EP0136582B1 - Entwicklerzusammensetzungen für photographische Silberhalogenidmaterialien - Google Patents

Entwicklerzusammensetzungen für photographische Silberhalogenidmaterialien Download PDF

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Publication number
EP0136582B1
EP0136582B1 EP84110559A EP84110559A EP0136582B1 EP 0136582 B1 EP0136582 B1 EP 0136582B1 EP 84110559 A EP84110559 A EP 84110559A EP 84110559 A EP84110559 A EP 84110559A EP 0136582 B1 EP0136582 B1 EP 0136582B1
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EP
European Patent Office
Prior art keywords
acid
grams per
per liter
amount
silver halide
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
Application number
EP84110559A
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English (en)
French (fr)
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EP0136582A3 (en
EP0136582A2 (de
Inventor
Carlo Marchesano
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3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
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Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Publication of EP0136582A2 publication Critical patent/EP0136582A2/de
Publication of EP0136582A3 publication Critical patent/EP0136582A3/en
Application granted granted Critical
Publication of EP0136582B1 publication Critical patent/EP0136582B1/de
Expired 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
    • G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents

Definitions

  • the present invention relates to developer compositions for silver halide photographic materials and, particularly, to photographic silver halide developer compositions having improved resistance to aerial oxidation.
  • treatment of black and white silver halide photographic materials is carried out in the order of development, stopping, fixing and washing.
  • Some compounds have been proposed to reduce or eliminate the catalytic effect of such metal ions, especially iron, on the aerial oxidation of developers by forming very stable complexes with said metal ions in alkaline solution, but their activity is reduced to a high degree when silver halide photographic materials are treated in continuous transport processing machines, especially at high temperatures. In that case, considerable quantities of air are introduced into developer solutions used in processing machines, this aeration oxidizing more of the developing agent than the real development process itself, causing a rapid degradation of the developer.
  • GB-A-2,010,514 describes a developer composition for silver halide photographic materials comprising hydroquinone, an alkali metal sulfite, an organic antifogging agent, inorganic alkali agents and an alkanolamine.
  • Research Disclosure (Dec. 1979) N. 188, pages 692-693 describes calcium sequestering agents for use in black and white developers including aminocarboxylic acid compounds, polyphosphonic acid compounds and combinations thereof.
  • GB-A-1,216,854 describes the combined use of a mercapto agent and a benzotriazole agent to maintain the contrast throughout the life of the developer.
  • C.A. Vol. 91 N. 149402u describes a photographic developing-fixing solution containing hydroquinone, Metol, Phenidone, benzotriazole and 1 - phenyl - 5 - mercaptotetrazole.
  • a developer composition for silver halide photographic materials has been found which has improved resistance to air oxidation, even in the presence of metal ion traces.
  • the composition can be left in continuous transport processing machines for several days, said developer compositions having the following constituents:
  • the present invention relates to a developer composition for silver halide photographic materials comprising hydroquinone or a substituted hydroquinone, an alkali metal sulfite, an organic antifoggant agent and inorganic alkali agents, characterized by further comprising an alkanolamine and a sequestering agent selected in the group of DTPA, DPTA and HEDP.
  • the above described developer composition comprises an additional compound selected in the group of polyphosphates, phosphoric acid, acetic acid, lactic acid and citric acid.
  • the developer composition above comprises an auxiliary developing agent selected from the class of substituted pyrazolidone and p-aminophenol compounds.
  • the organic antifoggant agent is selected from the group of mixtures of 5 - nitroindazole and benzimidazole nitrate, 5 - nitrobenzotriazole and 1 - phenyl - 5 - mercaptotetrazole, and benzotriazole and 1 - phenyl - 5 - mercaptotetrazole and the alkanolamine is selected from the group of diethanolamine, triethanolamine, 2 - benzylaminoethanol, 2 - methylaminoethanol, 2 - ethylaminoethanol and 2 - isopropylaminoethanol.
