with machine walls or air in an automatic processor.
• the water-soluble film of the present invention may preferably be thermoplastic, for the reason that not only heat sealing or ultrasonic welding can be readily carried out but also the effect as aimed in the present invention can be better obtained.
• the water-soluble film of the present invention may preferably have a tensile strength of from 0.5 x 10 6 to 50 x 10 6 kg/m 2 , more preferably from 1 x 10 6 to 25 x 10 6 kg/m 2 , and particularly preferably from 1.5 x 10 6 to 10 x 10 6 kg/m 2 .
• This tensile strength can be measured according to the method as prescribed in JIS Z-1521.
• the photographic processing chemicals may be shaped with use of the water-soluble binder by any desired means.
• liquid concentrates or finely powdered or granular photographic processing chemicals and the water-soluble binder may be kneaded into a form such as a mass or block, or on the surface of a provisional form (a mass or block) of photographic processing chemicals the water-soluble binder may be sprayed to form a coating layer thereon (see Japanese Patent Applications No. 135887/1990, No. 203165/1990, No. 203166/1990, No. 203167/1990, No. 203168/1990 and No. 300409/1990).
• the solid photographic processing chemicals in the case of the solid photographic processing chemicals, they may be used in the form of tablets, granules, powder, a mass or a paste. It may preferably in the form of tablets, granules or powder, and more preferably tablets. In particular, in view of storage stability, granules are more advantageous than powder, and tables, than granules.
• the tablet type photographic processing chemicals compared with tablet type ones other than the present invention, are expected to be moe effective for preventing the caking which is a phenomenon in which any particles settle down to the bottom of a container to form a mass during dissolution and for preventing stain from occurring at non-image areas of light-sensitive materials after processing.
• the powder refers to fine crystals, which is an aggregate of dust with a dry feeling.
• the granules refer to what has been subjected to the step of granulating the above powder, and is meant to be a granular substance with particle diameters of from 50 to 5,000 ⁇ m.
• the tablets refer to what has been subjected to the step of compression-molding the above powder into given shapes.
• the solid photographic processing chemicals used may be in the form of tablets, granules, powder, a mass or a paste. They may preferably be in the form of granules or powder.
• Tableted processing chemicals can be prepared by any usual methods as disclosed, for example, in Japanese Patent O.P.I. Publications No. 61837/1976, No. 155038/1979 and No. 88025/1977, and British Patent No. 1,213,808.
• Granulated processing chemicals can also be prepared by any usual methods as disclosed, for example, in Japanese Patent O.P.I. Publications No. 109042/1990, No. 109043/1990, No. 39735/1991 and No. 39739/1991.
• Powdered photographic processing chemicals can also be prepared by any usual methods as disclosed, for example, in Japanese Patent O.P.I. Publication No. 133332/1979, British Patents No. 725,829 and No. 729,862 and German Patent No. 37 33 861.
• the solid photographic processing chemicals used in the present invention may preferably have a bulk specific gravity of from 0.40 to 0.95 g/cm 3 , and particularly preferably from 0.50 to 0.85 g/cm 3 , from the view point of its solubility and also in view of the effect as aimed in the present invention.
• the tablet type solid photographic processing chemicals in the case when used, they may preferably have a bulk specific gravity of from 0.5 to 6.0 g/cm 3 , and particularly preferably from 1.0 to 2.5 g/cm 3 .
• the photographic processing chemicals that may preferably be formed into a solid in the present invention may include color developing chemicals, black and white developing chemicals, bleaching chemicals, fixing chemicals, bleach-fixing chemicals and stabilizing chemicals. Those for which the present invention can be better effective are color developing chemicals.
• alkali agents such as potassium carbonate, sodium carbonate, potassium hydroxide, potassium phosphate, potassium hydrogencarbonate and sodium hydroxide contained in the solid photographic processing chemicals may be covered with the water-soluble binder and packaged with the water-soluble film.
• the chemicals can be better prevented from being denatured because of the saponification due to the alkali agents contained in the water-soluble film, and also the effect as aimed in the present invention can be better obtained.
• materials for the water-soluble binder the same materials as those for the water-soluble film used in the present invention, or materials of different type may be used taking account of retardation or acceleration of the solubility.
• the processing chemical kit for light-sensitive silver halide photographic materials is comprised of photographic processing chemicals separated into at least two parts, in respect of agents having reactivities, for example, separation into acid agents and alkali agents, separation into oxidizing agents and reducing agents, or separation of agents that cause chemical reaction.
• the organic solvent used in at least one of the parts of photographic processing chemicals of the present invention may preferably be contained by 1/2 or more in that part, and is used in the state it is enveloped with the water-soluble film like the solid processing chemicals described above.
• the organic solvent used in the present invention refers to an organic solvent such as a development accelerator, a solubilizing agent, a surface active agent or a solvent commonly used in photographic processing chemicals.
• Organic solvents preferably used in the present invention are compounds represented by the following Formulas S1 to S4.
• R-OH wherein R represents a benzyl group or a lower alkyl group having 1 to 5 carbon atoms.
• R 1 -O-(-R 2 -0-) m -X 1 wherein R 1 represents a hydrogen atom or a monovalent organic group; R 2 represents an ethylene group, a propylene group or an isopropylene group; m represents an integer of 1 to 100; and X 1 represents a hydrogen atom, -SO 3 M or -PO 3 M, wherein M represents a hydrogen atom, an alkali metal or an ammonium group.
• R 9 represents a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxyl group
• R10, R11 and R12 each represent a hydrogen atom or a lower alkyl group, preferably an alkyl group having 1 to 4 carbon atoms as exemplified by a methyl group, an ethyl group or a propyl group, and these R10, R11 and R12 may be the same or different from each other.
• l1 to l 3 each represent an integer of 0 or 1 to 30, and p, q1 and q2 each represent an integer of 0 or 1 to 30.
• X 1 and X 2 each represent -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -,
• R 1 represents a hydroxyalkyl group having 2 to 6 carbon atom
• R 2 and R 3 each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, a benzyl group or a group represented by the formula: wherein n represents an integer of 1 to 6;
• X and Y each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.
• Examples of the compound represented by Formula S1 may be benzyl alcohol, methanol, isopropyl alcohol and n-propyl alcohol.
• R 1 in Formula S2 represents a monovalent organic group as exemplified by an alkyl group having 6 to 30, and preferably 6 to 20, carbon atoms, for example, a group such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl; or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, a substituent of which may preferably be an alkyl group having 3 to 12 carbon atoms, for example, a group such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
• the aryl group is exemplified by phenyl, tolyl, xylyl, diphenyl or naphthyl, and preferably phenyl or tolyl.
• the position at which the alkyl group is attached to the aryl group may be any of the ortho, meta and para positions.
