EP0611989B1 - Feste Zusammensetzung zur Verarbeitung von photographischen lichtempfindlichen Silberhalogenidfarbmaterialien und deren Verarbeitungsverfahren - Google Patents

Feste Zusammensetzung zur Verarbeitung von photographischen lichtempfindlichen Silberhalogenidfarbmaterialien und deren Verarbeitungsverfahren Download PDF

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EP0611989B1
EP0611989B1 EP19940300373 EP94300373A EP0611989B1 EP 0611989 B1 EP0611989 B1 EP 0611989B1 EP 19940300373 EP19940300373 EP 19940300373 EP 94300373 A EP94300373 A EP 94300373A EP 0611989 B1 EP0611989 B1 EP 0611989B1
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Prior art keywords
group
composition
tablet
granules
color developing
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English (en)
French (fr)
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EP0611989A1 (de
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Hiroshi Yamashita
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/261—Non-bath processes, e.g. using pastes, webs, viscous compositions
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/30—Developers
    • G03C5/3021—Developers with oxydisable hydroxyl or amine groups linked to an aromatic ring
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers
    • G03C7/4136—Developers p-Phenylenediamine or derivatives thereof

Definitions

  • This invention relates to a solid processing composition for a silver halide color photographic light-sensitive material suitable for preserving the environment of the earth and excellent in aging preservability; and to a method of processing a silver halide color photographic light-sensitive material in which the solid processing composition is used.
  • a concentrated replenisher When preparing a concentrated replenisher, there is a limit on the concentration which may be obtained because color developing agents are low in solubility. Further, a conventional color developing composition is normally supplied in several separate parts to prevent components of the developing composition reacting chemically with each other, because the necessary components are supplied in the state of an aqueous solution. When preparing a replenisher, the parts of the replenisher are added together and then dissolved. Therefore, once a replenisher is prepared, it cannot be preserved for a long period, because a chemical reaction gradually occurs and the replenisher deteriorates. Thus when a concentrated replenisher is used, not only is the undesirable chemical reaction accelerated because the component concentration in the replenisher is made higher, but also there may be a danger that variations in the photographic processing characteristics may be produced by the deterioration of the replenisher.
  • JP OPI Publication No. 2-109042/1990 discloses a granulated color developing composition
  • JP OPI Publication No. 51-61837/1976 discloses a tablet type processing composition.
  • USP-4756996 discloses the use of LiOH as an alkaline agent in aqueous colour developers.
  • a solid processing composition for a silver halide color photographic light-sensitive material which is a color developing composition comprising a p-phenylenediamine color developing agents and lithium hydroxide.
  • the solid type processing composition is preferably in tablet or granule form
  • the tablet is preferably obtained by compressing and molding particles.
  • the solid processing composition according to the invention preferably contains at least one of the compounds represented by the following Formula [A].
  • L represents an alkylene group
  • A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residual group, a hydroxy group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group
  • R represents a hydrogen atom or an alkyl group
  • the solid processing composition according to the invention preferably comprises a mixture of granules containing lithium hydroxide and granules containing a p-phenylenediamine type color developing agent. It preferably further comprises granules of formula (A) as defined above.
  • the invention further provides a process for the preparation of a solid processing composition in tablet form which comprises tabulating a mixture of granules containing lithium hydroxide and granules containing a p-phenylenediamine type color developing agent.
  • the mixture preferably contains granules of compounds of formula [A]. Each type of granule is preferably separately granulated before mixing.
  • Lithium hydroxide used in the invention may optionally be either in anhydride or hydrate form.
  • a granulated composition in the context of the invention means a granule that is prepared by applying a granulation process to a powder and has a granule size within the range of 50 to 5000 ⁇ m.
  • a tablet composition in the context of the invention means a tablet prepared by compression-molding a powder to take a specific configuration, or prepared by granulating a powder and then compression-molding the granule to take a specific configuration.
  • a tablet composition is preferably used because it more remarkably displays the effects of the invention.
  • Methods of preparing the preferable tablet composition include, for example, granulating a powder solid processing composition and then subjecting it to a tableting process.
  • the resulting tablet composition has improved solubility and preservability compared to a solid processing composition prepared simply by mixing the components of a solid processing composition and then tableting it in a tableting process.
  • the resulting composition can have the advantage that its photographic characteristics are stabilized.
  • Suitable granulating methods include for example, any well-known method such as a convoluting granulation method, an extruding granulation method, a compression granulation method, a pulverizing granulation method, a stirring granulation method, a fluidized-bed granulation method, and a spray-drying granulation method.
