Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
  • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets

Definitions

• This invention relates to a solid chemical for silver halide photographic light sensitive material (hereinafter referred also to as a light sensitive material), which is stable and uniformly contains the microconstituent components therein.
• Silver halide photographic light sensitive materials are usually subject to a development process by making use of the following processing solutions, namely, a black-and-white developer, a fixer, a color developer, a bleacher, a bleach-fixer and a stabilizer, so that images can be obtained imagewise.
• processing solutions namely, a black-and-white developer, a fixer, a color developer, a bleacher, a bleach-fixer and a stabilizer, so that images can be obtained imagewise.
• Each processing solution used there is put into a plastic-made bottle, in the form of a single concentrated solution part or plural parts thereof and is then supplied to the users as a processing chemical kit, so that they can easily be handled.
• the users dissolve the processing kit in water so as to prepare a solution (as a starting or replenishing solution) and then use them.
• the plastics are light in weight and strong in quality, they have been widely used not only for the bottles for photographic processing use, but also for the other purposes.
• the plastic outputs of the whole world have continuously been increased year by year and, in 1988, the yearly outputs thereof has reached over one hundred million tons.
• the plastic wastes have become seriously huge.
• Japan for example, about 40% of the outputs have been wasted yearly.
• the oceanic life environments are spoiled.
• the problems such as acid rain troubles are raised because the trash burning treatments are made at the imperfect gas exhaustion facilities. Therefore, many serious problems have been raised.
• JP OPI Publication No. 51-61837/1976 proposes a technique fortableting a processing chemical so as to utilize the advantages of the chemicals in a dry state.
• these tablet type photographic processing chemicals are not comprised of one and single tablet, but are comprised of the separated tablets. Because of the separated tablets, in a color developer, for example, two parts, which are double as much as the single tablets, should be added by an additional device. Therefore, another serious problem is raised from the viewpoint of making an automatic processor be compact in size.
• These tablets have the following defects that any satisfactory characteristics cannot be obtained as a photographic processing tablet; a defect that the preservability of the tablets are deteriorated, for example, in the case of the tablets for color development use, the developing agents thereof are reacted to be so oxidized as to produce a tar-like insoluble products in the course of the preservation, or, in the case of a bleach-fixer or a tablet for fixing use, an insoluble matter such as sulfur or a sulfide is produced.
• an additive such as an antifoggant is ordinarily used.
• These additives are used in a minute amount (such as an amount of not more than 1 g/liter in general), so that a satisfactory effect can be displayed. Accordingly, the characteristics of a processing solution are greatly influenced by only varying a minute amount thereof added. It is, therefore, required to delicately control the com- poundings of the additives.
• the conventional methods in which the above-mentioned powdered additives are added into the other photographic processing powder or granules it has been difficult to control the amounts thereof added and it has therefore been unable to solve the above-mentioned problems.
• the term, 'the solid chemicals of the invention for silver halide photographic light sensitive material use', means herein the granular type chemicals and the tablet type chemicals thereof.
• the granular type processing chemicals means a solid type chemical having a particle size within the range of not smaller than 100wm and 2000 ⁇ m and desirably 300wm and 1000wm.
• a 'tablet' means herein those prepared by pressing the above-mentioned granules or powder so as to mold into a specific configuration.
• Another object of the invention is to eliminate the use of any plastic-made bottles for a liquid type chemical, to prevent any bad influences of the powdered chemicals on human bodies and to solve the troubles produced in any photographic processes.
• a solid chemicals for light sensitive material use which is prepared by uniformly adding a minute amount each of at least one or more kinds of the components of the photographic processing chemicals into at least one kind of the chemicals for photographic processing use.
• the objects of the invention can be achieved with a solid chemicals prepared in the following method of preparing the solid chemicals.
• the primary processing chemicals thereof are each coated with a minute amount of a photographic processing chemical component by making use of a coating agent and the coated chemicals are then so compressed as to be tableted; or, the granules thereof prepared by making use of a binder are coated with a coating agent so that the solid chemicals for light sensitive material use can be prepared.
• a preferred embodiment of the invention is, for example, a solid chemical prepared in the following method of preparing a solid chemical.
• the primary processing chemicals thereof are added with a minute amount of a photographic processing chemical in a proportion within the range of 5 to 10% (by weight) to the primary processing chemicals and they are mixed up uniformly, further, the mixture is added with the primary processing chemicals one after another and mixed up repeatedly so as to make the total amount. After they are granulated in a wet process and dried, the dried granules are compressed and then tableted; or, they are granulated by making use of a binder.
• Another preferred embodiment of the invention is, for example, a solid chemical for light sensitive material prepared in the following solid chemical preparation method.