• R 2 represents a substituted or unsubstituted ethylene group or propylene group, and m represents an integer of 4 to 50.
• X 1 represents a hydrogen atom, -SO 3 M or -PO 3 M 2 , wherein M represents a hydrogen atom, an alkali metal atom such as Na, K or Li, or NH 4 +.
• R 1 preferably represents a hydroxyalkyl group having 2 to 4 carbon atoms
• R 2 and R 3 each preferably represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms.
• Preferred examples of the compound represented by Formula S4 are as follows: Ethanolamine, diethanolamine, triethanolamine, diisopropanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2-propanol, 3-diethylamino-1-propanol, 3-dimethylamino-1-propanol, isopropylaminoethanol, 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, ethylenediaminetetraisopropanol, benzyldiethanolamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol.
• any of these compounds represented by Formulas S1 to S4 may preferably be used in the processing chemicals of the present invention in an amount ranging from 0.1 to 40 g, and preferably from 0.3 to 20 g, per liter.
• the moistureproof packaging material of the present invention is a material capable of preventing any damage due to accidental contact with water in the atmosphere as in high humidity, rain and fog, and with splashes of water or wet hands, to protect therefrom the photographic processing chemicals having been packaged, bound or covered with the water-soluble film or binder, during their storage, transportation and operation.
• This packaging material may preferably comprise a film with a layer thickness of from 10 to 150 ⁇ .
• the moistureproof packaging material may preferably be comprised of at least one selected from a polyolefin film such as a polyethylene terephthalate, polyethylene or polypropylene film, craft paper capable of being made moistureproof with polyethylene, waxed paper, moistureproof cellophane, glassine, a polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate or acrylonitrile film, metal foil such as aluminum foil, and a metallized polymer film. It may also be a composite material making use of any of these.
• a polyolefin film such as a polyethylene terephthalate, polyethylene or polypropylene film
• craft paper capable of being made moistureproof with polyethylene, waxed paper, moistureproof cellophane, glassine
• a polyester polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate or acrylonitrile film
• metal foil such as aluminum foil,
• a moistureproof packaging material comprised of a degradable plastic, in particular, a biodegradable plastic or a photodegradable plastic.
• the above biodegradable plastic may include i) plastics comprised of a naturally occurring polymer, ii) polymers produced by microorganisms, iii) synthetic polymers with a good biodegradability and iv) plastics into which a biodegradable natural polymer has been incorporated.
• the photodegradable plastic may include v) those in which a group capable of causing a breakdown as a result of excitation with ultraviolet rays is present in the main chain.
• those having at the same time both functions of photodegradation and biodegradation may be included in the present invention.
• Biodegradable plastics may include;
• Examples of the v) photodegradable plastics are those into which a carbonyl group has been introduced for the purpose of photodegradability, to some of which an ultraviolet absorber has been added for the purpose of accelerating degradation.
• Such degradable plastics are commonly disclosed in "science and Industries", Vol 64, No. 10, pp.478-484 (1990), and "Functional Materials", the July, 1990 issue, those of which can be used. It is also possible to use BIOPOL (trade name; available from I.C.I Bio Products & Fine Chemicals) ECO (trade name; available from Union Carbide Corp.), ECOLITE (trade name; available from Eco Plastic Co.), ECOSTAR (trade name; available from St. Lawrence starch Co.) and NUCKLE-P (trade name; available from Nippon Unicar Co., Ltd.).
• BIOPOL trade name; available from I.C.I Bio Products & Fine Chemicals
• ECO trade name; available from Union Carbide Corp.
• ECOLITE trade name; available from Eco Plastic Co.
• ECOSTAR trade name; available from St. Lawrence starch Co.
• NUCKLE-P trade name; available from Nippon Unicar Co., Ltd.
• the moistureproof packaging material according to the present invention may preferably have a coefficient of moisture permeation of not higher than 10 g ⁇ mm/m 2 ⁇ 24 hrs, and preferably not higher than 5 g ⁇ mm/m 2 ⁇ 24 hrs.
• the photographic processing chemicals of the present invention may preferably be separated into a part comprising a color developing agent and a part comprising an alkali agent.
• a part comprising a color developing agent it is preferable in view of antifoaming, pH stability and solubility that the part comprising a color developing agent is first dissolved and thereafter the part comprising an alkali agent is dissolved.
• a p-phenylenediamine compound having a water-soluble group is preferably used since it can well bring about the effect as aimed in the present invention and also causes less fogging.
• the p-phenylenediamine compound of the present invention is not only advatageous in that it causes no contamination of light-sensitive materials and does not tend to cause the skin to erupt even if it has adhered to the skin, but also effective for more efficiently achieving the objects of the present invention particularly when it is used in the color developing chemical kit according to the present invention.
• a water-soluble group at least one group may be present on the amino group or benzene nucleus of the p-phenylenediamine compound.
• the group may preferably include the following: -(CH 2 ) n -CH 2 OH; -(CH 2 ) m -NHSO 2 -(CH 2 ) n -CH 3 ; -(CH 2 ) m -O-(CH 2 ) n -CH 3 ; -(CH 2 CH 2 O) n C m H 2m+1 ; wherein m and n each represent an integer of 0 or more; a -COOH group, and a SO 3 H group.
• Specific exemplary compounds of the color developing agent used in the present invention may include compounds C-1 to C-16 disclosed in Japanese Patent Application No. 203169/1990, pages 26 to 31 its specification.
• the color developing agent is used usually in the form of a salt such as hydrochloride, sulfate or p-toluene sulfonate.
• the color developing agent may also be used alone or in combination of two or more kinds. If necessary, it may also be used in combination with a black and white developing agent as exemplified by phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, or methol.
• R 1 and R 2 each represent an alkyl group, an aryl group, a group or a hydrogen atom provided that they are not hydrogen atoms at the same time.
• the alkyl group represented by R 1 and R 2 may be the same or different, and may be an alkyl group having 1 to 3 carbon atoms for each. such a alkyl group may also have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group or a hydroxyl group.
• R′ represents an alkoxyl group, an alkyl group or an aryl group.
• the alkyl group and aryl group represented by R 1 , R 2 and R′ may include those having a substituent, and R 1 and R 2 may combine to form a ring. For example, they may form a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.
• R11, R12 and R13 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group or heterocyclic group
• R14 represents a hydroxyl group, a hydroxyamino group, a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxyl group, aryloxy group, carbamoyl group or amino group.
• the heterocyclic group may be of 5 or 6 members, may be formed of C, H, O, N and a halogen atom, and may be substituted or unsubstituted.
• R15 represents a divalent group selected from -CO-, SO 2 - or and n is 0 or 1. In particular, when n is 0, R14 represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R13 and R14 may combine to form a heterocyclic group.