  • the average granule size of the resulting granules is within the range of, preferably, 100 to 800 ⁇ m and, more preferably, 200 to 750 ⁇ m. If the average granule size is smaller than 100 ⁇ m or larger than 800 ⁇ m, the components of the granule lack uniformity and may cause undesirable segregation when the granules are mixed up and then compressed.
  • not less than 60% of all the resulting granules have a granule-size distribution within the deviation range of ⁇ 100 of 150 ⁇ m.
  • any well-known compressor may be used, such as a hydraulic press, a single tableting machine, a rotary tableting machine and a briquetting machine.
  • a solid type processing composition prepared in a compression process can take any configuration.
  • a processing composition of a cylindrical type i.e. a so-called tablet type is preferably used, because of improved productivity and handling efficiency.
  • the color developing composition is preferably granulated separately from the alkali.
  • the bulk density of a solid processing composition is preferably within the range of 1.0 g/cm 3 to 2.5 g/cm 3 when the processing composition is of a tablet type. If the bulk density thereof is less than 1.0 g/cm 3 , the strength of the resulting solid is reduced and, if the bulk density is more than 2.5 g/cm 3 , the solubility of the resulting solid is decreased.
  • the bulk density thereof is preferably within the range of 0.40 to 0.95 g/cm 3 .
  • the amount replenished is preferably not more than 150 ml per m 2 of the light-sensitive material and particularly preferably not more than 100 ml.
  • an amount replenished herein stated also includes the amount of water supplied (i.e., the amount of water replenished) when the solid type color developing composition and the water for dissolving it are replenished separately. Further, when the time required for carrying out color development is not longer than 30 seconds, the effect of the invention can be better displayed.
  • L preferably represents a straight-chain or branched-chain alkylene group having 1 to 10 carbon atoms which may have a substituent and, among them, one having 1 to 5 carbon atoms is preferred.
  • a more preferred example of L includes a methylene group, an ethylene group, a trimethylene group and a propylene group.
  • the substituent thereof includes, for example, a carboxy group, a sulfo group, a phosphono group, a phcsphinic acid residual group, a hydroxy group, and an alkyl-substitutable ammonio group.
  • the preferable examples include a carboxy group, a sulfo group, a phosphono group and a hydroxy group.
  • A represents a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residual group, a hydroxy group, an alkyl-substitutable amino group, an alkyl-substitutable ammonio group (preferably having 1 to 5 carbon atoms), an alkyl-substitutable carbamoyl group (preferably having 1 to 5 carbon atoms) or an alkyl-substitutable sulfamoyl group (preferably having 1 to 5 carbon atoms).
  • the preferable examples include a carboxy group, a sulfo group, a hydroxy group, a phosphono group and an alkyl-substitutable carbamoyl group.
  • -L-A include, preferably, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group and a hydroxyethyl group and, among them, the particularly preferable examples include a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group.
  • R represents a hydrogen atom, a straight-chain or the branched-chain alkyl group having 1 to 10 carbon atoms, which may have a substituent and, among them, an alkyl group having 1 to 5 carbon atoms is preferred.
  • Suitable substituents include, for example, a carboxy group, a sulfo group, a phosphono group, a sulfinic acid residual group, a hydroxy group, an alkyl-substitutable amino group, an alkyl-substitutable ammonio group, an alkyl-substitutable carbamoyl group, an alkyl-substitutable sulfamoyl group, a substitutable alkylsulfonyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group, an alkyl-substitutable amino group, an ary
  • R there may optionally be two or more substituents.
  • the preferable examples of R include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group and a hydroxyethyl group.
  • the particularly preferable examples thereof include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group, provided that L and R may complete, together with the nitrogen atom to which they are attached, a ring.
  • particularly preferable compounds include, for example, those of (2), (7), (14), (38), (39), (40) and (55).
  • the compound may be used in the form of an alkali-metal salt or an ammonium salt.
  • the compounds represented by Formula [A] can be synthesized by alkylating (using, for example, nucleophilic substituting reaction, an adduct reaction and a Mannich reaction) hydroxylamines which are readily available on the market.
  • the synthesis can be performed with reference to the procedures described in, for example, West German Patent Publication "Inorganica Chimica Acta", 93, (1984), pp. 101-108, and so forth.
  • the solid processing composition of the invention may consist of a single unit comprising in admixture the total components for processing a silver halide color photographic light-sensitive material or separate units comprising one or more components which are readily reactive with each other. Between the two cases, however, the single unit is preferable because of handling convenience and working efficiency.
  • compounds readily chemically reactive with each other may optionally be present in a layer-shaped configuration in which one of the compounds is partitioned off from the other by a different compound inert to the above-mentioned two compounds or by a film or the like.
  • a conventional developer replenisher may consist of three units, i.e., a color developing agent unit, a preserver unit and an alkali agent unit in view of storage stability.
