EP0566323B1 - Developer for silver halide photographic light-sensitive material - Google Patents

Developer for silver halide photographic light-sensitive material Download PDF

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Publication number
EP0566323B1
EP0566323B1 EP19930302781 EP93302781A EP0566323B1 EP 0566323 B1 EP0566323 B1 EP 0566323B1 EP 19930302781 EP19930302781 EP 19930302781 EP 93302781 A EP93302781 A EP 93302781A EP 0566323 B1 EP0566323 B1 EP 0566323B1
Authority
EP
European Patent Office
Prior art keywords
developer
compound
mol
silver
per liter
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19930302781
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German (de)
English (en)
French (fr)
Other versions
EP0566323A2 (en
EP0566323A3 (enrdf_load_stackoverflow
Inventor
Kenichi Konica Corporation Inoue
Tsuyoshi Konica Corporation Mitsuhashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
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Filing date
Publication date
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0566323A2 publication Critical patent/EP0566323A2/en
Publication of EP0566323A3 publication Critical patent/EP0566323A3/xx
Application granted granted Critical
Publication of EP0566323B1 publication Critical patent/EP0566323B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • G03C5/29—Development processes or agents therefor
    • G03C5/305—Additives other than developers

Definitions

  • the present invention relates to a photographic developer for a silver halide photographic light-sensitive material capable of forming an image of high sensitivity and high density without silver sludge formation even when processed at low replenishing rates.
  • Sulfites such as sodium sulfite and potassium sulfite, used as antioxidants for photographic developers, have the ability to dissolve silver halide.
  • this silver sludge in suspension in the developer, adheres to the film and the rollers and belts of the automatic processing machine.
  • Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 114035/1983, using a thiouracil, Japanese Patent O.P.I. Publication No. 2043/1988, using a mercaptobenzoic acid, Japanese Patent Examined Publication No. 14953/1972, using an aliphatic mercaptocarboxylic acid, Japanese Patent O.P.I. Publication No. 178959/1987, Japanese Patent O.P.I. Publication No. 51844/1991, using a disulfide, Japanese Patent O.P.I. Publication No. 26136/1973, using a sulfur-containing ⁇ -amino acid, and various mercaptoazoles, all of which are compounds likely to form a water-soluble silver salt.
  • US-A-4141734 discloses a process for developing exposed photographic silver halide materials.
  • the aqueous developer preparation used contains a developer compound for the silver halide, a water-soluble solvent for the silver halide and an aliphatic, cycloaliphatic, aromatic or heterocyclic di-or trisulphide, such as L-cystine.
  • US-A-4254215 discloses a process for the prevention of darkening and the formation of a sediment in photographic developer solutions which contain a silver halide developer, a water-soluble silver halide solvent and, as sulphur compounds, a combination of (a) an organic thiol compound or thione compound capable of tautomerism and (b) a Bunte salt which contains groups conferring solubility in water such as penicillamine or cysteine.
  • An object of the present invention is to to provide a developer which allows an image of excellent finish quality to be easily obtained without silver sludge formation, photographic developer stain and roller/belt stain even when used at low replenishing rates in the continuous processing of a large amount of light-sensitive material using an automatic processing machine, and which has a sludge-preventing effect without affecting the photographic performance.
  • a developer for developing a silver halide photographic light-sensitive material which contains a compound represented by the following formula 1 or 2: wherein R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms provided that R1 and R2 do not represent hydrogen atoms at the same time. R3 and R4 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R5 represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms.
  • R6 and R7 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having up to 18 carbon atoms or a -COOM2 group, provided that R6 and R7 do not represent hydrogen atoms at the same time.
  • M1 represents a hydrogen atom, an alkali metal atom or an ammonium group, and m represents 0, 1 or 2.
  • M2 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group or an aralkyl group having not more than 15 carbon atoms.
  • Alkyl groups having 1 to 4 carbon atoms as described above include a methyl group, an ethyl group, a propyl group and a butyl group.
  • acyl groups having up to 18 carbon atoms include an acetyl group and a benzoyl group.
  • aralkyl groups having up to 15 carbon atoms include a benzyl group and a phenethyl group.
  • Aryl groups include a phenyl group and a naphthyl group.
  • alkali metal atoms for M1 examples include sodium ion and potassium ion.
  • Strecker's method of amino acid synthesis known to be an amino acid synthesis method, wherein amino acid acetylation is achieved by alternate addition of alkali and acetic anhydride in an aqueous solution.