• the primary processing chemicals thereof are added with a minute amount of a photographic processing chemical in a proportion within the range of 5 to 10% (by weight) to the primary processing chemicals and mixed up uniformly and the mixing- up thereof are repeatedly and the primary processing chemicals are added thereto one after another so as to make the total amount. After that, they are dry-increased in a dried state and the granules are prepared or the granules prepared in a dry process are compressed so as to be tableted.
• the weight ratio of the minute amount of a photographic processing chemical to the primary processing chemical is from 1/20 to 1/5000, preferably from 1/20 to 1/1000 and more preferably, from 1/20 to 1/500.
• a'minute granular component' means a component in an amount of not more than 1/50 of a total increased amount.
• the minute granular components are to be within the range of 1/100 to 1/20000 and, preferably, 1/150 to 1/15000.
• the processing chemicals of the invention for silver halide photographic light sensitive materials can be prepared in any ordinary methods such as those detailed in JP OPI Publication Nos. 51-61837/1976, 54-155038/1979 and 52-88025/1977, British Patent No. 1,213,808 and so forth.
• the photographic minute amount components in the invention mean the additives well-known in the skilled in the art. They include, for example, a development accelerator, an antifoggant, a fluorescent whitening agent, an antistaining agent and an antisludging agent.
• the other photographically effective components include the ordinary photographic additives.
• the processing tablets of the invention for silver halide photographic light sensitive materials include, for example, a color developer, a black-and-white developer, a bleacher, a fixer, a bleach-fixer, a stabilizer and so forth.
• a p-phenylenediamine type compound having a water-soluble group may preferably be used, because the effects of the invention can be excellently displayed and few fog can be produced thereby.
• p-phenylenediamine type compounds each having a water-soluble group have not only the advantages that no contamination of any light sensitive materials can be produced and that no skin can be suffered by dermatitis even if it comes into contact with the skin, but also the objects of the invention can effectively be achieved particularly when making use of the processing tablets of the invention.
• the color developers relating to the invention when the color developers relating to the invention contain the compounds represented by the following Formulas [A] and [B], it can be one of the preferred embodiments of the invention, because not only the effects of the invention can be more displayed, but also the effect of reducing the fog produced in an unexposed area.
• R 1 and R 2 represent each an alkyl group, an aryl group, an R 3 CO- group or a hydrogen atom, provided that R 1 and R 2 cannot represent each hydrogen atoms at the same time and that R 1 and R 2 are also allowed to form a ring.
• the substituted or non-substituted alkyl groups represented by R 1 and R 2 may be the same with each other and they include, preferably, an alkyl group having 1 to 3 carbon atoms. Further, these alkyl groups may have a carboxyl group, a phosphoric acid group, a sulfo group or a hydroxyl group.
• R 3 represents a substituted or non-substituted alkoxy group, a substituted or non-substituted alkyl group or a substituted or non-substituted aryl group.
• the rings which may be formed by R 1 and R 2 include, for example, a heterocyclic ring such as those of piperidine, pyridine, triazine or morpholine.
• R 11 , R 12 and R 13 represent each a hydrogen atom, a substituted or non-substituted alkyl group, an aryl group or a heterocyclic group
• R 14 represents a hydroxyl group, a hydroxyamino group, a substituted or non-substituted alkyl group, an aryl group, a hetercyclic group, an alkoxy group, an aryloxy group, a carbamoyl group or an amino group, provided that the heterocyclic groups have each a 5- or 6-membered ring, and they are each constituted of C, H, O, N, S and a halogen atom and they may also be either saturated or unsaturated;
• R 15 represents a divalent group selected from the group consisting of -CO-, -S
• the typical examples of the hydroxylamine type compounds represented by the above-given Formula [A] are given in, for example, U.S. Patent Nos. 3,287,125, 3,329,034 and 3,287,124.
• the particularly desirable exemplified compounds are typically include, for example, those of (A-1) through (A-39) given in JP Application No. 2-203169/1990, pp.36-38, (1) through (53) given in JP OPI Publication No. 3-33845/1991, pp.3-6, and (1) through (52) given in JP OPI Publication No. 3-63646/1991, PP-5-7.
• the compounds represented by Formulas [A] and [B] are ordinarily used in the forms of a free amine, a hydrochloric acid salt, a sulfuric acid salt, a p-toluenesulfinic acid salt, an oxalic acid salt and an acetic acid salt.
• hydroxylamine type compounds represented by the following Formula [A'] may also desirably be used as the preservatives for a color developer.
• L represents each a substituted or non-substituted alkylene group
• A represents a carboxyl group, a sulfo group, a phosphono group, a phosphino group, a hydroxyl group, an alkyl-substitutable amino group, an ammonio group, a carbamoyl group or a sulfamoyl group
• R represents a hydrogen atom or a substituted or non-substituted alkyl group.
• the typical examples of the compounds represented by Formula [A'] include (1) through (54) given in JP OPI Publication No. 3-184044/1991, the lower left column on P.4 to the lower right column on p.6. Among them, the following compounds (1) and (7) are desirably used.
