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(11) | EP 0 509 807 A1 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | Processing chemical kit for light-sensitive silver halide photographic material and method for its dissolution |
| (57) A processing chemical kit for light-sensitive silver halide photographic material
which is packaged with a water-soluble film and outer thereof, is further packaged
with a moistureproof packaging material, is disclosed. Use of the kit made it unnecessary
to use the conventional plastic bottles and has brought about a decrease in the quantity
of plastic material by as much as about 1/5 to 1/30 of those hitherto used. |
FIELD OF THE INVENTION
[0001] 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.
BACKGROUND OF THE INVENTION
[0002] 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. 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).
[0003] 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.
[0004] 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. On the other hand, waste plastic materials are also in an enormous amount. Taking an example in Japan, about 40 % of the whole production is disposed every year. Such waste plastic materials, when thrown away in the ocean, cause a pollution of inhabitation environment for orceanic life. In the area of Europe, waste plastic materials are burnt in incinerators having imperfect exhaust-gas disposal equipment to cause the problem of acid rain or the like.
[0005] For this reason, prompt countermeasures are earnestly sought to be taken. Under existing circumstances, it is active in Europe and America to recycle waste plastic materials or prohibit their dumping, or legally obligate to use degradable plastics.
[0006] Under such circumstances, it is very unpreferable to use plastic bottles in a large quantity for photographic processing chemicals even if their use is a part of the whole.
[0007] Now, one may contemplate to form liquid concentrates into powdered chemicals. In such an instance, there is a high possibility that fine powder rises or flies up when the powdered chemicals are dissolved in water and operators breathe the powder. This may bring about the problem of a possible influence on health, or the problem that any components of the processing chemicals that have flown about mix into other photographic processing solutions to contaminate them to cause troubles. On account of such problems, 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.
SUMMARY OF THE INVENTION
[0008] As a result of various studies, 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.
[0009] The water-soluble film or binder, however, 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.
[0010] To solve this problem, in the present invention, preferably 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.
[0011] To our surprise, it has been confirmed that the storage stability of processing chemicals can be remarkably improved in the case when 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 whole packaged, bound or covered parts are further packaged together using a moistureproof packaging material, compared with the case when photographic processing chemicals are merely packed with a moistureproof packaging material or a water-soluble film. An additional effect has been also confirmed to be obtainable such that less stain is caused at non-image portions of light-sensitive materials after storage of kits when photographic processing is carried out using processing chemicals to which the combination package of the present invention as described above has been applied. Another effect has been also confirmed such that crystals tending to be deposited at portions at which photographic processing solutions come into contact with machine walls or air in an automatic processor can be better prevented when the photographic processing chemical kit of the present invention is used. These are surprizing facts that can not be expected at all from any conventional findings.
[0012] 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.
[0013] 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.
[0014] 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.
[0015] 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.
[0016] 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.
[0017] 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.
DETAILED DESCRIPTION OF THE INVENTION
[0018] To achieve the above objects, the present inventors made extensive studies. As a result, they have discovered that the above objects can be achieved by 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, or 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. In the embodiment B), for example, 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.
[0019] 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.
[0020] In preferred embodiments of the present invention, 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/cm3; 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 µ; 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 binder comprises a material of a polyvinyl alcohol type; h) said water-soluble film has a layer thickness of from 10 to 120 µ; i) said photographic processing chemicals are at least one selected from color developing chemicals, black and white developing chemicals, bleaching chemicals, fixing chemicals, bleach-fixing chemicals and stabilizing chemicals; j) said water-soluble film is thermoplastic; k) said moistureproof packaging material contains at least one selected from polyethylene terephthalate, polyethylene, polypropylene, polystyrene, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and aluminum; l) at least one of said parts of photographic processing chemicals is a part comprising a developing agent and another of them is a part comprising an alkali agent; m) part or the whole of said alkali agent in said photographic processing chemicals is covered with a water-soluble binder; n) said alkali agent is a carbonate; and/or o) part or the whole of said moistureproof packaging material comprises a degradable plastic such as biodegradable plastic or photodegradable plastic.
[0021] Techniques making use of water-soluble films have been hitherto applied to packages for agricultural chemicals, water treatments, detergents, disinfectants, etc., and are disclosed, for example, in Japanese Patent O.P.I. Publications No. 155999/1990, No. 4800/1987, No. 12466/1985 and No. 57700/1986. However, no example is known in respect of the application of such water-soluble films to photographic processing chemicals. It was very surprising that the application of such water-soluble films to photographic processing chemicals brought about the effect of the present invention as described above.
[0022] 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. Of these, 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.
[0023] 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.
[0024] 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.
[0025] As these 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.
[0026] The water-soluble film of the present invention may preferably have a layer thickness of from 10 to 120 µ, more preferably from 15 to 80 µ, and particularly preferably ffrom 20 to 60 µ. This is because a water-soluble film with a thickness smaller than 10 µ 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 µ 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.
[0027] 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.
[0028] The water-soluble film of the present invention may preferably have a tensile strength of from 0.5 x 106 to 50 x 106 kg/m2, more preferably from 1 x 106 to 25 x 106 kg/m2, and particularly preferably from 1.5 x 106 to 10 x 106 kg/m2. This tensile strength can be measured according to the method as prescribed in JIS Z-1521.