  • the present invention provides a solid processing composition consisting of a single unit in solid form which contains all the components, and which has good storage stability. Further, the single unit has the advantage that it requires only one supplying means.
  • the solid color developing composition of the invention consists of a single unit, it is preferable to use anhydrous lithium hydroxide.
  • the solid type color developing composition contains a deliquescent substance such as potassium carbonate or an acidic substance such as an aminopolycarboxylic acid or a salt of a paraphenylenediamine type color developing agent, moisture absorption and internal reaction can be inhibited. Thereby the effect of the invention can be better displayed by making use of anhydrous lithium hydroxide as an alkali.
  • the solid color developing composition of the invention preferably contains an aromatic sulfonic acid or salt thereof which inhibits an internal chemical reaction.
  • an aromatic sulfonic acid or a salt thereof' used herein means a compound in which a sulfonate is directly bonded to an unsaturated conjugate ring showing aromaticity, provided that the sulfonic acid group or the sulfonate may comprise either one or more rings and the ring showing aromaticity may contain a hetero atom or any substituent.
  • a single compound may have plural rings showing aromaticity or may be a polymer.
  • the sulfonates include, for example, an alkali metal salt such as a salt of lithium, sodium or potassium, or an ammonium salt.
  • the aromatic sulfonic acid or salt thereof preferably used in the invention include, for example, the compound represented by the following Formula [1] or [2]. wherein at least one of A through F represents a sulfonic acid group or a sulfonate and the others represent each independently a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group. wherein at least one of G through N represents a sulfonic acid group or a sulfonate and the others represent each independently a hydrogen atom, a halogen atom, an alkyl group or an alkenyl group.
  • the alkyl or alkenyl group represented by A through F or G through N preferably has 1 to 10 carbon atoms, and the carbon chain may be either straight or branched.
  • exemplified compounds (1-2), (1-14), (2-6) or (2-8) are preferably used. It is also preferable to use the compounds in the form of an alkali metal salt and particularly in the form of a sodium salt.
  • polyethylene glycol in the solid color developing composition as a compound capable of effectively inhibiting an internal chemical reaction.
  • the average molecular weight of the above-mentioned polyethylene glycol suitable for use in the invention is preferably 300 to 50,000 and more preferably, 2,000 to 20,000.
  • polyethylene glycol is in the form of a liquid, it is preferably added in the course of granulating the solid composition. The effect of this compound is better when it is used together with the foregoing aromatic sulfonic acid or salt thereof.
  • the solid color developing composition of the invention contains a paraphenylenediamine type color developing agent.
  • the typical exemplified compounds of the color developing agent used in the invention include, for example, compounds (C-1) through (C-16) given in JP OPI Publication No. 4-86741/1992, pp. 26-31, compounds (1) through (8) given in JP OPI Publication No. 61-289350/1986, and compounds (1) through (26) given in JP OPI Publication No. 3-246543/1991, pp.6-9.
  • the particularly preferable include compounds (C-1) and (C-3) given in JP Application No. 2-203169/1990, Exemplified Compounds (2) given in JP OPI Publication No. 61-289350/1986 and Exemplified Compound (1) given in JP OPI Publication No. 3-246543/1991.
  • the solid color developing composition of the invention contains a triazinyl stilbene type fluorescent whitening agent.
  • fluorescent whitening agents include, preferably, a compound represented by the following Formula [E]. wherein X 1 , X 2 , Y 1 and Y 2 represent each a hydroxyl group a halogen atom such as those of chlorine or bromine, an alkyl group, an aryl group, or OR 25 , in which R 21 and R 22 represent each independently a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group (including a substituent thereof), R 23 and R 24 independently represent each an optionally substituted alkylene group, R 25 represents a hydrogen atom, an optionally substituted alkyl group or an optionally substituted aryl group, and M represents a cation.
  • the groups in Formula [E] and the substituents thereof are each synonymous with those described in JP OPI Publication No. 4-118649/1992, the 8th line from the bottom of p. 62 to the 3rd line from the bottom of p. 64.
  • the typical compounds thereof include, for example, E-1 to E-45 given in ibid., pp. 65-67. Among them, E-4, E-24, E-34, E-35, E-36, E-37 and E-41 may preferably be used. These compounds are each added in an amount within the range of, preferably, 0.2 to 10 g per liter of a color developing solution and, particularly, 0.4 to 5 g.
  • auxiliary developing composition can also be used together with a developing agent.
  • auxiliary developing compositions include, for example, N-methyl-p-aminophenol hexasulfate (that is so-called Metol), phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride. Usually, they are each added preferably in an amount within the range of 0.01 to 1.0 g per liter.