• the compounds represented by Formula [A'] can be prepared by making an alkylating reaction of any hydroxylamines available on the market. For example, they can be synthesized in the synthesizing processes detailed in, forexample, West German Patent No. 1,159,634, lnorganica Chemica Acta, 93,1984, pp.101 ⁇ 108, and so forth.
• preservatives include, for example, sugars.
• Sugars include a monosuccharide and a polysaccharide. Most of them are represented by the formula (C n H 2n O n ).
• the above-mentioned monosaccharide is general term for the aldehydes or ketones of polyhydric alcohol, the reduction derivatives, oxidation derivatives and dehydration derivatives thereof and the widely ranged derivatives of amino sugar or thio sugar.
• the above-mentioned polysaccharides mean a product obtained by dehydrating and condensing two or more of the above-mentioned monosaccharides.
• sugars include, desirably, aldose having a reducible aldehyde group and the derivatives thereof and, more desirably among them, those corresponding to the monosaccharides.
• the solid chemicals for color and black-and-white developments may necessarily be used with a buffer.
• the buffers applicable thereto include, for example, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (or boric acid), potassium tetraborate,, sodium o-hydroxybenzoate (or sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (or sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxy benzoate (or potassium 5-sulfosalicylate).
• a development accelerator including, for example, thioethertype compounds typified by those given in JP Examined Publication Nos. 37-16088/1962, 37-5987/1962, 38-7826/1963, 44-12380/1969 and 45-9019/1970 and U.S. Patent No. 3,813,247; p-phenylenediamine type compounds typified by those given in JP OPI Publication Nos. 52-49829/1977 and 50-15554/1975; quaternary ammonium salts typified by those given in JP Examined Publication No. 44-30074/1969 and JP OPI Publication Nos.
• thioethertype compounds typified by those given in JP Examined Publication Nos. 37-16088/1962, 37-5987/1962, 38-7826/1963, 44-12380/1969 and 45-9019/1970 and U.S. Patent No. 3,813,247
• p-phenylenediamine type compounds typified by those given in JP
• color developers are also allowed to contain chlorine ion and bromine ion.
• chlorine ions may be contained in a proportion within the range of, 1.0x10- 2 to 1.5x10 -1 mols per liter and, desirably, 3.5x10- 2 to 1.0x10 -1 mols per liter.
• concentration of the chlorine ions is higher than 1.5x10 -1 mols per liter, a high maximum density may not desirably be obtained, because the ions retard a development.
• concentration thereof is lower than 3.5x10- 2 mols per liter, the results may not become desirable, because stains may be produced and the photographic characteristics (including, particularly, a minimum density) may be varied seriously in the course of a continuous processing.
• a color developer contains bromide ions in an amount within the range of 3.0x10 -5 to 1.0x10- 3 mols per liter, desirably, 5.Ox10- 5 to 5x10-4 mols per liter and, more desirably, 1.Ox10- 4 to 3.Ox10- 4 mols per liter.
• the bromide ion concentration is higher than 1.0x10 -3 mols per liter, the development is retarded and the maximum density and sensitivity are lowered.
• concentration thereof is lower than 3.0x10 -5 mols per liter, stains are produced and the photographic characteristics (including particularly the minimum density) are varied in the course of carrying out a continuous processing. Therefore, the results may not become desirable.
• the chlorine ion supplying substances include, for example, sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride.
• sodium chloride and potassium chloride may desirably be added thereto.
• These substances may also be supplied in the form of the counter salts of a fluorescent whitening agent which is to be added into a color developer.
• the bromine ion supplying substances include, for example, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide.
• potassium bromide and sodium bromide may desirably be added thereto.
• any one of the desired antifoggants may be added, if required, into the solid chemicals for color development use of the invention.
• the above-mentioned antifoggants applicable thereto include, for example, an alkali-metal halide such as potassium iodide and an organic antifoggant.
• the organic antifoggants include, typically, nitrogen-containing heterocyclic compound such as benzotriazole, 6-nitrobenzoimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzoimidazole, 2-thiazolylmethylbenzoimidazole, indazole, hydroxyazaindolidine and adenine.
• nitrogen-containing heterocyclic compound such as benzotriazole, 6-nitrobenzoimidazole, 5-nitroindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzoimidazole, 2-thiazolylmethylbenzoimidazole, indazole, hydroxyazaindolidine and adenine.
• the above-mentioned fluorescent whitening agents include, desirably, the compounds represented by the following Formula [E].
• X 1 , X 2 , Y 1 and Y 2 represent each a hydroxyl group, a halogen atom such as those of chlorine and bromine, an alkyl group, an aryl group, a -N(R 21 )(R 22 ) group, or OR 25 , in which R 21 and R 22 represent each a hydrogen atom, a substituted or non-substituted alkyl group or a substituted or non-substituted aryl group; R 23 and R 24 represent each a substituted or non-substituted alkylene group; R 25 represents a hydrogen atom, a substituted or non-substituted alkyl group or a substituted or non-substituted aryl group; and M represents a cation.