• hydroxylamine compounds represented by Formula A are disclosed in U.S. Patents No. 3,287,125, No. 3293,034 and No. 3,287,124.
• Particularly preferred exemplary compounds are compounds A-1 to A-39 disclosed in Japanese Patent Application No. 203169/1990, pages 36 to 38 of its specification, compounds 1 to 53 disclosed in Japanese Patent O.P.I. Publication No. 33845/1991, pages 3 to 6 of its specification, and compounds 1 to 52 disclosed in Japanese Patent O.P.I. Publication No. 63646/1991, pages 5 to 7 of its specification.
• the compound represented by Formula A or B is used usually in the form of a free amine, a hydrochloride, a sulfate, a p-toluene sulfonate, an oxalate, a phosphate or an acetate.
• a hydrosulfite may be used in a small amount as a preservative.
• the hydrosulfite may include sodium sulfite, potassium sulfite, sodium bisulfite and a potassium bisulfite.
• the buffering agent may include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
• Development accelerators may include thioether compounds as disclosed in Japanese Patent Examined Publications No. 16088/1962, No. 5897/1962, No. 7826/1963, No. 12380/1969 and No. 9019/1970 and U.S. Patent No. 3,813,247; p-phenylenediamine compounds as disclosed in Japanese Patent O.P.I. Publications No. 49829/1977 and No. 15554/1975; quaternary ammonium salts as disclosed in Japanese Patent O.P.I. Publication No. 137726/1975, Japanese Patent Examined Publication No. 30074/1969 and Japanese Patent O.P.I. Publications No. 156826/1981 and No.
• the color developing chemicals may preferably contain substantially no benzyl alcohol. What is meant by “contain substantially no.." is that it is contained so as to be in an amount of not more than 2.0 ml per liter of a color developing solution, and more preferably not contained at all. When it is substantially not contained, better results can be obtained, as smaller variations of photographic performances during continuous processing, in particular, less increase in stain.
• the color developing chemicals must contain a chloride ion and a bromide ion.
• the chloride ion is contained preferably in an amount of from 1.0 x 10 ⁇ 2 to 1.5 x 10 ⁇ 1 mol/liter, and more preferably in an amount of from 4 x 10 ⁇ 2 to 1 x 10 ⁇ 1 mol/liter.
• a chloride ion concentration more than 1.5 x 10 ⁇ 1 mol/liter may cause retardation of development, and is not preferable to rapidly obtain a high maximum density.
• a chloride ion concentration less than 1.0 x 10 ⁇ 2 mol/liter is not preferable since it may cause stain and also make large the variations of photographic performances, in particular, minimum density, which accompany continuous processing.
• the color developing chemicals contains the bromide preferably so as to be in an amount of from 3.0 x 10 ⁇ 3 to 1.0 x 10 ⁇ 3 mol/liter, more preferably in an amount of from 5 x 10 ⁇ 3 to 5 x 10 ⁇ 4 mol/liter, and particularly preferably from 1 x 10 ⁇ 4 to 3 x 10 ⁇ 4 mol/liter.
• a bromide ion concentration more than 1 x 10 ⁇ 3 mol/liter may cause retardation of development, resulting in a decrease in maximum density and sensitivity.
• a bromide ion concentration less than 3.0 x 10 ⁇ 3 mol/liter is not preferable since it may cause stain and also make cause the variations of photographic performances, in particular, minimum density, which accompany continuous processing.
• a chloride ion source may include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Of these, sodium chloride and potassium chloride are preferred.
• Bromide ions may be fed in the form of counter salts of an optical brightening agent added in the color developing chemicals and black and white developing chemicals.
• a bromide ion source may include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide. Of these, sodium bromide and potassium bromide are preferred.
• an antifoggant may be optionally added in addition to the chloride ions and bromide ions.
• the antifoggant that can be used may include alkali metal halides such as potassium iodide, and an organic antifoggant.
• the organic antifoggant may include nitrogen-containing heterocyclic compounds as exemplified by benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolydine and adenine.
• nitrogen-containing heterocyclic compounds as exemplified by benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolydine and adenine.
• the color developing chemicals and black and white developing chemicals of the present invention may contain a triazinylstilbene optical brightening agent. This is preferable in view of the effect as aimed in the present invention.
• an optical brightening agent may preferably be a compound represent by the following Formula E.
• X 2 , X 3 , Y 1 and Y 2 each represent a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group, or -OR25, wherein R21 and R22 each represent a hydrogen atom, an alkyl group (including substituted groups) or an aryl group (including substituted groups); R23 and R24 each represent an alkylene group (including substituted groups); and R25 represents a hydrogen atom, an alkyl group (including substituted groups) or an aryl group (including substituted groups); and M represents a cation.
• R21 and R22 each represent a hydrogen atom, an alkyl group (including substituted groups) or an aryl group (including substituted groups)
• R23 and R24 each represent an alkylene group (including substituted groups)
• R25 represents a hydrogen atom, an alkyl group (including substituted groups) or an aryl group (including substituted groups)
• M represents a
• the above compounds can be synthesized by known methods.
• particularly preferably used are E-4, E-24, E-34, E-35, E-36, E-37 and E-41. Any of these compounds may preferably be added so as to be in an amount ranging from 0.2 g to 10 g, and more preferably from 0.4 g to 5 g, per liter of color developing solution.
• the color developing chemicals and black and white developing chemicals used in the present invention may optionally contain methyl cellosolve, methanol, acetone, dimethylfromamide, ⁇ -cyclodextrin or other compounds disclosed in Japanese Patent Examined Publications No. 33378/1972 and No. 9509/1969, which can be used as an organic solvent to improve solubility of the developing agent.
• an auxiliary developing agent may also be used.
• an auxiliary developing agent is known to include, for example, N-methyl-p-aminophenol hexasulfate (Methol), phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N′ ,N′-tetramethyl-p-aminophenilenediamine hydrochloride. It may preferably be added so as to be in an amount of usually from 0.01 to 1.0 g/liter.
• the chelating agent represented by the following Formula K as disclosed in Japanese Patent Application No. 240400/1990, page 63, line 8 from the bottom to page 64, line 3 from the bottom, or any of its exemplary compounds K-1 to K-22, may preferably be added from the viewpoint of effective achievement of the objects of the present invention.
• K-2, K-9, K-12, K-13, K-17 and K-19 may particularly preferably be used.
• the present invention can be well effective when K-2 or K-9 are added to the color developing chemicals.
• Any of these chelating agents may preferably be added so as to be in an amount ranging from 0.1 to 20 g, and more preferably from 0.2 to 8 g, per liter of a color developing solution or black and white developing solution.
• the color developing chemicals and black and white developing chemicals may also contain a surface active agent of various types such as anionic, cationic, amphoteric or nonionic ones.