[0029] In the present invention, the photographic processing chemicals may be shaped with use of the water-soluble binder by any desired means. For example, 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).
[0030] In the present invention, 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.
[0031] In the present invention, 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 µm. The tablets refer to what has been subjected to the step of compression-molding the above powder into given shapes.
[0032] In the present invention, 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 (processing tablets) 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.
[0033] 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/cm3, and particularly preferably from 0.50 to 0.85 g/cm3, from the view point of its solubility and also in view of the effect as aimed in the present invention.
[0034] In the present invention, in the case when the tablet type solid photographic processing chemicals are used, they may preferably have a bulk specific gravity of from 0.5 to 6.0 g/cm3, and particularly preferably from 1.0 to 2.5 g/cm3.
[0035] 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.
[0036] In the present invention, part or the whole of 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. In such an instance, 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. As 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.
[0037] It is preferable in view of the effect as aimed in the present invention, that the processing chemical kit for light-sensitive silver halide photographic materials (photographic processing chemical kit) 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.
[0038] 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.
Formula S1
Formula S2
[0040]
R1-O-(-R2-0-)m-X1
wherein R1 represents a hydrogen atom or a monovalent organic group; R2 represents an ethylene group, a propylene group or an isopropylene group; m represents an integer of 1 to 100; and X1 represents a hydrogen atom, -SO3M or -PO3M, wherein M represents a hydrogen atom, an alkali metal or an ammonium group.
wherein R9 represents a hydrogen atom, a hydroxyl group, a lower alkyl group, an alkoxyl group,
wherein 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.
X1 and X2 each represent -CH2CH2-, -CH2CH2CH2-,
[0041] In Formula S4, R1 represents a hydroxyalkyl group having 2 to 6 carbon atom; R2 and R3 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.
[0042] Examples of the compound represented by Formula S1 may be benzyl alcohol, methanol, isopropyl alcohol and n-propyl alcohol.
[0043] The compound represented by the above Formula S2 will be described in greater detail. R1 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. R2 represents a substituted or unsubstituted ethylene group or propylene group, and m represents an integer of 4 to 50. X1 represents a hydrogen atom, -SO3M or -PO3M2, wherein M represents a hydrogen atom, an alkali metal atom such as Na, K or Li, or NH4+.
[0046] Of the compound represented by Formula S4, R1 preferably represents a hydroxyalkyl group having 2 to 4 carbon atoms, R2 and R3 each preferably represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 4 carbon atoms.
[0047] 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.
[0048] 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.
[0049] 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 µ. 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.
[0050] Although they are preferable, it it more preferable in the present invention to use a moistureproof packaging material comprised of a degradable plastic, in particular, a biodegradable plastic or a photodegradable plastic.
[0051] 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. In addition to the polymers set forth above, those having at the same time both functions of photodegradation and biodegradation may be included in the present invention.
[0053] Biodegradable plastics may include;
i) Naturally occurring polymers:
Saccharides, celluloses, polylactic acids, chitin, chitosan, and polyamino acids,
or modified products thereof.
ii) Polymers produced by microorganisms:
"Biopol" mainly composed of PHB-PHV (a copolymer of 3-hydroxybutylate and 3-hydroxyvalerate),
and celluloses produced by microorganisms.
iii) synthetic polymers with a good biodegradability:
Polyvinyl alcohol and polycaprolactum, or copolymers or mixture of these.
iv) Plastics into which a biodegradable natural polymer has been incorporated:
Natural polymers with a good biodegradability include starches and celluloses,
which are added to plastics to impart shape collapsibility.
[0054] 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.
[0055] 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.).
[0056] The moistureproof packaging material according to the present invention may preferably have a coefficient of moisture permeation of not higher than 10 g·mm/m2·24 hrs, and preferably not higher than 5 g·mm/m2·24 hrs.
[0057] In the case when the photographic processing chemicals of the present invention is for use in color development, they may preferably be separated into a part comprising a color developing agent and a part comprising an alkali agent. In this instance, 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.
[0058] As the color developing agent used in the color developing chemicals in the present invention, 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.
[0059] 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.
[0060] As to such a water-soluble group, at least one group may be present on the amino group or benzene nucleus of the p-phenylenediamine compound. As specific water-soluble groups, the group may preferably include the following:
-(CH2)n-CH2OH;
-(CH2)m-NHSO2-(CH2)n-CH3;
-(CH2)m-O-(CH2)n-CH3;
-(CH2CH2O)nCmH2m+1;
wherein m and n each represent an integer of 0 or more;
a -COOH group, and a SO3H group.
[0061] 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.
[0062] The color developing agent is used usually in the form of a salt such as hydrochloride, sulfate or p-toluene sulfonate.
[0063] 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.
[0064] In the present invention, not only the effect as aimed in the present invention can be better obtained but also any fogging that may occur in non-image areas can be decreased, when the compound represented by the following Formulas A or B are contained in the color developing chemicals according to the present invention. This is one of preferred embodiments of the present invention.
wherein R1 and R2 each represent an alkyl group or a hydrogen atom, provided that the both R1 and R2 are not hydrogen atoms at the same time. R1 and R2 may also form a ring.
[0065] In Formula A, R1 and R2 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 R1 and R2 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.