• R 21 and R 22 represent each a hydrogen atom, a substituted or non-substituted alkyl group or a substituted or non-substituted aryl group
• the details of the groups or the substituents thereof each given in Formula [E] are each synonymous with those given in JP Application No. 2-240400/1990, the 8th line from the bottom on p.62 to the 3rd line from the bottom on p.64.
• the concrete compounds may include, for example, E-1 through E-45 given in the same JP Application, pp.65-67.
• the above-mentioned compounds can be synthesized in any well-known methods.
• the typical compounds will be exemplified below.
• E-4, E-24, E-34, E-35, E-36, E-37 and E-41 may desirably be used.
• These compounds may be added in an amount within the range of, desirably, 0.2 to 10 g per 1000 ml of a color developer and, more desirably, 0.4 to 5 g.
• Formula [F] wherein R 4 represents a hydroxyalkyl group having 2 to 6 carbon atoms; R 5 and R 6 represent each 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 formula of in which n is an integer of 1 to 6; and X and Z represent each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.
• ethanol amine, free amine of diethanolamine, a borate, a hydrochloride and a phosphate may desirably be used.
• free amine of ethanolamine, a borate, a hydrochloride and a phosphate may preferably be used.
• an auxiliary developing agent can also be used together with a developing agent.
• the known auxiliary developing agents include, for example, Metol, Phenidone, N,N-diethyl-p-aminophenol hydrochloride, N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride. They may be added usually in an amount within the range of, desirably, 0.01 to 1.0 g per liter.
• additives such as an antistaining agent and an interlayer effect accelerator may be used.
• K-2, K-9, K-12, K-13, K-17 and K-19 may desirably be used.
• the effects of the invention can be more displayed when adding K-2 and K-9 into a color developer.
• These chelating agents may be added in an amount within the range of, desirably, 0.1 to 20 g per 1000 ml of a color or black-and-white developer used and, more desirably, 0.2 to 8 g.
• the solid chemicals for color or black- and -white development use are allowed to contain each of anionic, cationic, amphoteric and nonionic surfactants. If required, it is also allowed to add a variety of surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid and aromatic carboxylic acid.
• the binders applicable to the invention include, for example, hydroxypropyl cellulose, hydroxypropyl methylcellulose, polyvinyl pyrrolidone, starch, gelatin, pullulan, carboxymethyl cellulose, sodium carboxymethyl cellulose, polyvinyl alcohol and hydroxyethyl cellulose.
• hydroxy propyl cellulose, pullulan and starch are desirable applicable thereto and hydroxypropyl cellulose is most desirably applicable thereto.
• the coating agents include, for example, hydroxypropyl cellulose, polyvinyl alcohol, pullulan, polyvinyl pyrrolidone and a water-dispersed product of poly(metha)acrylic acid and a poly(metha)acrylic acid ester.
• hydroxypropyl cellulose and hydroxypropylmethyl cellulose are desirably applicable thereto and hydroxypropyl cellulose is most desirably applicable thereto.
• Silver halide photographic light sensitive materials are exposed to light and are then processed in the processing steps such as a developing step, a desilvering step, a washing step and a stabilizing step.
• a black-and-white developer or a color developer is used in the developing step; a bleacher, a bleach-fixer or a fixer, in the desilvering step; city water or ion-exchange water, in the washing step; and a stabilizer, in the stabilizing step; respectively.
• Each of the processing solutions is thermally controlled at a temperature within the range of, usually, 30 to 40°C and the subject light sensitive materials are dipped in and processed in the above-mentioned processing solutions.
• the above-mentioned processing treatments are usually carried out through an automatic processor or the like and the subject light sensitive materials are transported one after another between the processing tanks in which the above-mentioned processing solutions are contained, respectively.
• the processing treatments are carried out so as to keep supplying the replenishers timely from the replenishing tanks into the processing tanks, respectively.
• the replenishers themselves reserved in the corresponding replenishing tanks are separately prepared and they are replenished into the corresponding replenishing tanks if occasion requires; and, in another system, the replenishers are prepared directly in the corresponding replenishing tanks.
• the processing chemicals are supplied in the form of powder or condensed liquid and they are used after dissolving or diluting them with a specific amount of water.
• the effects of the invention can be more excellently displayed when light sensitive materials are processed by making combination use of an automatic processor capable of solving the above-mentioned problems and a solid chemical of the invention.
• Fig. 1 is a schematic illustration of an example of the automatic processors relating to the invention, in which the control mechanism for a color negative film processing apparatus is briefly illustrated.
• replenishing solid chemical supply units 8, replenishing water supply unit 10 and electromagnetic valves 12 are each operated upon receipt of a signal sent from control section 11, so that replenishing processing chemicals and replenishing water can each be replenished in the necessary amounts into processing tanks 1, 2, 3 and 5, respectively.