• a surface active agent such as an alkylsulfonic acid, an aryl sulfonic acid, an aliphatic carboxylic acid or an aromatic carboxylic acid may also be added.
• a bleaching agent preferably used is a ferric complex salt of an organic acid represented by the following Formula L, M, N or P.
• a 1 to A 4 may be the same or different one another and each represent -CH 2 OH, -COOM or PO 3 M 1 M 2 , wherein M, M 1 and M 2 each represent a hydrogen atom, an alkali metal atom or an ammonium group; and
• X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms.
• a 1 to A 4 have the same definition as A 1 to A 4 described in Japanese Patent Application No. 260628/1989, page 12, line 15 to page 15, line 3, and hence detailed description therefor is omitted.
• Ferric complex salts of the compounds L-1 to L-12 may be sodium salts, potassium salts or ammonium salts of ferric complex salts of these compounds, any of which can be arbitrarily used. In view of the effect as aimed in the present invention and the solubility, ammonium salts of ferric complex salts of these compounds may preferably be used.
• L-1, L-3, L-4, L-5 and L-9 are particularly preferably L-1.
• a 1 to A 4 are the same as those defined in Formula L; n represent an integer of 1 to 8; B 1 and B 2 may be the same or different and each represent a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, as exemplified by ethylene, propylene, butylene or pentamethylene.
• the substituent may include a hydroxyl group, and an alkyl group having 1 to 3 carbon atoms as exemplified by a methyl, ethyl or propyl group.
• Ferric complex salts of the compounds M-1 to M-7 may be sodium salts, potassium salts or ammonium salts of ferric complex salts of these compounds, any of which can be arbitrarily used.
• the ferric complex salts of the organic acid represented by Formula L or M are particularly preferably used in view of the effect as aimed in the present invention.
• L-1, L-3, L-4, L-5, L-9, M-1, M-2 and M-7 are preferable, and particularly preferably L-1 or M-1.
• R 1 represents a hydrogen atom or a hydroxyl group
• n is 1 or 2
• x is 2 or 3
• y is 0 or 1
• the sum of x and y is always 3.
• Preferred compounds represented by Formula N are N-1 and N-2 shown below.
• a 1 to A 4 may be the same or different one another, and each represent -CH 2 OH, PO 3 M 1 M 2 or -COOM 3 , wherein M 1 M 2 and M 3 each represent a hydrogen atom, an alkali metal atom as exemplified by sodium and potassium, or other cation as exemplified by ammonium, methylammonium or trimethylammonium;
• X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms, or -(B 1 O) n -B 2 -.
• B 1 and B 2 may be the same or different each other, and each represent a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.
• the alkylene group represented by X may include ethylene, triethylene and tetramethylene.
• the alkylene group represented by B 1 or B 2 may include methylene, ethylene and trimethylene.
• the substitutent on the alkylene group represented by X, B 1 or B 2 may include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms as exemplified by a methyl group and an ethyl group
• the letter symbol n represents an integer of 1 to 8, and preferably 1 to 4.
• ferric complex salts of the compound represented by the above Formula IV ferric complex salts of the following compounds may also be used as the bleaching agent in the bleaching chemicals or bleach-fixing chemicals.
• any of the above ferric salts of organic acids may preferably be contained so as to be in an amount of from 0.1 mol to 2.0 mols, and more preferably from 0.15 mol to 1.5 mols, per liter of a bleaching solution or bleach-fixing solution.
• the bleaching chemicals, bleach-fixing chemicals and fixing chemicals may contain at least one of the imidazoles and derivatives thereof as disclosed in Japanese Patent O.P.I. Publication No. 295258/1989, compounds represented by Formulas I to IX and exemplary compounds thereof as also disclosed therein, which can be effective for rapid processability.
• the bleaching chemicals or bleach-fixing chemicals may also contain a halide such as ammonium bromide, potassium bromide or sodium bromide, every sort of optical brightening agent, a defoaming agent or a surface active agent.
• a halide such as ammonium bromide, potassium bromide or sodium bromide, every sort of optical brightening agent, a defoaming agent or a surface active agent.
• a thiocyanate and a thiosulfate may preferably be used.
• the thiocyanate may preferably be contained so as to be in an amount of not less than 0.1 mol/liter. In the case when color negative films are processed, it may more preferably be in an amount of not less than 0.5 mol/lit, and particularly preferably be not less than 1.0 mol/lit.
• the thiosulfate may preferably be contained so as to be in an amount of not less than 1.0 mol/liter.
• color negative films it may more preferably be in an amount of not less than 0.2 mol/lit, and particularly preferably be not less than 0.5 mol/lit.
• the objects of the present invention can be more effectively achieved when the thiocyanate and thiosulfate are used in combination.
• the fixing chemicals or bleach-fixing chemicals according to the present invention may also contain a buffering agent comprised of every sort of salt, which may be used alone or in combination of two or more kinds.
• the fixing chemicals or bleach-fixing chemicals may further contain a large quantity of a re-halogenating agent such as an alkali halide or ammonium halide, as exemplified by potassium bromide, sodium bromide, sodium chloride or ammonium bromide. It is also possible to appropriately add compounds which are known to be usually added to fixing chemicals or bleach-fixing chemicals, as exemplified by alkylamines and polyethylene oxides.
• the compound represented by the following Formula FA may preferably be added to the fixing chemicals or bleach-fixing chemicals, whereby not only the effect of the present invention can be well obtained but also an additional effect can be obtained such that sludge may much less occur in a processing solution having a fixing ability, when light-sensitive materials are processed in a small quantity over a long period of time.
• the compounds represented by Formula FA as described in that specification can be synthesized by usual methods as disclosed in U.S. Patents No. 3,335,161 and No. 3,260,718.
• the compounds represented by Formula FA may each be used alone or in combination of two or more kinds.
• the compound represented by Formula FA may be added so as to be in an amount of from 0.1 g to 200 g per liter of a processing solution, within the range of which good results can be obtained.
• the stabilizing chemicals may preferably contain a chelating agent having a chelate stability constant with respect to iron ions, of not less than 8.
• the chelate stability constant refers to the constant commonly known from L.G. Sillen and A.E. Martell, "Stability Constants of Metal-ion Complexes", The Chemical Society, London (1964), and S. Chaberek and A.E. Martell, "Organic Seqestering Agents", Wiley (1959).
• the chelating agent having a chelate stability constant with respect to iron ions, of not less than 8 may include those disclosed in Japanese Patent Applications No. 234776/1990 and No. 324507/1989.
• the above chelating agent may preferably be used so as to be in an amount of from 0.01 to 50 g, and more preferably from 0.05 to 20 g, per liter of a stabilizing chemicals, within the ranges of which good results can be obtained.