[0066] R′ represents an alkoxyl group, an alkyl group or an aryl group. The alkyl group and aryl group represented by R1, R2 and R′ may include those having a substituent, and R1 and R2 may combine to form a ring. For example, they may form a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.
wherein 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-, SO2- 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.
[0067] Examples of the 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.
[0068] Then, referring to examples of the compounds represented by Formula B, they are compounds B-1 to B-33 disclosed in Japanese Patent Application No. 203169/1990, pages 40 to 43 of its specification, and compounds 1 to 56 disclosed in Japanese Patent O.P.I. Publication No. 33846/1991, pages 4 to 6 of its specification.
[0069] 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.
[0070] In the color developing chemicals and black and white developing chemicals according to the present invention, 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.
[0071] In the color developing chemicals and black and white developing chemicals according to the present invention, a buffering agent must be used. 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).
[0072] 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. 43429/1977; p-aminophenols as disclosed in U.S. Patents No. 2,610,122 and No. 4,119,462; amine compounds as disclosed in U.S. Patents No. 2,494,903, No. 3,128,182, No. 4,230,796 and No. 3,253,919 and Japanese Patent Examined Publication No. 11431/1966, U.S. Patents No. 2,482,546, No. 2,596,926 and No. 3,582,346; polyalkylene oxides as disclosed in Japanese Patent Examined Publications No. 16088/1962 and No. 25201/1967, U.S. Patent No. 3,128,183, Japanese Patent Examined Publications No. 11431/1966 and No. 23883/1967 and U.S. Patent No. 3,532,501; as well as 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds,,and imidazoles; any of which may be optionally added.
[0073] 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.
[0074] For the purpose of preventing fog, the color developing chemicals must contain a chloride ion and a bromide ion. In the present invention, 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. On the other hand, 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.
[0075] In the present invention, 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. On the other hand, 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.
[0076] When chloride ions are directly added to the color developing chemicals, 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.
[0077] 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.
[0078] To the color developing chemicals and black and white developing chemicals of the present invention, 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.
[0079] 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. such an optical brightening agent may preferably be a compound represent by the following Formula E.
[0080] In the above formula, X2, X3, Y1 and Y2 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.
[0081] In detail, the groups or substituents thereof in Formula E have the same meaning as what are disclosed in Japanese Patent Application No. 240400/1990, page 63, line 8 from the bottom to page 64, line 3.
[0083] The above compounds can be synthesized by known methods. Of the above exemplary compounds, 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.
[0084] The color developing chemicals and black and white developing chemicals used in the present invention may optionally contain methyl cellosolve, methanol, acetone, dimethylfromamide, β-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.
[0085] Together with the developing agent, an auxiliary developing agent may also be used. such 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.
[0086] Besides, it is also possible to use various additives such as anti-stain agents, anti-sludge agents and interlayer effect accelerators.
[0087] To the color developing chemicals and black and white developing chemicals, 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.
[0088] Of these chelating agents, K-2, K-9, K-12, K-13, K-17 and K-19 may particularly preferably be used. In particular, the present invention can be well effective when K-2 or K-9 are added to the color developing chemicals.
[0089] 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.
[0090] 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.
[0091] If necessary, 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.
[0092] In the case when the photographic processing chemicals according to the present invention are bleaching chemicals or bleach-fixing chemicals, a bleaching agent preferably used is a ferric complex salt of an organic acid represented by the following Formula L, M, N or P.
wherein A1 to A4 may be the same or different one another and each represent -CH2OH, -COOM or PO3M1M2, wherein M, M1 and M2 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.
[0093] The compound represented by Formula L will be detailed below. In the formula, A1 to A4 have the same definition as A1 to A4 described in Japanese Patent Application No. 260628/1989, page 12, line 15 to page 15, line 3, and hence detailed description therefor is omitted.
[0094] Preferred examples of the compound represented by Formula L are shown below.
- L-1
- 1,3-Propanediaminetetraacetic acid
- L-2
- 2-Hydroxy-1,3-propanediaminetetraacetic acid
- L-3
- 2,3-Propanediaminetetraacetic acid
- L-4
- 1,4-Butandiaminetetraacetic acid
- L-5
- 2-Methyl-1,3-propanediaminetetraacetic acid
- L-6
- N-(2-hydroxyethyl)-1,3-propanediaminetetraacetic acid
- L-7
- 1,3-Propanediaminetetrakismethylenephosphonic acid
- L-8
- 2-Hydroxy-1,3-propanediaminetetrakismethylenephosphonic acid
- L-9
- 2,2-Dimethyl-1,3-propanediaminetetraacetic acid
- L-10
- 2,4-Butanediaminetetraacetic acid
- L-11
- 2,4-Pentanediaminetetraacetic acid
- L-12
- 2-Methyl-2,4-pentanediaminetetraacetic acid
[0095] 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.
[0096] Of the above exemplary compounds, particularly preferably be used in the present invention are L-1, L-3, L-4, L-5 and L-9, and still particularly preferably L-1.
[0097] The compound represented by Formula M will be detailed below.
wherein A1 to A4 are the same as those defined in Formula L; n represent an integer of 1 to 8; B1 and B2 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.
[0099] 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.
[0100] Of the organic ferric complex salts of the present invention, 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. In particular, 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.
[0101] The compound represented by Formula N is shown below.
wherein R1 represents a hydrogen atom or a hydroxyl group, n is 1 or 2, x is 2 or 3, y is 0 or 1, and the sum of x and y is always 3.