  • additives such as an antistaining agent, an antisludging agent and an interlayer-effect accelerating agent may also be used therein.
  • the color developing composition contains a chelating agent represented by the following Formula [K] and the exemplified compounds thereof K-1 through K-22, which are given in JP OPI Publication No. 4-118649/1992, the 9th line from the bottom of p. 69 to p. 75.
  • E represents an alkylene group, a cycloalkylene group, a phenylene group (each of which are optionally substituted), -R 5 OR 5 -, -R 5 OR 5 OR 5 - or -R 5 ZR 5 -;
  • R 1 through R 5 independently represent each an optionally substituted alkylene group;
  • a 1 through A 5 independently represent each a hydrogen atom, a hydroxyl group, -CO 2 M group or -PO 3 (M) 2 group; and
  • M represents a hydrogen atom or an alkali metal atom.
  • K-2, K-9, K-12, K-13, K-17 and K-19 may preferably be used.
  • K-2 and K-9 are added to a color developing solution, the effect of the invention is better displayed.
  • the chelating agent may be added in an amount of 0.1 to 20 g per liter of a color developing solution and more preferably 0.2 to 8 g.
  • a color developing composition is also allowed to contain such a surfactant as a anionic, cationic, amphoteric or nonionic surfactant.
  • the solid processing composition applicable to the invention can be embodied by solidifying an alkali, a color developing agent and a reducing agent.
  • the composition consists of not more than four units and most preferably a single unit in the case of preparing a tablet type processing composition.
  • a solid type processing composition is prepared by separating it into not less than two units, the resulting plural tablets or granules are preferably put in one package.
  • Procedure (C) when the alkaline agent was crushed at the relative humidity of 55 %, the deliquescence of potassium hydroxide and sodium was noticeable. After that, therefore, the crushing was conducted under a relative humidity of 40 % RH. With regard to the alkali used in the present invention, there was substantially no problem.
  • a sample of 5.0 g (one piece in the case of a tablet) was put in a sample bottle remaining uncapped and was preserved in a thermostat having a temperature of 30°C and a relative humidity of 40%RH. Three samples were prepared in each procedure and deliquescence of the samples was observed in terms of deformation or moisture adherence.
  • the hardness of 10 pieces of tablets was measured by means of a speed checker (produced by Okada Seiko Co., Ltd.), and the average value was defined to be degree of strength.
  • LiOH shall represent lithium hydroxide anhydride, unless otherwise mentioned.
  • Table 1 No. Alkali (Amount added) Deliquescence Angle of repose (degree) Hardness (Kg) 1-1 ⁇ ⁇ 46 Comparison 1-2 KOH 35g ⁇ 48 Comparison 1-3 KOH 70g ⁇ 50 Comparison 1-4 KOH 140g ⁇ unmeasurable Comparison 1-5 NaOH 25g ⁇ unmeasurable Comparison 1-6 NaOH 100g ⁇ unmeasurable Comparison 1-7 LiOH 15g ⁇ 43 Invention 1-8 LiOH 30g ⁇ 40 Invention 1-9 LiOH 60g ⁇ 39 Invention 1-10 LiOH 120g ⁇ 39 Invention 1-11 ⁇ ⁇ 20 Comparison 1-12 KOH 35g ⁇ 20 Comparison 1-13 KOH 70g ⁇ 19 Comparison 1-14 KOH 140g ⁇ 17 Comparison 1-15 NaOH 25g ⁇ 18 Comparison 1-16 NaOH 100g ⁇ 16 Comparison 1-17 LiOH 15g ⁇ 25 Invention 1-18 LiOH 30g ⁇ 30 Invention 1-19 LiOH 60g ⁇ 32 Invention 1-20 LiOH 120g
  • the alkaline agent of the present invention is not only excellent in deliquescence but also excellent in terms of fluidity after stored for a long time and also excellent in the strength of the tablets.
  • a solid color developing composition for color paper use was prepared by the following procedure.
  • an air-jet pulverizer was pulverized 1200 g of a developing agent CD-3, 4-amino-3-methyl-N-ethyl- ⁇ -(hydroxy)ethylaniline sulfate, to have an average particle size of 10 ⁇ m.
  • the resulting fine particles thereof were granulated by spraying 30 ml of water thereto at room temperature for about 5 minutes in a fluid-bed spray type granulator available on the market and the resulting granules were then dried at 60°C for 8 minutes. Thereafter, the granules were further dried in a vacuum at 40°C for 2 hours, so that the moisture of the granules was almost completely removed.
  • Procedure (A) In the same manner as in Procedure (A) was pulverized and granulated, 1200 g of a preservative shown in Table 2, except that only 1.0 ml of water was sprayed. After the granulation was completed the granules were dried at 50°C for 10 minutes. Thereafter, the granules were dried in a vacuum at 40°C for 2 hours, so that the moisture of the granules was almost completely removed.