  • the present invention relates to a developer composition for silver halide photographic materials comprising hydroquinone or a substituted hydroquinone in an amount of 10 to 30 grams per liter, an auxiliary developing agent in an amount of 0.2 to 5 grams per liter, an alkali metal sulfite in an amount of 20 to 50 grams per liter, an organic antifoggant selected in the group of mixtures of 5 - nitroindazole and benzimidazole nitrate, 5 - nitrobenzotriazole and 1 - phenyl - 5 - mercaptotetrazole and benzotriazole and 1 - phenyl - 5 - mercaptotetrazole in an amount of 0.2 to 1.5 grams per liter, inorganic alkali agents sufficient to provide a pH of at least 10 and water sufficient to make up one liter characterized by including:
  • the present invention relates to a single part concentrated developer composition for silver halide photographic materials, to be diluted with water and form a ready for use developer solution, comprising hydroquinone or a substituted hydroquinone, an alkali metal sulfite and inorganic alkali agents, characterized in that it contains an alkanolamine, an organic sequestering agent selected in the group of DTPA, DPTA and HEDP and a mixture of benzotriazole and 1 - phenyl - 5 - mercaptotetrazole antifogging agents.
  • the single part concentrated developer composition above further comprises a compound selected in the group of polyphosphates, phosphoric acid, acetic acid, lactic acid and citric acid.
  • the single part concentrated developer composition above comprises an auxiliary developing agent selected from the class of substituted pyrazolidone and para-aminophenol compounds.
  • the present invention relates to a concentrated developer composition for silver halide photographic materials to be diluted with water to form a ready-for-use developer composition, comprising hydroquinone or a substituted hydroquinone in an amount of 40 to 120 grams per liter, an auxiliary developing agent in an amount of 0.5 to 20 grams per liter, an alkali metal sulfite in an amount of 80 to 200 grams per liter, a mixture of benzotriazole and 1 - phenyl - 5 - mercaptotetrazole antifogging agents in an amount of 0.8 to 6 grams per liter, inorganic alkali agents sufficient to provide a pH of at least 11, and water sufficient to make up 1 liter, characterized by including:
  • the developing agents for silver halide photographic elements suitable for the purposes of the present invention include hydroquinone and substituted hydroquinones (e.g. t - butylhydroquinone, methylhydroquinone, dimethylhydroquinone, chlorohydroquinone, dichlorohydroquinone, bromohydroquinone, 1,4 - dihydroxynaphthalene, methoxyhydroquinone, ethoxyhydroquinone, etc.). Hydroquinone, however, is preferred.
  • Said silver halide developing agents are generally used in an amount from about 5 to 50, preferably 10 to 30 grams per liter of the developing solution.
  • Such developing agents can be used alone or in combination with auxiliary developing agents which show a superadditive developing effect, such as p-aminophenol and substituted p-aminophenols (e.g. N - methyl - p - aminophenol or metol and 2,4 - diaminophenol) and pyrazolidones (e.g. 1 - phenyl - 3 - pyrazolidone or phenidone) and substituted pyrazolidones (e.g. 4 - methyl - 1 - phenyl - 3 - pyrazolidone and 4,4' - dimethyl - 1 - phenyl - 3 - pyrazolidone). Phenidone, however, is preferred.
  • auxiliary developing agents are generally used in an amount from about 0.1 to 15, preferably 0.2 to 5 grams per liter of the developer.
  • alkali metal sulfites useful in the developer formulation of this invention as preservatives, include for example sodium and potassium metabisulfite. These are used in an amount from about 15 to 100, preferably 20 to 50 grams per liter of the developer solution.
  • organic antifoggant agents known in the art to eliminate fog on the developed photographic silver halide films, useful in the developer formulations of this invention include derivatives of benzimidazole, benzotriazole, tetrazole, indazole, thiazole, etc. It has been found, however, that particular mixtures of these antifoggant agents are particularly useful in the developer formulations of this invention to assure low fog levels in any working condition and in case of fast silver halide emulsion films having a greater tendency to fog.