[0103] The compound represented by Formula P is shown below.
wherein A1 to A4 may be the same or different one another, and each represent -CH2OH, PO3M1M2 or -COOM3, wherein M1 M2 and M3 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 -(B1O)n-B2-. B1 and B2 may be the same or different each other, and each represent a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms.
[0104] The alkylene group represented by X may include ethylene, triethylene and tetramethylene. The alkylene group represented by B1 or B2 may include methylene, ethylene and trimethylene. The substitutent on the alkylene group represented by X, B1 or B2 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.
[0105] Preferred examples of the compound represented by P are shown below. Examples are by no means limited to these.
[0106] In the present invention, besides the 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.
- [A′-1]
- Ethylenediaminetetraacetic acid
- [A′-2]
- Trans-1,2-cyclohexanediaminetetraacetic acid
- [A′-3]
- Dihydroxyethylglycidic acid
- [A′-4]
- Ethylenediaminetetrakismethylenephosphonic acid
- [A′-5]
- Nitrilotrismethylenephosphonic acid
- [A′-6]
- Diethylenetriaminepentakismethylenephosphonic acid
- [A′-7]
- Diethylenetriaminepentaacetic acid
- [A′-8]
- Ethylenediaminediorthohydroxyphenylacetic acid
- [A′-9]
- Hydroxyethylenediaminetriacetic acid
- [A′-10]
- Ethylenediaminedipropionic acid
- [A′-11]
- Ethylenediaminediacetic acid
- [A′-12]
- Hydroxyethyliminodiacetic acid
- [A′-13]
- Nitrilotriacetic acid
- [A′-14]
- Nitrilotripropionic acid
- [A′-15]
- Triethylenetetraminehexaacetic acid
- [A′-16]
- Ethylenediaminetetrapropionic acid
[0107] 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.
[0108] 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.
[0109] Besides the above accelerators, it is also possible to similarly use the exemplary compounds as disclosed in Japanese Patent O.P.I. Publication 123459/1987, pages 51 to 115 of its specification, the exemplary compounds as disclosed in Japanese Patent O.P.I Publication 17445/1985, pages 22 to 25 of its specification, and the compounds as disclosed in Japanese Patent O.P.I. Publications No. 95630/1978 and No. 28426/1978.
[0110] Besides the foregoing, 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.
[0111] As a fixing agent used in the fixing chemicals or bleach-fixing chemicals according to the present invention, 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. In the case when color negative films are processed, 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. In the present invention, the objects of the present invention can be more effectively achieved when the thiocyanate and thiosulfate are used in combination.
[0112] In addition to such a fixing agent, 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.
[0113] The compound represented by the following Formula FA, disclosed in Japanese Patent O.P.I. Publication No. 295258/1989, page 56 of its specification, together with its exemplary compounds, 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.
[0114] 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.
[0115] 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.
[0116] In the present invention, the stabilizing chemicals may preferably contain a chelating agent having a chelate stability constant with respect to iron ions, of not less than 8. Here, 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).
[0117] 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.
[0118] 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.
[0119] 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.
[0121] The stabilizing chemicals may preferably also contain a metal salt used in combination with the above chelating agent. such 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.
[0122] To the stabilizing chemicals, it is also possible to add 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. In the present invention, 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.
[0123] The light-sensitive material to which the processing chemicals of the present invention are applied will be described below.
[0124] In the case when the light-sensitive materials are light-sensitive material for photographing, 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 %. In particular, 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 %.
[0125] In the light-sensitive silver halide color photographic material used in the present invention, 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.
[0126] Silver halide emulsions having been subjected physical ripening, chemical ripening and spectral sensitization are used. Additives used in such steps are described in Research Disclosures No. 17643, No. 18716 and No. 308119 (hereinafter "RD17643", "RD18716" and "RD308119", respectively).
[0128] Photographic additives are also described in the above Research Disclosures. Items described and paragraphs thereof are shown in the following table.
[0129] Various 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.
[0131] In the present invention, the supports as described in the aforesaid RD17643, page 28, RD18716, pages 647 to 648 and RD308119, Paragraph XIX can be used.
[0132] 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.
[0133] A preferred color light-sensitive material to which the photographic processing chemicals of the present invention are applied will be described below.
[0134] 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 %.
[0135] 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. In this instance, 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 %. In the case when silver iodide is present, 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.
[0136] 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. With regard to the crystal structure, 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.
[0137] The silver halide grains may be those obtained by any preparation method such as the acid method, the neutral method or the ammonia method.
[0138] 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. When the silver halide grains are grown, it is preferred to control the pH, pAg, etc. in a reaction vessel and to successively and simultaneously add and mix silver ions and halide ions in the amounts corresponding to the rate of growth of silver halide grains, as in the manner disclosed, for example, in Japanese Patent O.P.I. Publication No. 48521/1979.
[0139] In the case when the light-sensitive material processed using the photographic processing chemicals of the present invention is for use in color photography, silver halide emulsion layers contain color couplers.
[0140] 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 α-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.
[0141] In the color light-sensitive material to which the photographic processing chemicals of the present invention is applied, two-equivalent couplers are particularly preferred.