  • Tinopar SFP manufactured by Ciba-Geigy AG.
  • 300 g, 400 g of sodium sulfite, 3500 g of potassium carbonate, 3.0 g of potassium bromide, 250 g of diethylene triamine penta acetic acid penta sodium salt and an alkali shown in Table 2 were pulverized in the same manner as in Procedure (A).
  • the resulting pulverized matter was mixed by a mixer available on the market.
  • the resulting mixtures were granulated in the same manner as in Procedure (A), except that 150 ml of water was used.
  • the granules were dried in a vacuum at 40°C for 2 hours, so that the moisture of the granules was almost completely removed.
  • a sample of 10.0 g (one piece in the case of a tablet) was put in a sample bottle remaining uncapped and was preserved in a thermostat having a temperature of 30°C and a relative humidity of 40%RH. Three samples were prepared in each procedure and deliquescence of the samples was observed in terms of deformation or moisture adherence.
  • a sample of 10.0 g (or, one piece in the case of a tablet) was put in a polyethylene bag (having a size of 10cm x 10cm) and then tightly sealed by applying heat.
  • the sealed bag was preserved for 3 weeks in a thermostat having a temperature of 50°C.
  • the resulting sample was dissolved in a specific amount of water, and the concentration of the color developing agent remaining in the solution was measured.
  • Fluidity of granules and strength of tablets were measured in the same manner as in Example 1.
  • Table 2 shows that when lithium hydroxide is used as an alkali, deliquescence is low and the residual concentration of a color developing agent is also high. The granule shows improved fluidity and the tablet shows improved strength. Further, when making use of a compound represented by Formula (A) as a preservative, better results are obtained. Table 2 also shows that better results can further be obtained when sodium p-toluene sulfonate is used as an aromatic sulfonate or when polyethylene glycol is used.
  • the preferable shape of the composition is of the tablet type.
  • Granules were prepared in the same manner as in Procedure (A), (B) or (C) of Example 2 and were tableted in the same manner as in Procedure (E), so that three kinds of tablets were prepared separately.
  • Disodium salt of Exemplified Compound (7) was used as a preservative and the compound shown in Table 2 (in an amount of 0.94 mols/kg) was used as an alkali.
  • the weight of each tablet was 0.45 g for (A), 0.45 g for (B) and 1.60 g for (C).
  • a one-part tablet comprising a mixture of (A), (B) and (C) similar to those prepared in Example 2 was also prepared.
  • a solid color developing composition is more preferable when the color developing agent and an alkali are separated into plural units than when put into one unit, from the viewpoints of deliquescence and prevention of developing agent oxidation.
  • deterioration can be inhibited by making use of anhydrous lithium hydroxide.
  • a tablet for processing a color paper was prepared by the following procedure.
  • the resulting granules thereby prepared and 150 g of polyethylene glycol 6000 were uniformly mixed for 10 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. Then, 4 g of sodium N-lauroylalanine was added and mixed together, taking 3 minutes. Thereafter, the resulting mixture was compression-tableted varying the filled amount per tablet as shown in Table 3, by a tableting machine, a remodeled Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that Tablet (A) for replenishing a color developing composition for color paper use was prepared.
  • Disodium disulfoethyl hydroxylamine was pulverized and granulated in the same manner as in Procedure (A), except that 60ml of water was added. After completing the granulation, the resulting granules were dried at 50°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom. Then, 4 g of sodium N-lauroylalanine was added to the resulting granules and mixed together by a mixer for 3 minutes in a thermo-hydrostatic room at 25°C and not higher than 40%RH.
  • the resulting mixture was compression-tableted to have a filled amount of 1.0 g per tablet by a tableting machine, a remodeled Tough-Pressed-Collect Model 1527HU manufactured by Kikusui Mfg. Works, so that 1,000 tablets B for replenishing a color developing composition for color paper use were prepared.
  • Tinopar SFP manufactured by Ciba-Geigy AG.
  • 37 g of sodium sulfite 37 g of potassium bromide, 250 g of diethylene triamine pentaacetic acid, 2800 g of sodium p-toluene sulfonate, an alkali shown in Table 3, and 106 g of mannitol were pulverized in the same manner as in Procedure (A). Thereafter, the resulting pulverized matter was uniformly mixed by a mixer available on the market. Then, granulation was carried out in the same manner as in Procedure (A), except that 150 ml of water was added.