• Preferred compounds that can be added to the stabilizing solution may include ammonium compounds. These are fed by ammonium salts of various inorganic compounds. The ammonium compound may be added so as to be in an amount preferably ranging from 0.001 mol to 1.0 mol, and more preferably ranging from 0.002 mol to 2.0 mols, per liter of a stabilizing solution.
• the stabilizing chemicals may preferably contain a sulfite.
• the stabilizing chemicals may preferably also contain a metal salt used in combination with the above chelating agent.
• a metal salt may include salts of metals such as Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr. It can be fed in the form of an inorganic salt such as a halide, a hydroxide, a sulfate, a carbonate, a phosphate and an acetate, or in the form of water-soluble chelating agents.
• the metal salt may preferably be used in an amount ranging from 1 x 10 ⁇ 4 to 1 x 10 ⁇ 1 mol, and more preferably ranging from 4 x 10 ⁇ 4 to 2 x 10 ⁇ 2 mol, per liter of the stabilizing solution.
• a salt of an organic acid such as citric acid, acetic acid, succinic acid, oxalic acid or benzoic acid, a pH adjuster such as phosphate, borate, hydrochloric acid or sulfate, and so forth.
• a known mildewproofing agent agent may also be used alone or in combination, so long as the effect of the present invention is not lost.
• silver halide grains used may comprise silver iodobromide or silver iodochloride with an average silver iodide content of not less than 3 mol %, and particularly preferably silver iodobromide with a silver iodide content of from 4 mol % to 15 mol %.
• an average silver iodide content preferable for the present invention is in the range of from 5 mol % to 12 mol %, and most preferably from 8 mol % to 11 mol %.
• RD308119 the silver halide emulsions as disclosed in Research Disclosure No. 308119 (hereinafter "RD308119”) can be used. Items described and paragraphs thereof are shown in the following table.
• Photographic additives are also described in the above Research Disclosures. Items described and paragraphs thereof are shown in the following table.
• Couplers can be used in the light-sensitive material to be processed using the photographic processing chemicals of the present invention. Examples thereof are described in the above Research Disclosures. Related items described and paragraphs thereof are shown in the following table.
• the additives can be added by the dispersion method as described in RD308119, Paragraph XIV.
• the light-sensitive material may also be provided with the auxiliary layers such as filter layers and intermediate layers as described in RD308119, Paragraph VII-K.
• the light-sensitive material used in the present invention may be comprised of various layers of conventional layer order, inverse layer order or unit structure as described in the aforesaid RD308119, Paragraph VII-K.
• Silver halide grains used in the light-sensitive material may be silver halide grains mainly composed of silver chloride with a sliver chloride content of not less than 80 mol %, preferably not less than 90 mol %, particularly preferably not less than 95 mol %, and most preferably not less than 99 mol %.
• the above silver halide grains mainly composed of silver chloride may contain, in addition to silver chloride, silver bromide and/or silver iodide as silver halide composition.
• silver bromide may preferably in a content of not more than 20 mol %, more preferably not more than 10 mol %, and still more preferably not more than 3 mol %.
• silver iodide it may preferably be in a content of not more than 1 mol %, more preferably 0.5 mol %, and most preferably 0 mol %.
• the silver halide grains mainly composed of silver chloride, comprising 50 mol % or more of silver chloride may be applied to at least one silver halide emulsion layer, and preferably applied to all the light-sensitive silver halide emulsion layers.
• the crystals of the silver halide grains described above may be regular crystals or twinned crystals, or may be of any other form. Those having any ratio of [1.0.0] face to [1.1.1] face can be used.
• these silver halide grains may have a structure which is uniform from the interior to the outer surface, or a layer structure wherein the inside and the outer surface are of different nature, i.e., a core/shell type.
• These silver halide grains may be of the type wherein a latent image is mainly formed on the surface, or the type wherein it is formed in the interior of grains.
• Tabular silver halide grains (see Japanese Patent O.P.I. Publications No. 113934/1983 and No. 47959/1986) may also be used. It is also possible to use the silver halides as disclosed in Japanese Patent O.P.I. Publications No. 26837/1989, No. 26838/1989 and No. 77047/1989.
• the silver halide grains may be those obtained by any preparation method such as the acid method, the neutral method or the ammonia method.
• They may also be those prepared, for example, by a method in which seed grains are formed by the acid method, which are then made to grow by the ammonia method capable of achieving a higher grow rate, until they come to have a given size.
• seed grains are formed by the acid method, which are then made to grow by the ammonia method capable of achieving a higher grow rate, until they come to have a given size.
• silver halide emulsion layers contain color couplers.
• a red-sensitive emulsion layer may contain, for example, a non-diffusible color coupler capable of forming a cyan-part color image, usually a phenol or ⁇ -naphthol coupler.
• a green-sensitive emulsion layer may contain, for example, at least one non-diffusible color coupler capable of forming a magenta-part color image, usually a 5-pyrazolone type color coupler and pyrazolotriazole.
• a blue-sensitive emulsion layer may contain, for example, at least one non-diffusible color coupler capable of forming a yellow-part color image, usually a color coupler having a open chain ketomethylene group.
• the couplers may be, for example, six-, four- or two-equivalent couplers.
• two-equivalent couplers are particularly preferred.
• Suitable couplers are disclosed in the following publications: W. Pelz, "Farbkuppler (Color Couplers)” in Mitanderlnausden Anlagenslaboratorien der Afga (Afga Research Reports), Leverkusen/München, Vol. III, p.111 (1961); K. Venkataraman, The Chemistry of synthetic Dyes, Vol. 4, pp.341-387, Academic Press; The Theory of the Photographic Process, Fourth Edition, pp.353-362; and Research Disclosure No. 17643. section VII.
• magenta coupler represented by Formula M-1 as described on page 29 of the specification in Japanese Patent O.P.I. Publication No. 106655/1985 (including as specific exemplary magenta couplers, the compounds No. 1 to No. 77 described on pages 26 to 34 of the specification in Japanese Patent O.P.I. Publication No.
• the above color developing chemicals (parts of powdered processing chemicals for a 10 liter developing solution) were each put in the inner package as shown in Table 1, and then all the packages were put in the outer package as shown in Table 1 to make storage tests.
• the storage tests were made under conditions of 50°C and 65 % RH for 1 month.
• the processing chemicals were dissolved using a chemical mixer, and then developing was carried out.
• the outer package was cut open with a cutter, and the whole inner packages were put into water to dissolve the processing chemicals. On that occasion, whether or not the powder flew up and how the powdered chemicals dissolved were observed.
• reflection yellow densities at maximum density areas and non-image areas of color paper samples were measured.
• Second- to seventh-layer coating solutions were also prepared in the manner similar to the above first-layer coating solution.
• a hardening agent H-1 was also added to the second layer and the fourth layer each, and H-2, to the seventh layer.