[0142] Suitable couplers are disclosed in the following publications: W. Pelz, "Farbkuppler (Color Couplers)" in Mitteilunglnausden Forschungslaboratorien 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.
[0143] In the color light-sensitive material to which the photographic processing chemicals of the present invention is applied, it is particularly preferred in view of the effect as aimed in the present invention, in particular, the rapid-processing performance, to use in combination with the light-sensitive material of the present invention the 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. 106655/1985), the cyan couplers represented by Formula C-I or C-II also described on pages 34 (including as specific exemplary cyan couplers, the compounds C′-1 to C′-82 and C˝-1 to C˝-36 described on pages 37 to 42 of the specification in same the publication), the high-speed yellow couplers also described on page 20 (including as specific exemplary yellow couplers, the compounds Y′-1 to Y′-39 described on pages 21 to 26 of the specification in the same publication and the compounds Y-1 to Y-31 described on pages 280 to 283 of the specification in Japanese Patent O.P.I. Publication No. 180542/1989).
EXAMPLES
Example 1
[0145] The following color developing chemicals for color papers were thoroughly mixed, and used as powdered processing chemicals for a 10 liter developing solution.
- Powdered processing chemicals for 10 liter developing solution; color developing chemicals -
(Part A)
(Part B)
(Part C)
[0149] 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. Thereafter, the processing chemicals were dissolved using a chemical mixer, and then developing was carried out. Here, 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. After developing, reflection yellow densities at maximum density areas and non-image areas of color paper samples were measured. A portion of 1 liter of the color developing solution obtained after dissolution was taken out and put in a container with an open top area of 10 cm2, made of hard vinyl chloride. This developing solution was stored at room temperature for 3 weeks, and thereafter observed to examine whether or not any deposition of crystals occurred at the boundary where the container wall came in contact with the surface of the developing solution inside the container. Results obtained are shown in together in Table 1. The following was used as the color paper.
- Color paper -
[0150] Layers with the following constitution were provided on a paper support to one side of which polyethylene was laminated and to the other side of which, the first layer side, polyethylene containing titanium oxide was laminated. A color paper thus obtained was used.
First-layer coating solution:
[0151] In 0.67 g of high-boiling solvent (DNP), 26.7 g of of yellow coupler Y-1, 10 g and 6.67 g of dye-image stabilizing agents ST-1 and ST-2, respectively, and 0.67 g of additive HQ-1 were dissolved with addition of 60 ml of ethyl acetate. The resulting solution was emulsifyingly dispersed in 220 ml of aqueous 10 % gelatin solution containing 7 ml of surface active agent SU-1, using an ultrasonic homogenizer, to produce a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 10 g of silver) produced under conditions as shown later. A first-layer coating solution was thus prepared.
[0152] Second- to seventh-layer coating solutions were also prepared in the manner similar to the above first-layer coating solution.
[0153] A hardening agent H-1 was also added to the second layer and the fourth layer each, and H-2, to the seventh layer. As coating aids, surface active agents SU-2 and SU-3 were added to adjust surface tension.
Preparation of blue-sensitive silver halide emulsion:
[0154] In 1,000 ml of an aqueous 2 % gelatin solution kept at a temperature of 40°C, the following solution A and solution B were simultaneously added in 30 minutes while controlling the pAg and pH to be 6.5 and 3.0,
respectively, and the following solution C and solution D were further simultaneously added over a period of 180 minutes while controlling the pAg and pH to be 7.3 and 5.5, respectively.
[0155] At this time, 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.
Solution A:
Solution B:
Solution C:
Solution D:
[0160] After completion of the addition, 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 µm, a variation coefficient (σ/r) of 0.07 and a silver chloride content of 99.5 mol %.
[0161] 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.
Preparation of green-sensitive silver halide emulsion:
[0162] 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 µm, a variation coefficient (σ/r) of 0.08 and a silver chloride content of 99.5 mol %.
[0163] 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.
Preparation of red-sensitive silver halide emulsion:
[0164] 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 µm, a variation coefficient (σ/r) of 0.08 and a silver chloride content of 99.5 mol %.
[0165] 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.
[0166] The sample thus obtained was subjected to wedge exposure by a conventional method, and then processed under the following conditions.
[0168] As a color developing solution, the solution obtained by dissolving the color developing chemicals after its storage was used.
[0169] As 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.
[0170] As a stabilizing solution, 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.
[0171] In Table 1, PVA-1 denotes a polyvinyl alcohol water-soluble film (trade name: HICELLON S-Type, 30 µ; available from Nichigo Film Co., Ltd.); PVA-2, a polyvinyl alcohol water-soluble film (trade name: SOLUBLON PH, 30µ; Aicello Chemical Co., Ltd.); PVA-3, a polyvinyl alcohol water-soluble film (trade name: SOLUBLON PW, 40µ; Aicello Chemical Co., Ltd.); PVA-4, a polyvinyl alcohol water-soluble film (trade name: HICELLON C-Type 30 µ; available from Nichigo Film Co., Ltd.); and PL-1, a pullulan film (a natural polysaccharide having glucose as a minimum unit, 20 µ; available from Hayashibara Company, Ltd.). In Table 1, in the item "Deposition of crystals", "A" indicates that no deposition of crystals is seen as a good result; "B", slightly seen; and "C", so conspicuous as to be problematic. The larger the number of "C" is, the worse the results are.