  • Such preferred mixtures include mixtures of 5-nitroindazole and benzimidazole nitrate, 5 - nitrobenzotriazole and 1 - phenyl - 5 - mercaptotetrazole and benzotriazole and 1 - phenyl - 5 - mercaptotetrazole.
  • the most preferred combination is benzotriazole and 1 - phenyl - 5 - mercaptotriazole, especially when the developer composition ready for use undergoes a storage prolonged in time, for instance more than 15 days at room temperature, before being used.
  • These mixtures are used in a total amount of from about 0.1 to 3, preferably 0.2 to 1.5 grams per liter of the developer composition.
  • Inorganic alkali agents are used in the developer formulations of this invention to achieve the preferred pH range which is above 10.
  • Such inorganic alkali agents include KOH, NaOH, potassium and sodium carbonate, etc.
  • adjuvants well known in the art can be used in the developer formulation of the present invention, these include restrainers, such as soluble halides (e.g. KBr and NaBr), solvents, buffers (e.g. borates and carbonates), development accelerators, and the like.
  • restrainers such as soluble halides (e.g. KBr and NaBr), solvents, buffers (e.g. borates and carbonates), development accelerators, and the like.
  • the developer compositions according to the present invention are characterized by the combination of an alkanolamine with the selected sequestering agents above.
  • Alkanolamines suitable for the purpose of the present invention include the hydroxyalkylamines having the general formula: wherein R 1 and R 2 each are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group, R 3 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and n is an integer of from 1 to 10.
  • Preferred alkanolamines include 2 - benzylaminoethanol, ethanolamine, diethanolamine, triethanolamine, choline chloride, 3 - amino - 1 - propanol, 1 - amino - 2 - propanol, 2 - amino - 2 - methyl - 1,3 - propanediol, tris - (hydroxymethyl) - aminopropane, 2 - methylamino - ethanol, 2 - dimethylamino - ethanol, 2 - ethylamino - ethanol, bis - (2 - hydroxypropyl) - amine, 3 - dimethyl- amino - 1 - propanol and 2 - isopropylaminomethanol.
  • alkanolamines include the ethanolamines such as diethanolamine, triethanolamine, methylaminoethanol, ethylaminoethanol, isopropylaminoethanol and benzylaminoethanol.
  • the alkanolamines are used in an amount from about 10 to 30, preferably 15 to 20 grams per liter of the developer composition.
  • the sequestering agents which combined with alkanolamines render the developer composition more stable to aerial oxidation are selected from the group of diethylenetriaminepentacetic acid (DTPA), 1,3 - diamino - 2 - propanoltetracetic acid (DPTA) and 1 - hydroxyethyliden - 1,1' - diphosphonic acid (HEDP).
  • DTPA diethylenetriaminepentacetic acid
  • DPTA 1,3 - diamino - 2 - propanoltetracetic acid
  • HEDP 1 - hydroxyethyliden - 1,1' - diphosphonic acid
  • a still more stable combination in addition includes a compound selected from the group of polyphosphates, phosphoric acid, acetic acid, lactic acid and citric acid.
  • the sequestering agents of the former group are used in an amount from about 5 to 50, preferably 10 to 30 grams per liter of the developer solution and the compounds of the latter are used in an amount from about 5 to 100, preferably 15 to 50 grams per liter of the developer solution.
  • Sequestering agents such as ethylenediaminotetracetic acid (EDTA), nitrilotriacetic acid (NTA) and nitrilotrimethylenephosphonic acid (NTPA), having chemical structures similar to those of some compounds of the former group, and compounds such as aminoacetic acid, oxalic acid, glycolic acid, malic acid, aspartic acid, glutammic acid and tartaric acid, having chemical structures similar to those of some compounds of the latter group, used in combination with alkanolamines, did not prove to be as effective as the selected ones in order to prevent developer degradation.