• processing solutions 17 are evaporated from each of processing tanks 1 through 5.
• liquid level detection sensors 9 are operated and replenishing water supply unit 10 and electromagnetic valves 12 are then operated upon receipt of a signal from control section 11, so that replenishing water for compensating the evaporation can be supplied until the upper liquid level detection mechanisms of liquid level detection sensors 9 are operated.
• warm washing water 14, that is replenishing water supplied through replenishing water supply pipe 15, is to be made thermostatic together with replenishing water for preparing the solutions and replenishing water for compensating the evaporation.
• 1 is a color developing tank
• 2 is a bleaching tank
• 3 is a fixing tank
• 4 is a washing tank
• 5 is a stabilizing tank.
• 6 is a drying section.
• Fig. 2 shows a schematic illustration of an embodiment of replenishing solid chemical supply units 8, in the case where the tablet-shaped, solid type replenishing processing chemicals are used.
• control section 11 When control section 11 is operated upon receipt of a signal from light sensitive material area detection sensor 7 and thereby stepping motor 95 for supplying solid type replenishing processing chemicals is then operated, driving pinion 96 directly coupling to the motor 95, which is engaged with rack 94A of extrusion plunger 94 for supplying the replenishing solid chemicals, such driving pinion 96 lifts up plunger 94 having the foregoing rack 94A by one step that is as same as a pitch length P of the thickness of a processing chemical, so that the uppermost solid chemical 24Acan be ready in the dropping position of supply tray 91.
• processing chemicals 24 stored in supply tray 91 is completed to make it ready for dropping into filtration unit 21 provided to the inside of processing chemical supply tank (hereinafter called a subtank) which is a replenishing processing chemical dissolving section for each of processing tanks 1, 2, 3 and 5.
• a subtank processing chemical supply tank
• Solid chemical 24A ready at the uppermost position is slided laterally, by the forwarding movement of plunger 99 which horizontally reciprocates on the upper portion of piston sliding table 92, through a tunnel formed of guide plate 20A on the upper part of subtank 20 and top cover 20B, so that solid chemical 24A can be dropped on the liquid surface of filtration unit 21 of subtank 20.
• Plunger 99 is reciprocated by the foregoing stepping motor 97 started in motion by a demand signal, because rack 99A provided to a part of the foregoing plunger 99 is engaged with pinion 98 directly coupled to stepping motor 97.
• stepping motor 97 is reversely rotated so as to make plunger 99 backward to restore it to the original position and plunger 99 is then made ready for taking an action until the next signal is given.
• a demand signal demands to supply plural solid chemicals.
• the replenishing processing chemicals 24 thus supplied are gradually dissolved and are then supplied by circulation pump 18 into main processing tanks 16 each of processing tanks 1, 2, 3 and 5.
• supply tray body 91 of solid chemical supply unit 8 is so constructed as to be covered by the vertical walls on four sides and to reciprocate plunger 94 in the vertical direction.
• solid chemicals are protected in the supply tray in almost the sealed state and the uppermost solid chemical 24A is so extruded in almost the sealed state from the tunnel to subtank 20 as mentioned above. Therefore, the processing chemicals are neither contaminated by splashing any processing solutions nor affected by any evaporations.
• the reciprocation speed of plunger 99 is properly controlled and the solid chemicals are fed to such a direction that the flat surfaces of the solid chemicals can be vertical as shown in Fig. 2. Therefore, the water scattering can extremely be reduced.
• Replenishing water for preparing solutions can be supplied in the following manner.
• the control section 11 When control section 11 is operated upon receipt of a signal from light sensitive material area detection sensor 7, the control section 11 demands to operate replenishing solid chemical supplying stepping motors 95 and 97, pinions 96 and 98 each driven by the above-mentioned motors, plunger 94 having rack 94Aand plunger 99 having rack 99Aeach linearly moved by the above-mentioned pinions, and, at the same time when supplying replenishing solid chemicals 24, replenishing water supply unit 10 and electromagnetic valves 12 are operated, so that replenishing water for preparing solutions can be supplied.
• the amounts of supplying the replenishing water for preparing solutions may be enough, provided that replenishing solid chemicals 24 can be dissolved.
• the amounts thereof can be controlled by inputting a operation time for both electromagnetic valves 12 and replenishing water supply unit 10 in advance to control section 11.
• liquid level detection sensors 9 detect the lowered liquid level and send a signal to control section 11 so as to operate electromagnetic valves 12 and replenishing water supply unit 10, so that replenishing water for compensating the evaporation can be supplied.
• liquid level detection sensors 9 detect the regular liquid level and send a signal to control section 11, so that electromagnetic valves 12 and replenishing water supply unit 10 are stopped in operation.
• a solid type color development processing chemicals for color negative use was prepared in the following procedures.