[0172] With regard to the item "Flying of powder during dissolution", "A" indicates that no flying at all; and "C", flying is slightly seen. The larger the number of "C" is, the worse the results are.
[0173] With regard to the item "Solubility of processing chemicals", "A" indicates that the chemicals immediately dissolves; and "C", it takes a long time to dissolve. The larger the number of "C" is, the worse the results are.
[0174] As is seen from Table 1, 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.
[0175] Moreover, use of the photographic processing chemical kit of the present invention makes it unnecessary to use the plastic bottles conventionally used to hold therein photographic processing concentrated solutions, and leaves only the outer packages moistureproof bags. As a result, the quantity of use of plastics decreased to as much as 1/5 to 1/30. The volume of the processing chemical kit has been reduced to 1/3 to 1/10.
Example 1-a
[0176] 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.
Example 2
[0177] The following bleach-fixing chemicals for color papers were thoroughly mixed to produce powdered processing chemicals for a 10 liter bleach-fixing solution.
- Powdered processing chemicals for 10 liter bleach-fixing solution; bleach-fixing chemicals -
(Part A)
(Part B)
[0180] 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 3
[0181] 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 4
[0182] 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.
[0183] As is seen from Table 2, in the present invention, good results are obtained when the layer thickness of the water-soluble film is in the range of from 10 to 120 µ, and particularly preferably from 15 to 80 µ, and a water-soluble film with a thickness of from 20 to 60 µ gives still particularly good results.
Example 5
[0184] 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.
Experimental optical brightening agent (1)
Experimental optical brightening agent (2)
Experimental optical brightening agent (3)
[0189] As is seen from Table 3, use of a specific optical brightening agent in combination in the processing chemical kit of the present invention brings about better effects of the present invention.
Example 6
[0190] 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.
Example 7
[0191] With regard to Test No. 1-7 in Example 1, 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. Here, the granules were made to have a bulk density as shown in the following Table 4. Using this granular processing chemicals, the same tests as in Example 1 were made. Results obtained are shown together in Table 4.
[0192] As is seen from Table 4, particularly good results can be obtained when the solid processing chemicals in the photographic processing chemical kit of the present invention have a bulk density of from 0.4 to 0.95 g/cm3, and still particularly good results, a bulk density of from 0.5 to 85 g/cm3.
Example 8
[0194] In the following, the amounts of the components added in the light-sensitive silver halide photographic material are indicated as gram number per 1 m2 unless particularly noted. Those of silver halides and colloidal silver are indicated in terms of silver.
- Color negative film -
[0195] One side (the front) of a triacetylcellulose film support (thickness: 50 µ) was subbed. Then, with the support between, on the opposite side (the back) of the surface having been subbed, the following layers were formed successively from the support side.
Back-side first layer:
[0197] Subsequently, on the surface having been subbed, of the triacetylcellulose film, the following layers were formed successively from the support side. Thus a multilayer light-sensitive color photographic material a-1 was produced.
[0198] 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/m2).
Compound A
Compound B
Preparation of emulsions
[0202] The silver iodobromide emulsion used in the tenth layer was prepared in the following manner.
[0203] Using, as seed crystals, monodisperse silver iodobromide grains with an average grain size of 0.33 µm (silver iodide content: 2 mol %) were prepared by double-jet precipitation.
[0204] 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.
(Formation of inside iodide-rich phase, core phase)
[0205] Thereafter, 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.
(Formation of outside phase with low iodide content, shell phase)
[0206] Subsequently, while maintaining the pAg and pH at 10.1 and 6.0, respectively, 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.
[0207] 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.
[0208] The emulsion thus obtained was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 µm, a breadth of distribution of 12.4 % and a silver iodide content of 8.5 mol %.
Compound-1
[0210] According to the same procedure, but changing the average grain size of seed grains, the temperature, the pAg, the pH, the flow rate, the addition time and the halide composition, the above respective emulsions having different average grain size and silver iodide content were prepared.
[0211] All of them were core/shell type monodisperse emulsions with a breadth of distribution of 20 % or less Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and then spectral sensitizers, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added.
[0212] The color film sample thus produced is processed according to the following processing steps. :
- Color developing chemicals - (Powdered processing chemicals for 1 liter developing solution)
(Part A)
(Part B)
(Part C)
- Bleach-fixing chemicals - (Powdered processing chemicals for 1 liter bleach-fixing solution)
(Part A)
(Part B)
- Stabilizing chemicals - (Liquid and powdered processing chemicals for 1 liter stabilizing solution)
(Part A)
(Part B)
[0220] 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.
X: Comparative Example
[0221]
(a): Bleach-fixing chemicals caused sulfiding.
(b): All processing chemicals absorbed moisture and solidified.
Y: Present Invention
[0222] In Table 5, PVA-1 to -4 and PL-1 denote the same as in Table 1 of Example 1. The above Table 5 clearly show the effect of the present invention.
Example 9
[0223] An 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 µ. To laminate two film sheets thus formed, 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/m2, 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. Thus a perfectly integral laminated film was produced, having a thickness of 150 µ and a water content of 8 % by weight. This laminated film was cut into a sample of 100 x 100 mm. 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 µ. In the same way, 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.
Example 10
[0224] The following color paper color developing chemicals were thoroughly mixed, and used as powdered processing chemicals for a 10 liter developing solution.