  • the above compounds used in the present invention may be used singly or in combination. It is also acceptable to use in combination at least one compound of formula 1 and at least one compound of formula 2.
  • the compounds of formulas 1 and 2 are used in amounts of preferably 1 ⁇ 10 ⁇ 5 to 3 ⁇ 10 ⁇ 2 mol, more preferably 1 ⁇ 10 ⁇ 4 to 1 ⁇ 10 ⁇ 2 mol per liter of developer.
  • the replenishing rate for the developer of the present invention is normally 0.05 to 0.65 l, preferably 0.10 to 0.35 l per m2 of light-sensitive material, though it varies depending on the kinds of light-sensitive material, automatic processing machine, and other factors.
  • the developing through drying processes are completed within 90 seconds when an automatic processing machine capable of developing, fixing and washing or stabilizing is used to process a silver halide light-sensitive material.
  • the time from initiation of immersion of the tip of the light-sensitive material in the developer, via the various processes, to discharge of the same tip from the drying zone is preferably not longer than 90 seconds, more preferably not longer than 60 seconds.
  • Fixing temperature and time are preferably about 20 to 50°C and 6 to 20 seconds, more preferably 30 to 40°C and 6 to 15 seconds.
  • developing time is normally 5 to 45 seconds, preferably 8 to 30 seconds, and developing temperature is preferably 25 to 50°C, more preferably 30 to 40°C.
  • Drying may be achieved by hot air blowing at normally 35 to 100°C, preferably 40 to 80°C.
  • a drying zone equipped with a far infrared heating means may be arranged in the automatic processing machine.
  • the automatic processing machine may be equipped with a mechanism for adding either water or an acidic rinsing solution having no fixing capability to the light-sensitive material, among the above developing, fixing and washing processes such as those described in Japanese Patent O.P.I. Publication No. 264953/199.
  • the automatic processing machine may also have therein equipment for preparing developers and fixers.
  • the developer of the present invention preferably contains as a developing agent a 1,4-dihydroxybenzene compound or, if necessary, a p-aminophenol compound and/or a pyrazolidone compound.
  • 1,4-dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and hydroquinone monosulfonate, with preference given to hydroquinone.
  • p-aminophenol-based developing agents include N-methyl-p-aminophenol, p-aminophenol, N-( ⁇ -hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol and p-benzylaminophenol, with preference given to N-methyl-p-aminophenol.
  • the amount of 1,4-dihydroxybenzene added is preferably 0.01 to 0.7 mol, more preferably 0.1 to 0.5 mol per liter of developer.
  • the amounts of p-aminophenol compound and pyrazolidone compound added are preferably 0.0005 to 0.2 mol, more preferably 0.001 to 0.1 mol per liter of developer.
  • sulfites optionally used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and potassium metasulfite.
  • the amount of these sulfites used is preferably 0.1 to 2.0 mol, more preferably 0.1 to 1.0 mol per liter of developer.
  • the upper limit is preferably 3.0 mol per liter of developer for a concentrated developer.
  • the developer may optionally contain a chelating agent having an iron ion chelating stability constant of over 8.
  • the preferred iron ion mentioned herein is ferric ion (Fe3+).
  • Chelating agents having an iron ion chelating stability constant of over 8 include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents and polyhydroxyl compounds.
  • such chelating agents include ethylenediamine-di-o-hydroxyphenylacetic acid, triethylenetetramineacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diamino-2-propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether amine tetraacetic acid, ethylenediamine-N,N,N′,N′-tetrakismethylenephosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, 1-hydroxyethyliden
  • the developer of the present invention may optionally contain a hardener which enhances the film physical properties by reacting with the gelatin in the light-sensitive material during the developing process.
  • hardeners include glutaraldehyde, ⁇ -methylglutaraldehyde, ⁇ -methylglutaraldehyde, maleic dialdehyde, succinic dialdehyde, methoxysuccinic dialdehyde, methylsuccinic dialdehyde, ⁇ -methoxy- ⁇ -ethoxyglutaraldehyde, ⁇ -n-butoxyglutaraldehyde, ⁇ , ⁇ -dimethoxysuccinic dialdehyde, ⁇ -isopropylsuccinic dialdehyde, ⁇ , ⁇ -diethylsuccinic dialdehyde, butylmaleic dialdehyde and bisulfite adducts thereof.
  • the developer may further contain developing inhibitors such as sodium bromide and potassium iodide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, mercapto compounds such as 1-phenyl-5-mercaptotetrazole and sodium 2-mercaptobenzimidazole-5-sulfonate, and antifoggants such as 5-methylbenzotriazole and other benzotriazole compounds.
  • organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol
  • mercapto compounds such as 1-phenyl-5-mercaptotetrazole and sodium 2-mercaptobenzimidazole-5-sulfonate