• Hydroxylamine sulfate of 150 g was milled in an air-jet fine mill, until the average particle size thereof could be 10 ⁇ .
• Water of 10 ml was sprayed for about 7 minutes over to the resulting fine particles at room temperature in a fluidized bed spray granulator available on the market. After granulating them to have an average particle size of 150 ⁇ m, the resulting granules were dried up at an air temperature of 63°C for 8 minutes. Next, the granules were dried up in vacuum at 40°C for 90 minutes and the moisture of the granules was almost completely removed.
• the resulting uniform mixture was pulverized in an air-jet fine mill in the same manner as in Procedure (1).
• the resulting pulverized mixture was granulated by spraying the solution prepared by dissolving 40 g of sodium bromide in 150 ml of an aqueous 1% hydroxypropyl cellulose solution. After completing the granules, they were dried at 65°C for 15 minutes and the granules were then dried up in vacuum at 40°C for 90 minutes, so that the moisture thereof could be almost completely removed.
• the granules prepared in the above-described procedures (1) through (3) were screened to obtain 500 g of the granular chemicals having a particle size within the range of 1000 ⁇ m to 300 ⁇ m, so that granular chemical sample 1 for color film development use could be prepared.
• the granules prepared in Procedure (4) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm 2 by making use of a tablet machine, so that 50 pieces of tablet type chemical sample 2 for color film development use could be prepared.
• the resulting uniformed mixture was pulverized in an air-jet fine mill in the same manner as in Procedure (1).
• the resulting pulverized mixture was granulated.
• the resulting granules were dried at 70°C for 10 minutes and the resulting granules were then dried up in vacuum at 40°C for 90 minutes, so that the moisture thereof were almost completely removed.
• the granules granulated in the above-described procedures (1) and (2) were added to the granules granulated in the above-described procedure (5) and the mixture thereof were screened in the same manner as in Procedure (4) to obtain 500 g of the granules having a particle size within the range of 1000 ⁇ m to 300 ⁇ m so as to serve as a granular chemicals, so that granular sample 3 for color film development use could be prepared.
• a mixture was made by-mixing up 150 g of hydroxylamine sulfate, 300 g of CD-4, 125 g of sodium 1-hydroxyethane-1,1-diphosphonate, 100 g of sodium diethylenetriamine pentaacetate, 175 g of sodium sulfite, 1540 g of potassium carbonate and 75 g of sodium hydrogen carbonate by making use of a mixer for 5 minutes.
• the resulting mixture was pulverized by an air-jet fine mill, until the average particle size thereof could be 10 ⁇ m.
• Sodium bromide of 40 g was pulverized by an air-jet mill, until the average particle size thereof could be 10 ⁇ m.
• the pulverized mixture of 360 g obtained in Procedure 9 was added to 40 g of sodium bromide finely pulverized in Procedure 10 and both of them were mixed up by a mixer for 10 minutes. Further, all the remaining pulverized mixture obtained in Procedure 9 were added thereto so as to be mixed up further for 10 minutes.
• the mixture prepared in Procedure 11 was sprayed with 120 ml of water by making use of a fluidized bed spray granulator, so that they could be granulated to have an average particle size of 800 ⁇ m. After that, the resulting granules were dried at 60°C for 20 minutes. Next, the resulting granules were dried up in vacuum at 40°C for 120 minutes, so that the moisture content of the granules could be almost completely removed.
• the granules obtained in the above-described Procedure 12 were screened so as to obtain 400 g of granules having a particle size within the range of 1000 f..lm to 300 ⁇ m and they were served as a granular chemical, so that granular chemical sample 5 for color film development use could be prepared.
• the granules prepared in Procedure (12) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm 2 by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 6 for color film development use could be prepared.
• a mixture was made by mixing up 150 g of hydroxylamine sulfate, 300 g of CD-4, 125 g of sodium 1-hydroxyethane-1,1-diphosphonate, 100 g of sodium diethylenetriamine acetate, 175 g of sodium sulfite, 1540 g of potassium carbonate, 75 g of sodium hydrogen carbonate and 40 g of sodium bromide by making use of a mixer for 5 minutes.
• the resulting mixture was pulverized by an air-jet fine mill, until the average particle size thereof could be 10 ⁇ m.
• the mixture prepared in Procedure 15 was sprayed with 135 ml of water by making use of a fluidized bed spray granulator, so that they could be granulated to have an average particle size of 800 ⁇ m. After that, the resulting granules were dried at 60°C for 20 minutes. Next, the resulting granules were dried up in vacuum at 40°C for 120 minutes, so that the moisture content of the granules could be almost completely removed.
• the granules obtained in the above-described Procedure 16 were screened so as to obtain 400 g of granules having a particle size within the range of 1000 ⁇ m to 300 ⁇ m and they were served as a granular chemical, so that granular chemical sample 7 for color film development use could be prepared.