  • EDTA ethylenediaminotetracetic acid
  • NTA nitrilotriacetic acid
  • NTPA nitrilotrimethylenephosphonic acid
  • a particular preferred developer formulation will comprise the following ingredients:
  • Exposed black-and-white silver halide photographic films e.g. Rapid Access films, X-ray films, Printing Papers, Reversal films
  • the developer formulation of the present invention may also be prepared from concentrated parts to be diluted with water and from the working solution just prior to its use.
  • concentrated parts must be stable in the various storage conditions, problems may arise in making a single concentrated part of the developer solution as such for stability and it is normal practice in the art to divide and package it in two concentrated parts. These parts are combined and diluted with water to the desired strength and placed in the developing tank of the machine.
  • the developer formulations of the present invention may be advantageously prepared in a single concentrated part comprising a mixture of benzotriazole and 1 - phenyl - 5 - mercaptotetrazole as antifoggant agent.
  • a single concentrated part comprising a mixture of benzotriazole and 1 - phenyl - 5 - mercaptotetrazole as antifoggant agent.
  • the choice of such organic antifoggant agents appears not so critical and any mixture of antifoggant agents above described may be used.
  • a particular preferred concentrated formulation made in a single part according to the present invention will comprise the following ingredients:
  • the developer solution containing DTPA alone at the end of the experiment, resulted to be strongly colored and showed a pH increase higher than 0.5.
  • a liquid concentrated developer (Concentrated Developer XIX), consisting of two parts, was prepared as follows:
  • a second liquid concentrated developer (Concentrated Developer XX) was prepared in a single part having the components of Parts A and B of Conc. Developer XIX, according to the following composition:
  • a third liquid concentrated developer (Concentrated Developer XXI), consisting of two parts, was prepared as follows:
  • a fourth liquid concentrated developer (Concentrated Developer XXII) was prepared in a single part having the components of Parts A and B of Conc. Developer XXI, according to the following composition:
  • a fifth liquid concentrated developer (Concentrated Developer XXIII) was prepared as follows:
  • Sheets of unexposed 3M LOC4 Contact Film were developed in the above described ready-for-use developers for 60" at 35°C, treated in a stop bath comprising 4% acetic acid for 15" at 35°C, fixed in 3M Fix Roll M for 30" at 35°C and finally washed for 5' at 35°C.
  • Table 11 reports the minimum density (fog) values of the developed sheets.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (11)

1. Entwicklerzusammensetzung für photographisches Silberhalogenid-Material, umfassend Hydrochinon oder ein substituiertes Hydrochinon, ein Alkalimetallsulfit, ein organisches Antischleiermittel und anorganische alkalische Mittel, dadurch gekennzeichnet, daß die Entwickler - Zusammensetzung ein Alkanolamin und ein sequestrierendes Agens aus der Gruppe Diäthylentriaminpentaessigsäure, 1,3 - Diamino - 2 - propanoltetraessigsäure und 1 - Hydroxyäthyliden - 1,1' - diphosphonsäure umfaßt.
2. Entwickler - Zusammensetzung für photographisches Silberhalogenid - Material nach Anspruch 1, umfassend ferner eine Verbindung aus der Gruppe Polyphosphate, Phosphorsäure, Essigsäure, Milchsäure und Citronensäure.
3. Entwickler - Zusammensetzung für photographisches Silberhalogenid - Material nach Anspruch 1, umfassend ferner ein Entwicklungs - Hilfsmittel aus der Gruppe der substituierten Pyrazolidone und p - Aminophenol - Verbindungen.
4. Entwickler - Zusammensetzung für photographisches Silberhalogenid - Material nach Anspruch 1, in dem das organische Antischleiermittel aus der Gruppe der Gemische von 5 - Nitroindazol und Benzimidazolnitrat, 5 - Nitrobenzotriazol und 1 - Phenyl - 5 - mercaptotetrazol, und Benzotriazol und 1 - Phenyl - 5 - mercaptotetrazol ausgewählt ist.