  • antifoggants such as 5-methylbenzotriazole and other benzotriazole compounds.
  • Other additives such as
  • the pH of the developer is preferably 9.0 to 12, more preferably 9.0 to 11.5.
  • Examples of the alkali or buffer used for pH adjustment include pH regulators such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium tertiary phosphate and potassium tertiary phosphate.
  • a fixer used for fixing the light sensitive material developed by the developer of the invention may contain a fixing agent such as sodium thiosulfate or ammonium thiosulfate, with preference given to ammonium thiosulfate from the viewpoint of fixing speed.
  • fixing agents are usually used in amounts of about 0.1 to 6 mol/liter.
  • the fixer may also optionally contain a water-soluble aluminum salt as a hardener, such as aluminum chloride, aluminum sulfate or potassium alum.
  • a water-soluble aluminum salt as a hardener, such as aluminum chloride, aluminum sulfate or potassium alum.
  • the fixer may optionally incorporate malic acid, tartaric acid, citric acid, gluconic acid and derivatives thereof, singly or in combination. These compounds are effective when contained at not less than 0.001 mol per liter of fixer, with a greater effect obtained at 0.005 to 0.03 mol per liter of fixer.
  • Fixer pH is normally not lower than 3.8, preferably 4.2 to 7.0. In view of hardening in the fixer and the emission of sulfurous acid gas odor the pH is more preferably 4.3 to 4.8.
  • Silver halide photographic light-sensitive material emulsions to which the developer of the present invention is applicable include medical radiographic materials, photographic materials for printing plate making and direct positive photographic materials.
  • the silver halide photographic light-sensitive material to which the developer of the present invention is applied may comprise a silver halide such as silver iodobromide, silver iodochloride or silver iodochlorobromide, with preference given to silver iodobromide from the viewpoint of high sensitivity.
  • a silver halide such as silver iodobromide, silver iodochloride or silver iodochlorobromide, with preference given to silver iodobromide from the viewpoint of high sensitivity.
  • Suitable emulsions for the silver halide photographic light-sensitive material include monodispersed grains of high inner iodine content such as those disclosed in Japanese Patent O.P.I. Publication Nos. 177535/1984, 802237/1986, 132943/1986 and 49751/1988. Crystalline form may be, for example, cubic, tetradecahedral or octahedral, and intermediate (111) and (100) planes may be present in any ratio.
  • the emulsion may be of tabular grains having an aspect ratio of not less than 2. Such tabular grains have advantages such as improvements in spectral sensitizing efficiency, image granularity and sharpness, and are disclosed in British Patent No. 2,112,157, US Patent Nos. 4,439,520, 4,433,048, 4,414,310 and 4,434,226, and Japanese Patent O.P.I. Publication Nos. 113927/1983, 127921/1983, 138342/1988, 284272/1988 and 305343/1988.
  • the emulsion can be prepared as described in these publications.
  • Additives and other substances used in the silver halide photographic light-sensitive material include those described in Research Disclosure Nos. 17643 (December, 1978), 18716 (November, 1979) and 308119 (December, 1989) (hereinafter referred to as RD17643, RD18716 and RD308119, respectively). The following table shows where they are described.
  • the resulting reaction mixture was desalinized at 40°C, using an aqueous solution of Demol-N (produced by Kao Atlas) and an aqueous solution of magnesium sulfate, after which it was re-dispersed in an aqueous gelatin solution, to yield a seed emulsion.
  • grains were grown as follows: First, the seed emulsion was dispersed in an aqueous gelatin solution being kept at 40°C, and aqueous ammonia and acetic acid were added to obtain a pH of 9.7. An aqueous solution of ammoniacal silver nitrate and an aqueous solution of potassium bromide and potassium iodide were then added to the dispersion by the double jet method, while maintaining a pAg of 7.3 and a pH of 9.7, to yield a layer containing 35 mol% silver iodide. Next, another aqueous solution of ammoniacal silver nitrate and an aqueous solution of potassium bromide were added by the double jet method.
  • the pAg was kept at 9.0, with the pH varied continuously over the range of 9.0 to 8.0. The pAg was then changed to 11.0, and while keeping the pH at 8.0, grains were grown up to the desired grain size. Subsequently, acetic acid was added to obtain a pH of 6.0, after which 400 mg of the anhydride of 5,5′-dichloro-9-ethyl-3,3′-di(3-sulfopropyl)oxacarbocyanine sodium salt was added per mol of silver halide. This mixture was then desalinized with the above aqueous solution of Demol-N and an aqueous solution of magnesium sulfate, and then re-dispersed in a gelatin solution.
  • Monodispersed silver iodobromide emulsions A, B and C comprising tetradecahedral grains with round tips having an average silver iodide content of 2.0 mol%, were thus prepared, having average grain sizes of 0.40, 0.65 and 1.00 ⁇ m and variation coefficients of grain size distribution ( ⁇ / r ) of 0.17, 0.16 and 0.16, respectively, in which ⁇ is the standard deviation of grain size distribution and r is the average grain size.