• the granules prepared in Procedure (16) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm 2 by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 8 for color film development use could be prepared.
• the fine powder prepared in the same manner as in Procedure 11 was prepared to be a flake-shaped compressively formed product by making use of a roller compacting type dry granulator. After the resulting compressively formed products is roughly ground, they were graded so as to be granules having an average particle size of 700 ⁇ m. Further, the resulting granules were dried up in vacuum at 40°C for 60 minutes, so that the moisture of the granules could be almost completely removed.
• the granules obtained in the above-described Procedure 19 were screened so as to obtain 300 g of granules having a particle size within the range of 1000 f..lm to 300 ⁇ m and they were served as a granular chemical, so that granular chemical sample 9 for color film development use could be prepared.
• the granules prepared in Procedure (19) were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm 2 by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 10 for color film development use could be prepared.
• the fine powder prepared in the same manner as in Procedure 15 was prepared to be a flake-shaped compressively formed product by making use of a roller compacting type dry granulator. After the resulting compressively formed products is roughly ground, they were graded so as to be granules having an average particle size of 700 ⁇ m. Further, the resulting granules were dried up in vacuum at 40°C for 60 minutes, so that the moisture of the granules could be almost completely removed.
• the granules obtained in the above-described Procedure 22 were screened so as to obtain 400 g of granules having a particle size within the range of 1000 ⁇ m to 300 ⁇ m and they were served as a granular chemical, so that granular chemical sample 11 for color film development use could be prepared.
• the granules prepared in Procedure 22 were tableted into those having a diameter of 30 mm and a weight of 10 g by applying a compression of 800 kg/cm 2 by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 12 for color film development use could be prepared.
• a granulation was made in the same manner as in Procedure 15 of Example 2 by making use of 90 g of ferric potassium 1,3-propylenediamine tetraacetate, 20 g of ferric sodium ethylenediamine tetraacetate, 2.5 g of sodium ethylenediamine tetraacetate and 2.5 g of sodium hydrogen carbonate.
• the sprayed amount of water was 27.5 ml, the drying temperature was 80°C and the time was 10 minutes, respectively.
• a granulation was made in the same manner as in Procedures 15 and 16 by making use of 150 g of potassium bromide, 17.5 g of sodium nitrate and 14.5 g of maleic acid.
• the sprayed amount of water was 25 ml, the drying temperature was 77°C and the time was 10 minutes, respectively.
• the granulation was made in the same manner as in Procedure (3) by making use of 150 g of sodium thiosulfate, 10 g of sodium sulfite, 37.5 g of potassium thiocyanate, 1.0 g of sodium ethylenediamine tetraacetate and 1.0 g of sodium hydrogen carbonate.
• the sprayed amount of water was 12.0 ml, the drying temperature was 77°C and the time was 10 minutes, respectively.
• the granules prepared in Procedure (28) were solidified in the same manner as in Procedure (18).
• 25 pieces of solid type replenishing fixer chemicals for color negative film use were prepared in the same manner as in Procedure (18), except that the amount of the solidified granules filled in a solid chemical tableting machine was 9.96 g.
• the granulation was made in the same manner as in Procedure (15) by making use of 3.0 g of hexamethylene tetramine, 2.0 g of polyethylene glycol (having a molecular weight of 1540), 0.05 g of 1,2-benzisothiazolone-3-one, 0.12 g of polyvinyl pyrrolidone (having a polymerization degree of about 17) and 0.35 g of sodium hydrogen carbonate. While keeping the resulting granules be sprayed with 6 g of (P)-C 8 H 17 -C 6 H 4 -O-(CH 2 CH 2 0) 10 H for about 20 minutes, the granulation was continued on. Next, the granules were dried at an air temperature of 65°C for 10 minutes and the dried granules were then dried up in vacuum at 40°C for 90 minutes.
• the stabilizing tanks were constructed in a cascade system in which a stabilizer was replenished to the third tank and the overflow was flowed in order into the second and then first tanks.
• the processing solutions for the automatic processors were prepared in the following procedures.
• Table 8 shows the results of measuring the minimum and maximum transmission magenta densities.
• Dmin represents a minimum density
• Dmax a maximum density
• G a green filter density
• Solid type color development processing chemicals for color paper use were prepared in the following procedures.
• Cinopar SFP manufactured by Ciba-Geigy AG
• 25.0 g of diethylene triamine pentaacetic acid 51.0 g of dimethoxyethylene hydroxylamine oxalate
• 100.0 g of polyethylene glycol 6000 120 g of CD-3 [1-(N-ethyl-N-methanesulfonamidoethyl)-3-methyl-p-phenylenediamine sesquisulfate.monohydrate
• the resulting mixture was pulverized by an air-jet fine mill, until they could have an average particle size of 10 ⁇ m.
• microconstituent consisting of 0.5 g of potassium bromide and 0.1 g g of benzyl adenine was pulverized by an air-jet fine mill, until they could have an average particle size of 10 ⁇ m.