  • the granules were dried at 60°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom. Then, 4 g of sodium N-lauroylalanine was added to the resulting granules and mixed together by a mixer for 3 minutes in a thermo-hydrostatic room at 25°C and not higher than 40%RH. The resulting mixture was compression-tableted to give a filled amount of 3.2 g per tablet by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 1,000 tablets C for replenishing a color developing composition for color paper use were prepared.
  • Potassium carbonate of 3,500 g was pulverized and then granulated in the same manner as in Procedure (A). 150ml of water was added in the granulation. Thereafter, the resulting granules were dried at 700°C for 30 minutes, so that the moisture of the granules was almost completely removed therefrom.
  • the resulting granules thereby prepared and 150 g of polyethylene glycol 6000 were uniformly mixed for 10 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH. Then, 4 g of sodium N-lauroylalanine was added and mixed together taking 3 minutes. Thereafter, the resulting mixture was compression-tableted to give a filled amount of 3.0 g per tablet as shown in Table 3, by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 1,000 Tablets D for replenishing a color developing composition for color paper use were prepared.
  • the resulting mixture was then compression-tableted so as to have a filled amount of 4.3 g per tablet by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 340 Tablets A for replenishing a bleach-fixing composition for color paper use were prepared.
  • the resulting mixture was then compression-tableted so as to give a filled amount of 3.35 g per tablet by a tableting machine obtained by modifying Tough Press Correct Model 1527HU manufactured by Kikusui Mfg. Works, so that 720 Tablets B for replenishing a bleach-fixing composition for color paper use were prepared.
  • a tablet supplying function, a liquid level detecting function, and a water supplying function were provided to a Konica Color Paper Type QA Processor Model CL-PP-718, and the following processing experiments were carried out.
  • the tablet supplying function, liquid level detecting function, water supplying function and so forth the devices shown in Figs. 3 and 5 illustrated in JP OPI Publication No. 5-119454/1993 were used. The devices thereof shown in the figures are detailed in the same application, pp. 44-53.
  • the standard processing conditions of the processor were as follows. Processing step Temperature Time Color developing 39 ⁇ 0.3°C 22sec. Bleach-fixing 35 ⁇ 1.0°C 22sec. Stabilizing-1 33 ⁇ 3.0°C 20sec. Stabilizing-2 33 ⁇ 3.0°C 20sec. Stabilizing-3 33 ⁇ 3.0°C 20sec. Drying 72 ⁇ 5.0°C 40sec.
  • a stabilizer was replenished to the 3rd tank (for stabilizing step-3) and the overflow flowed into the 2nd tank (for stabilizing step-2) and then into the 1st tank (for stabilizing step-1) in this order, which is a so-called cascade system.
  • the processing solutions for an automatic processor were prepared by the following procedures.
  • Konica Color QA Paper, Type A5, manufactured by Konica Corp. was used as the light-sensitive material subject to the tests. After imagewise exposing the light-sensitive material to light in an ordinary method, the exposed light-sensitive material was running processed in the foregoing processing steps. The running process was continuously carried out until the replenishment amount was twice the capacity of the color developing tank, which is referred to as 2R. The quantity of the light-sensitive materials processed per day was 0.05R.
  • a wedgewise exposed light-sensitive material was processed when at the start of the running process and when completing the running process, and the density of the processed light-sensitive materials was measured. Each maximum density (Dmax) in blue, green and red was also measured. For 20 of each of the tablets present in the replenishing tablet supplying device of the automatic processor, an observation was made on how the tablet shape varied until all the tablets C for replenishing a color developing solution were used up. The results are shown in Table 4.
  • Table 3 show that the effects of the invention are a prevention of the variation of the tablet shape and of the processing stability when water was replenished to a color developing tank in an amount of not more than 150 ml per m 2 of a light-sensitive material, with a greater effect being obtained when water was replenished in an amount of not more than 100 ml per m 2 of the light-sensitive material.
  • This example was performed in the same manner as in Example 4, in that each tablet was prepared and was then running processed; except that the time required for carrying out the color developing step was varied as shown in Table 5, and, the filled amount of tablet A for replenishing a color developing composition and the alkali contained in tablet C were each varied as shown in Table 5.
  • the color developing agent contained in tablet A and the preservative contained in tablet B were each varied as shown in Table 5. Further, the amount of water replenished to the color developing tank was 81 ml per m 2 of the light-sensitive material and 7.0 g of potassium chloride was added as a starter when starting the running process.
  • a tablet for processing a color negative film was prepared by the following procedure.
  • the tablets of the invention show improved deliquescence and hardness.
  • a tablet for processing a color negative film was prepared by the following procedure.
  • a developing agent CD-4 [that is 4-amino-3-methyl-N-ethyl- ⁇ -(hydroxy)ethylaniline sulfate]
  • a stirring type granulator available on the market, the resulting fine powder was granulated by adding 10 ml of water at room temperature for about 7 minutes and was then dried by a fluid-bed type drier at 40°C for 2 hours, so that the moisture of the granules was almost completely removed therefrom.