- Powdered processing chemicals for 10 liter developing solution; color developing chemicals -
[0226] 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. Thereafter, the processing chemicals were dissolved using a chemical mixer, and then developing was carried out. Here, 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. A portion of 1 liter of the color developing solution obtained after dissolution was taken out and put in a container with an open top area of 10 cm2, made of hard vinyl chloride. This developing solution was stored at room temperature for 3 weeks, and thereafter observed to examine whether or not any deposition of crystals occurred at the boundary where the container wall came in contact with the surface of the developing solution inside the container. Results obtained are shown in together in Table 6. The color paper was prepared in the same manner as previously described, except for the formation of the third layer as shown below. After the test exposure, developing was also carried out in the same way. Evaluation was made and its results were indicated also in the same way.
[0227] As is seen from Table 6, 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.
[0228] Moreover, use of the photographic processing chemical kit of the present invention makes it unnecessary to use the plastic bottles conventionally used to hold therein photographic processing concentrated solutions, and leaves only the outer packages moistureproof bags. As a result, the quantity of use of plastics decreased to as much as 1/5 to 1/30. The volume of the processing chemical kit has been reduced to 1/3 to 1/10.
Example 11
[0229] The following bleach-fixing chemicals for color papers were thoroughly mixed to produce powdered processing chemicals for a 10 liter bleach-fixing solution.
- Powdered processing chemicals for 10 liter bleach-fixing solution; bleach-fixing chemicals -
[0231] 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 12
[0232] 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 13
[0233] 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.
[0234] As is seen from Table 7, in the present invention, good results are obtained when the layer thickness of the water-soluble film is in the range of from 10 to 120 µ, and particularly preferably from 15 to 80 µ and a water-soluble film with a thickness of from 20 to 60 µ gives still particularly good results.
Example 14
[0235] 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.
[0236] Experimental optical brightening agents (1) to (3) in Table 8 are the same as those used in Example 5.
[0237] As is seen from Table 8, use of a specific optical brightening agent in combination in the processing chemical kit of the present invention brings about better effects of the present invention.
Example 15
[0238] 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.
Example 16
[0239] With regard to Test No. 10-7 in Example 10, 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. Here, the granules were made to have a bulk density as shown in the following Table 9. Using this granular processing chemicals, the same tests as in Example 10 were made. Results obtained are shown together in Table 9.
[0240] As is seen from Table 9, particularly good results can be obtained when the solid processing chemicals in the photographic processing chemical kit of the present invention have a bulk density of from 0.4 to 0.95 g/cm3, and still particularly good results, a bulk density of from 0.5 to 85 g/cm3.
Example 16a
[0241] 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.
[0242] In the following, the amounts of the components added in the light-sensitive silver halide photographic material are indicated as gram number per 1 m2 unless particularly noted. Those of silver halides and colloidal silver are indicated in terms of silver.
[0243] The color film sample thus produced is processed according to the following processing steps.
- Color developing chemicals - (Powdered processing chemicals for 1 liter developing solution)
[0244]
- Sodium sulfite
- 3.5 g
- Hydroxylamine sulfate
- 2.8 g
- Sodium bromide
- 1.3 g
- Potassium iodide
- 0.6 mg
- Bleaching chemicals - (Powdered processing chemicals for 1 liter bleaching solution)
- Fixing chemicals - (Powdered processing chemicals for 1 liter fixing solution)
- StabilizIng chemicals - (Slurry processing chemicals for 1 liter stabilizing solution)
[0248] The stabilizing chemicals were formed into a slurry by means of a commercially available kneading machine, and then put into use.
[0249] 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.
[0250] In Table 10, PVA-1 to -4 and PL-1 denote the same as in Table 6 of Example 10. The above Table 10 clearly show the effect of the present invention.
[0251] As having been described above, 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.
Example 17
[0252] 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.
- Granulated processing chemicals for 10 liter developing solution; color developing chemicals -
[0254] 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.
[0255] After the storage, 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.
[0256] 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 cm2 beaker, and days before occurrence of a tar product at 38°C were observed. Results obtained are shown together in Table 11.
[0257] Here, 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.
[0258] Letter symbols denote the following:
- PVA-1
- A water-soluble polymer of polyvinyl alcohol (trade name: HICELLON S-Type 30 µ; available from Nichigo Film Co., Ltd.)
- PVA-2
- A water-soluble polymer of polyvinyl alcohol (trade name: SOLVLON PH 30 µ; available from Aicello Chemical Co., Ltd.)
- PVA-3
- A water-soluble polymer of polyvinyl alcohol (trade name: SOLVLON PW 40 µ; available Aicello Chemical Co., Ltd.)
- PVA-4
- A water-soluble polymer of polyvinyl alcohol (trade name: HICELLON C-Type 30 µ; available from Nichigo Film Co., Ltd.)
- PLA-1
- Pullulan Film (trade name: a natural polysaccharide 20 µ; comprised of glucose as a minimum unit; from Hayashibara Company, Ltd.)
- Criterions of evalutation -
[0259] Caking :
- AA:
- Good in entirety.
- A:
- Slightly seen.
- B:
- Slightly seen, with a little large mass.
- C:
- Caking occurred.
The more the number of C is, the larger the number and size of caking is.
Solubility:
[0260]
- AA:
- Immediately soluble.