  • a hexagonal tabular seed emulsion was prepared as follows:
  • solution A After stopping the addition of solutions B and C, the temperature of solution A was increased to 60°C over a period of 60 minutes, and solutions B and C were again added by the double jet method at a flow rate of 68.5 ml/min over a period of 50 minutes, while keeping the silver potential (determined using a silver ion selective electrode in combination with a saturated silver-silver chloride electrode as a reference electrode) at +6 mV using solution D.
  • Grains were grown at 60°C by adding all of solutions B and C to solution A at a flow rate of 21.26 ml/min over a period of 111 minutes, using the mixer stirrer described in Japanese Patent Examined Publication Nos. 58288/1983 and 58289/1983 as above.
  • the silver potential was kept at +25 mV using solution D.
  • the following spectral sensitizing dyes A and B were added in amounts of 300 mg and 15 mg, respectively, per mol of silver halide.
  • a 200:1 (w/w) mixture of the above sensitizing dyes A and B was added at 975 mg, 600 mg, 390 mg and 500 mg per mol of silver halide, respectively.
  • emulsion II Of the four ripened emulsions, A, B and C were mixed in a weight ratio of 15:65:20, to yield emulsion I, while emulsion D, designated as emulsion II, was used by itself.
  • aqueous solution a 9.3% aqueous solution of gelatin containing 1.35 kg of an anionic surfactant AS was prepared. This solution is called the aqueous solution.
  • the oily solution and the aqueous solution were placed in a dispersing vessel and dispersed while keeping the liquid temperature at 40°C.
  • To the resulting dispersion were added appropriate amounts of phenol and 1,1-dimethylol-bromo-1-nitromethane, and water was added to 240 kg.
  • composition of the protective layer is as follows: The amounts of addition are shown per liter of coating solution.
  • the resulting coating solution was coated and dried uniformly on a blue-colored subbed polyethylene terephthalate film base 180 ⁇ m thick.
  • both the emulsion layer and the protective layer were coated simultaneously at a coating speed of 90 m per minute, to yield samples, wherein coating rates were 1.7 g/m2 as of silver for the emulsion layer and 0.99 g/m2 as of gelatin for the protective layer.
  • developing sample 1 was obtained from emulsion I, and developing sample 2 obtained from emulsion II.
  • compositions of the developer and fixer used in the present invention are as follows:
  • fixer replenisher To prepare the fixer, parts A and B were added at the same time to about 5 liters of water, and while stirring and dissolving the mixture, water was added to 18 liters, and sulfuric acid or NaOH were added to obtain a pH of 4.4, to yield a fixer replenisher.
  • Comparative Compounds 1 - 12 were used as comparative compounds.
  • Processing temperatures were 35°C for developing, 33°C for fixation, 20°C for washing and 50°C for drying.
  • the sample inserted between two sheets of fluorescent sensitizing paper KO-250, manufactured by Konica Corp., was subjected to exposure through an aluminum wedge of at a tube voltage of 80 kV, a tube amperage of 100 mA and an irradiation time of 50 msec, after which it was processed using the above automatic processing machines.
  • the reciprocal of the exposure amount required to obtain a density of base density + fog density + 1.0 was calculated as a percent sensitivity relative to the sensitivity of sample No. 1 processed with the above developer and fixer of basic composition using automatic processing machine No. 2 (experiment No. 15).
  • the density in the unexposed portion of the exposed sample was determined using Konica PDA-65 densitometer, and the base density was subtracted therefrom to obtain the fog density, and the maximum density was expressed as Dm. 2. Silver sludge evaluation
  • the developing samples used were the above sample Nos. 1 and 2.
  • silver sludge is substantially prevented without photographic performance deterioration even at reduced developer replenishing rates.
  • Table 1 shows that the addition of the compound used in the present invention to the developer did not lower the sensitivity or Dm (maximum density), while the addition of a comparative compound significantly lowered the sensitivity, though it had a slight preventative effect on silver sludge at high replenishing rates.
  • Results of experiment Nos. 1 through 10 demonstrate that developers containing a compound used in the present invention remain excellently effective without deterioration of the silver sludge preventing effect even when the replenishing rate is reduced to 200 ml/m2. Also, the results of experiment Nos. 12 and 14 demonstrate that there is no difference in silver sludge preventing effect among different automatic processing machines.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19930302781 1992-04-13 1993-04-08 Developer for silver halide photographic light-sensitive material Expired - Lifetime EP0566323B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP92947/92 1992-04-13
JP4092947A JP2955906B2 (ja) 1992-04-13 1992-04-13 ハロゲン化銀写真感光材料用現像液