• surface active agents SU-2 and SU-3 were added to adjust surface tension.
• the pAg was controlled by the method disclosed in Japanese Patent O.P.I. Publication No. 45437/1984 and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.
• the emulsion was desalted using an aqueous 5 % solution of Demol-N, produced by Kao Atlas Co and an aqueous 20 % solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to give a monodisperse cubic emulsion EMP-1 having an average grain size of 0.85 ⁇ m, a variation coefficient ( ⁇ /r) of 0.07 and a silver chloride content of 99.5 mol %.
• the above emulsion EMP-1 was subjected to chemical sensitization at 50°C for 90 minutes using the following compounds to give a blue-sensitive silver halide emulsion Em-B.
• EMP-1 The same procedure for the preparation of EMP-1 was repeated except that the addition time of the solutions A and B and the addition time of the solutions C and D were changed, to give a monodisperse cubic emulsion EMP-2 having an average grain size of 0.43 ⁇ m, a variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol %.
• the emulsion EMP-2 was subjected to chemical sensitization at 55°C for 120 minutes using the following compounds to give a green-sensitive silver halide emulsion EmG.
• EMP-1 The same procedure for the preparation of EMP-1 was repeated except that the addition time of the solutions A and B and the addition time of the solutions C and D were changed, to give a monodisperse cubic emulsion EMP-3 having an average grain size of 0.50 ⁇ m, a variation coefficient ( ⁇ /r) of 0.08 and a silver chloride content of 99.5 mol %.
• the emulsion EMP-3 was subjected to chemical sensitization at 60°C for 90 minutes using the following compounds to give a red-sensitive silver halide emulsion EmR.
• the sample thus obtained was subjected to wedge exposure by a conventional method, and then processed under the following conditions.
• the solution obtained by dissolving the color developing chemicals after its storage was used.
• a bleach-fixing solution a solution with the following composition was used. Made up to 1 liter by adding water, and adjusted to pH 6.5 using acetic acid or sodium hydroxide.
• a solution with the following composition was used. Made up to 1 liter by adding water, and adjusted to pH 8.0 using 50 % sulfuric acid or 25 % ammonia water.
• PVA-1 denotes a polyvinyl alcohol water-soluble film (trade name: HICELLON S-Type, 30 ⁇ ; available from Nichigo Film Co., Ltd.);
• PVA-2 a polyvinyl alcohol water-soluble film (trade name: SOLUBLON PH, 30 ⁇ ; Aicello Chemical Co., Ltd.);
• PVA-3 a polyvinyl alcohol water-soluble film (trade name: SOLUBLON PW, 40 ⁇ ; Aicello Chemical Co., Ltd.);
• PVA-4 a polyvinyl alcohol water-soluble film (trade name: HICELLON C-Type 30 ⁇ ; available from Nichigo Film Co., Ltd.);
• PL-1 a pullulan film (a natural polysaccharide having glucose as a minimum unit, 20 ⁇ ; available from Hayashibara Company, Ltd.).
• the powder does not fly during dissolution, the processing chemicals well dissolves, less fogging occurs even after storage of the processing chemicals, and a photographic processing chemical kit capable of giving a satisfactory dye density can be obtained, when the solid photographic processing chemicals separated into a plurality of parts are packaged with the water-soluble film and the whole is further packaged with the moistureproof packaging material.
• Example 1 was repeated except that only the part C of the color developing chemicals for color paper as used therein was packaged with the water-soluble polymer as shown in Table 1, and further packaged with the outer package as also shown in Table 1.
• the part A and part B were packaged with a polyethylene bag. Tests were similarly made. As a result, substantially the same results as in Example 1 were obtained.
• bleach-fixing chemicals for color papers were thoroughly mixed to produce powdered processing chemicals for a 10 liter bleach-fixing solution.
• the bleach-fixing parts thus prepared were each put in the same inner package and outer package as those shown in Table 1 of Example 1, and then the storage stability was similarly tested. As a result, substantially the same results as in Example 1 were obtained in respect of the deposition of crystals, the flying of powder during dissolution and the solubility of processing chemicals.
• Example 1 was repeated except that the color developing chemicals used therein were granulated using a commercially available fluidized bed spray granulator, according to the method as disclosed in Japanese Patent O.P.I. Publication No. 109042/1990. Granulated processing chemicals were thus produced, and tests were similarly made. As a result, the solubility of processing chemicals was more improved, and the fog density of color paper was improved by 15 to 20 %.
• Example 1 was repeated except that the layer thickness of PVA-2 (a polyvinyl alcohol water-soluble film) as used in Test No. 1-5 in Example 1 was varied as shown in the following Table 2, and tests were similarly made. Results obtained are shown together in Table 2.
• PVA-2 a polyvinyl alcohol water-soluble film
• the layer thickness of the water-soluble film is in the range of from 10 to 120 ⁇ , and particularly preferably from 15 to 80 ⁇ , and a water-soluble film with a thickness of from 20 to 60 ⁇ gives still particularly good results.
• Example 1 was repeated except that the optical brightening agent (TINOPAL SFP) in the part A of the color developing chemicals used in Test No. 1-6 was replaced with the one as shown in the following Table 2, and tests were similarly made. Results obtained are shown together in Table 3.
• the optical brightening agent TINOPAL SFP
• Example 1 was repeated except that the outer package (polyethylene bag) used therein was replaced with NUCKLE-P (trade name; available from Nippon Unicar Co., Ltd.) or ECHOSTAR (trade name; available from saint Lawrence starch Co.), and tests were similarly made. Results obtained were substantially the same as those in Example 1. It has been confirmed that photographic processing chemical kits have become available using degradable polymer bags, promising that the products are suited to social environment.
• NUCKLE-P trade name; available from Nippon Unicar Co., Ltd.
• ECHOSTAR trade name; available from saint Lawrence starch Co.
• granular processing chemicals (corresponding to the color developing chemicals in Example 1) were produced by the method as disclosed in Japanese Patent O.P.I. Publication No. 109043/1990 or No. 39739/1991, and then put into use.
• the granules were made to have a bulk density as shown in the following Table 4.
• Results obtained are shown together in Table 4.
• the amounts of the components added in the light-sensitive silver halide photographic material are indicated as gram number per 1 m 2 unless particularly noted. Those of silver halides and colloidal silver are indicated in terms of silver.
• the above color negative film further contains compounds Su-1 and Su-2, a viscosity regulator, hardening agents H-1 and H-2, stabilizer ST-1, antifoggants AF-1 and two kinds of AF-2 with weight average molecular weights of 10,000 and 1,100,000. dyes AI-1 and AI-2, and compound DI-1 (9.4 mg/m 2 ).
• the silver iodobromide emulsion used in the tenth layer was prepared in the following manner.