- A:
- Soluble.
- B:
- Slowly soluble.
- C:
- Insoluble matters remain.
The more the number of C is, the more the insoluble matters remain.
Deposition of crystals:
[0261]
- A:
- No deposition of crystals is seen; good.
- B:
- Slightly seen.
- C:
- So conspicuous as to be problematic.
The more the number of C is, the worse its state is.
[0262] As is clear from Table 11, 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.
[0263] Use of the 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.
Example 18
[0264] 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.
[0265] The strength of tablets was examined by naturally dropping tablets from a position of 2 m high to visually observe the state of tablets.
- Evaluation -
strength of tablets:
[0266]
- AA:
- Not broken at all
- A:
- A little broken on their edges (probability: 2 %)
- B:
- A little broken on their edges (probability: 10 %)
- C:
- Broken.
The more the number of C is, the more the tablets had broken.
[0267] As is clear from Table 12, 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.
[0268] Use of the 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.
Example 19
[0269] 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.
- Color developing chemicals for 10 liter developing solution -
[0271] 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.
[0272] After the storage, 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.
[0273] Here, 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.
Letter symbols denote the following:
[0275]
- PVA-1
- A water-soluble polymer of polyvinyl alcohol (trade name: HICELLON S-Type; available from Nichigo Film Co., Ltd.)
- PVA-2
- A water-soluble polymer of polyvinyl alcohol (trade name: SOLVLON PH; available from Aicello Chemical Co., Ltd.)
- PVA-3
- A water-soluble polymer of polyvinyl alcohol (trade name: SOLVLON PW; available Aicello Chemical Co., Ltd.)
- PVA-4
- A water-soluble polymer of polyvinyl alcohol (trade name: HICELLON C-Type; available from Nichigo Film Co., Ltd.)
- PL-4
- Pullulan (trade name: a natural polysaccharide comprised of glucose as a minimum unit; available from Hayashibara Company, Ltd.)
- Criterions of evaluation -
Skin irritation:
[0276]
- A
- No trouble of skin irritation occurs.
- B
- Trouble of skin irritation occurs when touched for a long time.
- C
- Trouble of skin irritation occurs.
[0277] As is clear from Table 13, 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.
[0278] Use of the 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.
1. A processing kit for a light-sensitive silver halide photographic material comprising
a photographic processing chemical enclosed within a water-soluble film, said enclosure
being packaged with a moistureproof packaging material.
2. A processing kit for a light-sensitive silver halide photographic material comprising
a processing chemical coated with, or bound with, a water-soluble binder, said chemical
being packaged with a moistureproof packaging material.
3. A kit according to claim 2 wherein the water-soluble binder is a polyvinyl alcohol
or polysaccharide binder.
4. A kit according to any one of claims 1 to 3 wherein the photographic processing chemical
is solid.
5. A kit according to claim 4 wherein the photographic processing chemical is a powder,
a granule, a tablet or a block.
6. A kit according to claim 1, 2 or 3 further comprising an organic solvent.
7. A kit according to any one of the preceding claims which comprises at least two parts,
one of which comprises the photographic processing chemical enclosed with the water-soluble
film.
8. A processing kit for a light-sensitive silver halide photographic material comprising:
a plurality of photographic processing chemicals at least two of which are coated with a water-soluble film or bound with a water-soluble binder; said chemicals being packaged with a moistureproof packaging material, the photographic processing chemicals being in the form of a powder, granules, tablets or blocks.
a plurality of photographic processing chemicals at least two of which are coated with a water-soluble film or bound with a water-soluble binder; said chemicals being packaged with a moistureproof packaging material, the photographic processing chemicals being in the form of a powder, granules, tablets or blocks.
9. A kit according to any one of claims 1 and 4 to 8, wherein the water-soluble film
is a polyvinyl alcohol, methyl cellulose, polyethylene oxide, starch, polyvinyl pyrrolidone,
hydroxypropyl cellulose, polysaccharide, dextran or gum arabic film.
10. A kit of claim 9, wherein the thickness of the water-soluble film and/or moisture
proof packaging material is 10 to 150 µm.
11. A kit according to any one of the preceding claims wherein the water-soluble film
is thermoplastic.
12. A kit according to any one of the preceding claims wherein the waterproof packaging
material is a polyethylene terephthalate, polyethylene, polypropylene, polystyrene,
polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile or aluminium.
13. A kit according to any one of claims 1 to 11 wherein the moistureproof packaging material
is a biodegradable plastic or a photodegradable plastic.
14. A kit according to any one of the preceding claims wherein the photographic processing
chemical is a color developing chemical, black and white developing chemical, bleaching
chemical, fixing chemical, bleach-fixing chemical, or a stabilizing chemical.
15. A kit according to any one of the preceding claims wherein a mixture of photographic
processing chemicals is present.
16. A kit according to any one of the preceding claims wherein the photographic processing
chemical containing an alkali compound which is, or a part of which is, coated with
the water-soluble binder.
17. A kit according to claim 16, wherein the alkali compound is a carbonate.
18. A kit according to any one of the preceding claims wherein the photographic chemicals
are granules having a bulk density of 0.40 to 0.95 g/cm3.
19. A kit according to any one of claims 1 to 17 wherein the photographic chemicals are
tablets having a bulk density of 1.0 to 2.5 g/cm3.