Publications (3)

Publication Number Publication Date
EP0566323A2 EP0566323A2 (en) 1993-10-20
EP0566323A3 EP0566323A3 (enrdf_load_stackoverflow) 1994-03-23
EP0566323B1 true EP0566323B1 (en) 1995-10-11

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EP19930302781 Expired - Lifetime EP0566323B1 (en) 1992-04-13 1993-04-08 Developer for silver halide photographic light-sensitive material

Country Status (3)

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EP (1) EP0566323B1 (enrdf_load_stackoverflow)
JP (1) JP2955906B2 (enrdf_load_stackoverflow)
DE (1) DE69300613T2 (enrdf_load_stackoverflow)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5510231A (en) * 1993-04-27 1996-04-23 Konica Corporation Solid developing composition for silver halide photographic light-sensitive material and processing method using the same
US5506092A (en) * 1993-12-06 1996-04-09 Konica Corporation Method of processing black and white silver halide photographic compositions with a developer containing an anti sludgant
US5824458A (en) * 1994-02-28 1998-10-20 Fuji Photo Film Co., Ltd. Developer and fixing solution for silver halide photographic material and processing method using the same
DE69516054T2 (de) 1994-07-18 2000-10-26 Konica Corp., Tokio/Tokyo Photographisches Silberhalogenidelement und sein Verarbeitungsverfahren
GB0103527D0 (en) * 2001-02-13 2001-03-28 Eastman Kodak Co Photographic developing composition and use thereof in the development of a photographic element

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4141734A (en) * 1975-09-11 1979-02-27 Ciba-Geiby Ag Photographic developing process
US4254215A (en) * 1978-03-31 1981-03-03 Ciba-Geigy Ag Process for the prevention of darkening and the formation of a sediment in photographic developer solutions

Also Published As

Publication number Publication date
JPH05289255A (ja) 1993-11-05
EP0566323A2 (en) 1993-10-20
DE69300613T2 (de) 1996-04-04
JP2955906B2 (ja) 1999-10-04
EP0566323A3 (enrdf_load_stackoverflow) 1994-03-23
DE69300613D1 (de) 1995-11-16

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