• Solution G-1 shown below was maintained at a temperature of 70°C, pAg 7.8 and pH 7.0, and a seed emulsion corresponding to 0.34 mol was added thereto with thorough stirring.
• H-1 and S-1 shown below were added at accelerated flow rates (flow rate at initial stage: 3.6 times the flow rate at the time the addition was completed) over a period of 86 minutes, while keeping their flow rate ratio at 1:1.
• H-2 and S-2 shown below were added at accelerated flow rates (flow rate at initial stage: 5.2 times the flow rate at the time the addition was completed) over a period of 65 minutes, while keeping their flow rate ratio at 1:1.
• the pAg and pH in the course of the formation of grains were controlled using an aqueous potassium bromide and an aqueous 56 % acetic acid solution. After the formation of grains was completed, washing with water was applied by conventional flocculation. Thereafter, gelatin was added to effect re-dispersion, and the pH and pAg were adjusted to 5.8 and 8.06, respectively, at 40°C.
• the emulsion thus obtained was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 ⁇ m, a breadth of distribution of 12.4 % and a silver iodide content of 8.5 mol %.
• Average molecular weight about 1,300.
• the above respective emulsions having different average grain size and silver iodide content were prepared.
• the color film sample thus produced is processed according to the following processing steps. :
• Example 2 Each part of the respective processing chemicals thus prepared was put in the water-soluble film inner package in the same manner as in Example 1. Using the moistureproof packaging material as the outer package therefor, the same tests as in Example 1 were made, provided that, as measurement of density at non-image areas, transmission green density was measured using a photoelectric densitometer. Results obtained are shown together in Table 5.
• aqueous 25 % by weight solution of a composition comprised of 100 parts by weight of polyvinyl alcohol with an average degree of polymerization of 1,200 and a degree of saponification of 99 % and 5 parts by weight of glycerol was casted over a mirror-finished stainless steel plate, followed by drying at 90°C under reduced pressure to form a film with a thickness of 75 ⁇ .
• a solution prepared by dissolving 20 parts by weight of lithium nitrate as an adhesive in 100 parts by weight of a mixed solvent of 60 % by volume of methanol and 40 % by volume of water was coated on one side of one of the film sheet in a coating weight of about 10 g/m 2 , and, immediately thereafter, the other film sheet was superposed thereon, and contact-bonded using rubber rolls, in the state of which the bonded film sheets were left to stand for about 1 hour under application of a load.
• a perfectly integral laminated film was produced, having a thickness of 150 ⁇ and a water content of 8 % by weight.
• This laminated film was cut into a sample of 100 x 100 mm.
• Example 3 Using an experimental biaxial stretcher (manufactured by Iwamoto Seisakusho), at a temperature of 130°C and at a stretch rate of 30 mm/min, the cut film was successively biaxially stretched by 2.5 times in the longitudinal direction in the primary stretch, 2.5 times in the transverse direction in the secondary stretch, and about 6 times in terms of area stretch ratio, followed by heat treatment fixing at 160°C for 30 seconds to give a stretched film with a thickness of 25 ⁇ .
• water-soluble films with the layer thicknesses as shown in Table 2 of Example 4 were prepared. Except for use of these films, tests were made in the same manner as in Example 4. As a result, substantially the same results as in Example 3 were obtained.
• the above color developing chemicals (powdered processing chemicals for a 10 liter developing solution) were each put in the inner package as shown in Table 6, and then all the package was put in the outer package as shown in Table 6 to make storage tests.
• the storage tests were made under conditions of 50°C and 65 % RH for 1 month.
• the processing chemicals were dissolved using a chemical mixer, and then developing was carried out.
• the outer package was cut open with a cutter, and the whole inner package was put into water to dissolve the processing chemicals. On that occasion, whether or not the powder flew up and how the powdered chemicals dissolved were observed. After developing, reflection green densities at non-image areas of color paper samples were measured.
• the powder does not fly during dissolution, the processing chemicals well dissolves, less fogging occurs even after storage of the processing chemicals, and a photographic processing chemical kit capable of giving a satisfactory dye density can be obtained, when the solid photographic processing chemicals are packaged with the water-soluble film and the whole is further packaged with the moistureproof packaging material.
• bleach-fixing chemicals for color papers were thoroughly mixed to produce powdered processing chemicals for a 10 liter bleach-fixing solution.
• the bleach-fixing chemicals thus prepared were put in the same inner package and outer package as those shown in Table 6 of Example 10, and then the storage stability was similarly tested. As a result, substantially the same results as in Example 10 were obtained in respect of the deposition of crystals, the flying of powder during dissolution and the solubility of processing chemicals.
• Example 1 was repeated except that the color developing chemicals used therein were granulated using a commercially available fluidized bed spray granulator, according to the method as disclosed in Japanese Patent O.P.I. Publication No. 109042/1990. Granulated processing chemicals were thus produced, and tests were similarly made. As a result, the solubility of processing chemicals was more improved, and the fog density of color paper was improved by 20 to 30 %.
• Example 10 was repeated except that the layer thickness of PVA-2 (a polyvinyl alcohol water-soluble film) as used in Test No. 10-5 in Example 10 was varied as shown in the following Table 7, and tests were similarly made. Results obtained are shown together in Table 7.
• PVA-2 a polyvinyl alcohol water-soluble film
• the layer thickness of the water-soluble film is in the range of from 10 to 120 ⁇ , and particularly preferably from 15 to 80 ⁇ and a water-soluble film with a thickness of from 20 to 60 ⁇ gives still particularly good results.
• Example 10 was repeated except that the optical brightening agent (TINOPAL SFP) in the color developing chemicals used in Test No. 10-6 was replaced with the one as shown in the following Table 8, and tests were similarly made. Results obtained are shown together in Table 8.
• the optical brightening agent TINOPAL SFP
• Example 10 was repeated except that the outer package (polyethylene bag) used therein was replaced with NUCKLE-P (trade name; available from Nippon Unicar Co., Ltd.) or ECHOSTAR (trade name; available from saint Lawrence starch Co.), and tests were similarly made. Results obtained were substantially the same as those in Example 10. It has been confirmed that photographic processing chemical kits have become available using degradable polymer bags, promising that the products are suited to social environment.
• NUCKLE-P trade name; available from Nippon Unicar Co., Ltd.
• ECHOSTAR trade name; available from saint Lawrence starch Co.
• granular processing chemicals (corresponding to the color developing chemicals in Example 10) were produced by the method as disclosed in Japanese Patent O.P.I. Publication No. 109043/1990 No. 39739/1991, and then put into use.
• the granules were made to have a bulk density as shown in the following Table 9.
• Results obtained are shown together in Table 9.
• a color negative film was produced in the same manner as in Example 8 except that the magenta coupler M-B was replaced with M-C shown below.