• the finely pulverized matter of 5.4 g prepared in Procedure (32) were added to the mixture of 0.5 g of potassium bromide and 0.1 g of benzyl adenine prepared in Procedure (33) and they were uniformly mixed up for 10 minutes. Further, the finely pulverized matter prepared in Procedure (32) were added thereto little by little and then mixed together. After repeating the mixing them, all the finely pulverized matters prepared in Procedure (32) were finally mixed up.
• the finely pulverized matter prepared in Procedure (34) was subjected to a roller compacting type dry granulator so as to prepare a flake-shaped compressed product and they were roughly grained. After that, the resulting rough grains were made to be the granules having an average grain size of 500 ⁇ m through a grading step. Further, the resulting graded granules were dried in vacuum at 40°C for 60 minutes and the moisture thereof was almost completely removed.
• the granules obtained in the above-described Procedure (35) were screened so as to obtain 600 g of granules having a particle size within the range of 1000 ⁇ m to 300 ⁇ m and they were served as a granular chemical, so that granular chemical sample 13 could be prepared.
• the granules prepared in Procedure (35) were tableted into those having a diameter of 30 mm and a weight of 9.32 g by applying a compression of 700 kg/cm 2 by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 14 for color paper development use could be prepared.
• Cinopar SFP manufactured by Ciba-Geigy AG
• 25.0 g of diethylene triamine pentaacetic acid 51.0 g of dimethoxyethylene hydroxylamine oxalate
• 100.0 g of polyethylene glycol 6000 120 g of CD-3 [1-(N-ethyl-N-methanesulfonamidoethyl)-3-methyl-p-phenylenediamine sesquisulfate.monohydrate
• the resulting mixture was pulverized by an air-jet fine mill, until they could have an average particle size of 10 ⁇ m.
• the finely pulverized matter prepared in Procedure (38) was subjected to a roller compacting type dry granulator used in Procedure (38) so as to prepare a flake-shaped compressed product and they were roughly grained. After that, the resulting rough grains were made to be the granules having an average grain size of 500 ⁇ m through a grading step. Further, the resulting graded granules were dried in vacuum at 40°C for 60 minutes and the moisture thereof was almost completely removed.
• the granules obtained in the above-described Procedure (39) were screened so as to obtain 600 g of granules having a particle size within the range of 1000 f..lm to 300 ⁇ m and they were served as a granular chemical, so that granular chemical sample 15 could be prepared.
• the granules prepared in Procedure (39) were tableted into those having a diameter of 30 mm and a weight of 9.32 g by applying a compression of 700 kg/cm 2 by making use of a tableting machine, so that 50 pieces of tablet type chemical sample 16 for color paper development use could be prepared.
• the mixture of 1350 g of ferric ammonium ethylenediamine tetraacetate, 20.0 g of disodium ethylenediamine tetraacetate, 1550.0 g of ammonium thiosulfate and 400.0 g of sodium metabisulfate was made, and the mixture was then pulverized by an air-jet mill, until the pulverized grains could have an average of 10 ⁇ m.
• the finely pulverized matter prepared in Procedure (42) was subjected to a roller compacting type dry granulator so as to prepare a flake-shaped compressed product and they were roughly grained. After that, the resulting rough grains were made to be the granules having an average grain size of 500 ⁇ m through a grading step. Further, the resulting graded granules were dried in vacuum at 40°C for 60 minutes and the moisture thereof was almost completely removed.
• the granules prepared in Procedure (43) were tableted into those having a diameter of 30 mm and a weight of 9.0 g by applying a compression of 600 kg/cm 2 by making use of a tableting machine, so that 50 pieces of solid type chemicals for bleach-fixing color papers.
• Table 11 shows the standard processing conditions of the automatic processor.
• the stabilizing tanks were constructed in a cascade system, in which a stabilizer was replenished to the third tank and the overflow was flowed in order into the second and then first tanks.
• the processing solutions used in the automatic processor were prepared in the following procedures.
• Konica Color Paper Type QA photographed thereon was set on the automatic processor and 15 m 2 of the color paper were then processed every day for one month, while printing thereon. The resulting stability of the processed characteristics for the month period was checked up and evaluated. Also, for the comparison purpose, replenishing solutions were each prepared and were then put in the conventional replenishing tanks, so as to evaluate the system in which the replenishments are made through bellows pumps, respectively.
• control slips CPK-2 of the top and every 30m 2 of the color papers were processed and the stabilities of the processed characteristics thereof were evaluated by confirming the resulting photographic densities.
• Table 12 shows the results of the photographic density measurements obtained in Example 9. Wherein, Dmin represents a minimum density; Dmax, a maximum density; and G, green filter density.

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• 1992
  • 1992-11-30 EP EP92310912A patent/EP0547796A1/fr not_active Withdrawn

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