  • the granules prepared in the above-mentioned Procedures (4) through (6) were uniformly mixed together for 10 minutes by a mixer in a thermo-hydrostatic room at 25°C and not higher than 40%RH.
  • 6 g of sodium N-lauroylsarcosine was added and then mixed for 3 minutes.
  • the resulting mixture was compression-tableted to give an amount of 6.78 g per tablet by a tableting machine obtained by modifying Tough Press Correct 1527HU manufactured by Kikusui Mfg. Works, so that 80 tablets for replenishing a bleaching solution for color negative film use were prepared.
  • the granules prepared in the above-mentioned Procedure (10) were compression-tableted to give an amount of 0.48 g per tablet by a tableting machine obtained by modifying Tough Press Correct 1527HU manufactured by Kikusui Mfg. Works in a thermo-hydrostatic room at 25°C and not higher than 40%RH, so that 280 tablets for replenishing a stabilizing solution for color negative film use were prepared.
  • a Konica Color Negative Film Processor Model CL-KP-50QA was modified so as to be provided with a tablet supplying function, a liquid level detecting function, a warm water supplying function and so forth.
  • the following processing experiments were carried out by making use of the above-mentioned automatic processor.
  • the standard processing conditions for the automatic processor were as follows. Processing step Temperature Time Color developing 38 ⁇ 0.3°C 3min.15sec. Bleaching 38 ⁇ 1.0°C 45sec. Fixing-1 38 ⁇ 1.0°C 45sec. Fixing-2 38 ⁇ 1.0°C 45sec. Stabilizing-1 38 ⁇ 3.0°C 20sec. Stabilizing-2 38 ⁇ 3.0°C 20sec. Stabilizing-3 38 ⁇ 3.0°C 20sec. Drying 60°C 60sec.
  • the stabilizing solution was replenished to the 3rd tank (for stabilizing step-3) and the overflow therefrom flowed into the 2nd tank (for stabilizing step-2) and then to the 1st tank (for stabilizing step-1); and the fixing solution was replenished to the 2nd tank (for fixing step-2) and the overflow therefrom flowed into the 1st tank (for fixing step-1) and then to the 1st tank (for stabilizing step-1); that is a so-called cascade system.
  • Processing solutions applicable to the automatic processor were prepared by the following procedures.
  • Each of the tablets was prepared in the same manner as in Example 4.
  • a series of 20 fractionized packages were packaged in a 4-side sealing system by making use of a peel-open type packaging material.
  • One tablet for replenishing a stabilizing composition was packed as one package and then 20 packages were prepared as above.
  • the peel-open packaging material was prepared by making use of Tocello CMPSO11C as a sealant film and then laminating the sealant film on a non-stretched polypropylene film surface of a non-stretched polypropylene film/a stretched polypropylene film.
  • the prepared peel-open film and a non-stretched polypropylene film/a stretched polypropylene film were heat-sealed together in a manner such that the above-mentioned tablets were packed between them.
  • Water-supplying device and so forth were arranged in the same as in Example 4, that is, based upon those described in JP Application No. 4-111502/1992.
  • Fig. 1 illustrates a perspective view showing an example of solid processing composition supplying devices 140 suitable for use with the invention, wherein the solid processing composition was supplied to a processing tank by peeling off a package containing the solid type processing composition.
  • the leading edge of a 4-side sealed package containing a solid type processing composition was attached to take-up spool 142 serving as a fixing means through roller 141.
  • take-up spool 142 serving as a fixing means through roller 141.
  • a processed quantity information detecting means When a subject light-sensitive material was processed, it was detected by a processed quantity information detecting means.
  • a signal is sent from a processing composition supply controlling means, to the motor of take-up spool 142, that was also serving as a processing composition supplying means, so that it rotates.
  • a package containing a solid type processing composition is moved forward by a specified length, so that the necessary amount of the solid type processing composition is put in the processing tank.
  • Any means for moving a package may be used, for example, a means for detecting a notch provided in advance to a package, means for detecting a printed pattern, or means for detecting a processing composition contained in a package.
  • such means for moving a package as mentioned above is to be capable of precisely detecting the number of necessary solid type processing compositions and moving them through roller 141 or take-up spool 142.
  • Roller 141 was provided for the purpose of fixing or positioning a package and, thereby, a package is peeled off by two take-up spools and the required amount of the solid type processing composition is put into the processing tank.
  • Figs. 2(a) and 2(b) illustrate each a system for dividing and cutting a series of packages into two parts.