• the amounts of the components added in the light-sensitive silver halide photographic material are indicated as gram number per 1 m 2 unless particularly noted. Those of silver halides and colloidal silver are indicated in terms of silver.
• the color film sample thus produced is processed according to the following processing steps.
• the stabilizing chemicals were formed into a slurry by means of a commercially available kneading machine, and then put into use.
• Example 10 Each of the respective processing chemicals thus prepared was put in the water-soluble film inner package in the same manner as in Example 10. Using the moistureproof packaging material as the outer package therefor, the same tests as in Example 10 were made, provided that, as measurement of density at non-image areas, transmission green density was measured using a photoelectric densitometer. Results obtained are shown together in Table 10.
• the present invention makes it possible to provide a photographic processing chemical kit for light-sensitive silver halide photographic materials, that does not require, or greatly decrease, use of plastic bottles and hence can exhibit a suitability to social environment, that can be free from flying up of fine powder of solid photographic processing chemicals and hence can exhibit a suitability to work environment, that has been improved in its storage stability and can better prevent occurrence of stain at non-image areas of light-sensitive silver halide photographic materials, that can better prevent crystals from being deposited at portions at which photographic processing solutions come into contact with machine walls or air in an automatic processor, and also that has been made light-weight because of the processing chemicals formed into solids, promises reduction of transportation cost and requires no wide space for keeping processing chemical kits in photofinishing laboratories.
• a developing agent (CD-3) of a developer of color developing chemicals for color papers was granulated using a commercially available fluidized bed spray granulator by the method as disclosed in Japanese Patent O.P.I. Publication No. 109042/1990 to give a granular developing agent. Thereafter, the granular developing agent was coated with a water-soluble polymer by the conventional method as disclosed in Japanese Patent O.P.I. Publications No. 109042/1990, No. 109043/1990, No. 39735/1991 and No. 39739/1991, and then thoroughly blended with other component chemicals. The resulting blend was used as GRANULATEDed processing chemicals for a 10 liter developing solution.
• the color developing chemicals were put in a polyethylene bag (hereinafter "packaging material") and hermetically packaged to make a storage test.
• the storage test was made under conditions of 50°C and 85 % RH in an autocalve under application of a pressure of 2.0 kg with oxygen gas.
• the developing chemicals were stored for 1.5 months.
• the packaging material was cut with a cutter, and the processing chemicals were emptied into a chemical mixer filled with water, followed by dissolution. During the dissolution, visual observation was made on whether the caking of processing chemicals occurred or how the processing chemicals were dissolved. In respect of color paper samples processed using the resulting color developing solution, reflection red densities at non-image areas were measured.
• the developing tank solution having been used for the color paper processing was dispensed in a quantity of 1,000 ml, which was then put in a 35 cm 2 beaker, and days before occurrence of a tar product at 38°C were observed. Results obtained are shown together in Table 11.
• the color papers were exposed and processed in the same manner as in Example 1, using the same bleach-fixing solution and stabilizing solution as used therein.
• the granular processing chemicals of the present invention can give processing chemicals remarkably improved in anti-caking or solubility, also improved in anti-tar and anti-staining, and promising scratch-free light-sensitive materials after their processing.
• processing chemical kit of the present invention made it unnecessary to use the conventional plastic bottles containing photographic processing liquid concentrates, and has brought about a decrease in the quantity of plastic materials by as much as about 1/5 to 1/30 of those hitherto used. It was also possible to decrease the volume of a processing chemical kit by as much as 1/3 to 1/10.
• Tablet type processing chemicals were produced in the same manner as in Example 17 except that the color developing agent used therein was tableted using a tableting machine which is a modified machine of TOUGHPRESS CORRECT 1527HU (trade name; manufactured by Kikusui Seisakusho, Ltd.). The same test as in Example 17 was also made. As a result, the processing chemicals showed more improved solubility. In addition, it was also found that the present invention is effective for the strength of tablets. Data of the strength of tables are shown together in Table 12.
• the strength of tablets was examined by naturally dropping tablets from a position of 2 m high to visually observe the state of tablets.
• the present invention can be more effective when the developing agent was formed into granules and coated with the soluble polymer.
• the coating weight may preferably be not less than 0.01 g, and more preferably from 1.0 g to 3.0 g.
• processing chemical kit of the present invention also made it unnecessary to use the conventional plastic bottles containing photographic processing liquid concentrates, except for the remaining packaging material, and has brought about a decrease in the quantity of plastic materials by as much as about 1/5 to 1/30 of those hitherto used. It was also possible to decrease the volume of a processing chemical kit by as much as 1/3 to 1/10.
• a developing agent (CD-3) of a developer of color developing chemicals for color papers was granulated using a commercially available fluidized bed spray granulator by the method as disclosed in Japanese Patent O.P.I. Publication No. 109042/1990 to give a granular developing agent. Thereafter, the granular developing agent and other component chemicals were tableted together dividedly into 100 tablets for each 10 liter developing solution, using a tableting machine which is a modified machine of TOUGHPRESS CORRECT 1527HU (trade name; manufactured by Kikusui Seisakusho, Ltd.), to produce tablet type color paper color developing chemicals. The tablet surfaces were further coated with a water-soluble polymer by spray coating.
• the color developing chemicals were put in a polyethylene bag (hereinafter "packaging material") and hermetically packaged to make a storage test.
• the storage test was made under conditions of 50°C and 85 % RH in an autoclave under application of a pressure of 2.0 kg with oxygen gas.
• the developing chemicals were stored for 1.5 months.
• the packaging material was cut with a cutter, and the processing chemicals were emptied into a chemical mixer filled with water, followed by dissolution. During the dissolution, visual observation was made on how the processing chemicals were dissolved. In respect of color paper samples processed using the resulting color developing solution, reflection red densities at non-image areas were measured.
• the color papers were exposed and processed in the same manner as in Example 1, using the same bleach-fixing solution and stabilizing solution as used therein.
• the present invention can achieve a good stability of the photographic processing chemicals, can prevent stain from occurring, and can give tablet type photographic processing chemicals having prevented the trouble of skin irritation from occurring.
• processing chemical kit of the present invention also made it unnecessary to use the conventional plastic bottles containing photographic processing liquid concentrates, and has brought about a decrease in the quantity of plastic materials by as much as about 1/5 to 1/30 of those hitherto used. It was also possible to decrease the volume of a processing chemical kit by as much as 1/3 to 1/10.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (4)

Publications (1)

Family

ID=26449469

Family Applications (1)

Country Status (1)

Cited By (2)

Citations (8)

• 1992
  • 1992-04-15 EP EP92303419A patent/EP0509807A1/de not_active Withdrawn

Patent Citations (8)

Non-Patent Citations (1)

Similar Documents

Legal Events