  • a subject light-sensitive material when processed, it is detected by a processed quantity information detecting means.
  • a signal is sent from the processing composition supplying means to transport rollers 502.
  • the ceramic or stainless steel-made circular edge 301 is rotated to cut the lower part of the series of packages 603 into 2 parts, so that solid type processing composition 10 is put into the processing tank.
  • the packages are spread out towards both sides of suction guide 202 by suction so that solid type processing composition can readily drop.
  • Empty package 603 containing no solid type processing composition 10 was moved out of position by transport rollers 401 when the next solid processing composition 10 is ready to be dropped and is then scrapped in package container 101.
  • the above-mentioned processing composition supplying means can be applied to compositions not only of a solid tablet type but also of a powder or granule type.

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

Claims (12)

  1. Festes Behandlungsmittel für ein lichtempfindliches farbphotographisches Silberhalogenid-Aufzeichnungsmaterial, umfassend eine Farbentwicklerzusammensetzung mit einem Farbentwickler vom p-Phenylendiamintyp und Lithiumhydroxid.
  2. Festes Behandlungsmittel nach Anspruch 1, umfassend wasserfreies Lithiumhydroxid.
  3. Festes Behandlungsmittel nach Anspruch 1 oder 2 in Form einer Tablette oder in Granulatform.
  4. Festes Behandlungsmittel nach Anspruch 1, 2 oder 3, welches zusätzlich eine Verbindung der folgenden Formel (A):
    Figure imgb0042
     worin bedeuten:
    L eine Alkylengruppe;
    A eine Carboxyl-, Sulfo-, Phosphono-, Phosphinsäure-, Hydroxy-, Amino-, Ammonio-, Carbamoyl- oder Sulfamoylgruppe und
    R ein Wasserstoffatom oder eine Alkylgruppe
    enthält.
  5. Festes Behandlungsmittel nach einem der vorhergehenden Ansprüche, welches zusätzlich eine aromatische Sulfonsäure oder ein Salz derselben enthält.
  6. Festes Behandlungsmittel nach einem der vorhergehenden Ansprüche, wobei die Farbentwicklerzusammensetzung ein Gemisch aus einem Lithiumhydroxid enthaltenden Granulat und einem eine Farbentwicklerverbindung vom p-Phenylendiamintyp enthaltenden Granulat umfaßt.
  7. Festes Behandlungsmittel nach Anspruch 6, wobei das Gemisch zusätzlich ein eine Verbindung der Formel (A) entsprechend der Definition von Anspruch 4 enthaltendes Granulat umfaßt.
  8. Festes Behandlungsmittel nach einem der vorhergehenden Ansprüche in Tablettenform.
  9. Verfahren zur Herstellung des festen Behandlungsmittels nach Anspruch 8 durch Tablettieren eines Gemischs des Lithiumhydroxid enthaltenden Granulats und des die Farbentwicklerverbindung vom p-Phenylendiamintyp enthaltenden Granulats.
  10. Verfahren nach Anspruch 9, wobei das Gemisch zusätzlich das in Anspruch 7 definierte Granulat enthält.
  11. Verfahren nach Anspruch 9 oder 10, wobei vor dem Vermischen jede Art Granulat im Granulatgemisch getrennt granuliert wird.
  12. Verfahren zum Behandeln eines lichtempfindlichen farbphotoqraphischen Silberhalogenid-Aufzeichnungsmaterials durch
    (a) Entwickeln des belichteten Aufzeichnungsmaterials mit einem Entwickler und
    (b) Ergänzen des Entwicklers mit einem festen Behandlungsmittel gemäß der Definition in einem der Ansprüche 1 bis 8 oder hergestellt nach dem Verfahren gemäß der Definition in Anspruch 9, 10 oder 11.
EP19940300373 1993-01-19 1994-01-19 Feste Zusammensetzung zur Verarbeitung von photographischen lichtempfindlichen Silberhalogenidfarbmaterialien und deren Verarbeitungsverfahren Expired - Lifetime EP0611989B1 (de)

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EP0687950A1 (de) * 1994-05-27 1995-12-20 Konica Corporation Verarbeitungszusammensetzung in Granulat- oder Tablettenform für die Verarbeitung eines photographischen lichtempfindlichen Silberhalogenidmaterials
DE19719117A1 (de) * 1997-05-06 1998-11-12 Grabig Tetenal Photowerk Farbentwickler in Form eines Feststoffes

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US4756996A (en) * 1986-11-03 1988-07-12 Polaroid Corporation Photographic processing composition for processing a photosensitive element of the self-developing type
DE3830023A1 (de) * 1988-09-03 1990-03-15 Agfa Gevaert Ag Granulierter, farbfotografischer entwickler und seine herstellung

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