5. Entwickler - Zusammensetzung für photographisches Silberhalogenid - Material nach Anspruch 1, in dem das Alkanolamin aus der Gruppe Diäthanolamin, Triäthanolamin, 2 - Benzylaminoäthanol, 2 - Methylaminoäthanol, 2 - Äthylaminoäthanol und 2 - Isopropylaminoäthanol ausgewählt ist.
6. Entwickler - Zusammensetzung für photographisches Silberhalogenid - Material, umfassend Hydrochinon oder ein substituiertes Hydrochinon in einer Menge von 10 bis 30 g/Liter, ein Hilfsentwickler in einer Menge von 0,2 bis 5 g/Liter, ein Alkalimetallsulfit in einer Menge von 20 bis 50 g/Liter, ein organisches Antischleiermittel aus der Gruppe der Gemische von 5 - Nitroindazol und Benzimidazolnitrat, 5 - Nitrobenzotriazol und 1 - Phenyl - 5 - mercaptotetrazol und Benzotriazol und 1 - Phenyl - 5 - mercaptotetrazol in einer Menge von 0,2 bis 1,5 g/Liter, ausreichend anorganisches alkalische Stoffe um einen pH-Wert von mindestens 10 zu ergeben, und ausreichend Wasser, um einen Liter zu ergeben, dadurch gekennzeichnet, daß sie einschließt:
(a) ein Alkanolamin in einer Menge von 5 bis 20 g/Liter,
(b) ein sequestrierendes Agens aus der Gruppe Diäthylentriaminpentaessigsäure, 1,3 - Diamino - 2 - propanoltetraessigsäure und 1 - Hydroxyäthyliden - 1,1' - diphosphonsäure in einer Menge von 10 bis 30 g/Liter und
(c) eine Verbindung aus der Gruppe Polyphosphate, Phosphorsäure, Essigsäure, Milchsäure und Citronensäure in einer Menge von 15 bis 50 g/Liter.
7. Konzentrierte Entwickler - Zusammensetzung für photographisches Silberhalogenid - Material, das mit Wasser zu einer gebrauchsfertigen Entwickler - Zusammensetzung verdünnt werden kann, umfassend Hydrochinon oder ein substituiertes Hydrochinon, ein Alkalimetallsulfit und anorganische alkalische Stoffe, dadurch gekennzeichnet, daß es ein Alkanolamin, ein sequestrierendes Agens aus der Gruppe Diäthylentriaminpentaessigsäure 1,3 - Diamino - 2 - propanoltetraessigsäure und 1 - Hydroxyäthyliden - 1,1' - diphosphonsäure und ein Gemisch aus Benzotriazol und 1 - Phenyl - 5 - mercaptotetrazol als Antischleiermittel enthält.
8. Konzentrierte Entwickler - Zusammensetzung für photographisches Silberhalogenidmaterial nach Anspruch 7, das eine Verbindung aus der Gruppe Polyphosphate, Phosphorsäure, Essigsäure, Milchsäure und Citronensäure umfaßt.
9. Konzentrierte Entwickler - Zusammensetzung für photographisches Silberhalogenidmaterial nach Anspruch 7, welches Diäthanolamin als Alkanolamin umfaßt.
10. Konzentrierte Entwickler-Zusammensetzung für photographisches Silberhalogenid - Material nach Anspruch 7, das ein Hilfsentwickler aus der Gruppe der substituierten Pyrazolidone und p - Aminophenolverbindungen umfaßt.
11. Konzentrierte Entwickler - Zusammensetzung für photographisches Silberhalogenid - Material, die mit Wasser zu einer gebrauchsfertigen Entwickler - Zusammensetzung verdünnt werden kann, umfassend Hydrochinon oder ein substituiertes Hydrochinon in einer Menge von 40 bis 120 g/Liter, einen Hilfsentwickler in einer Menge von 0,5 bis 20 g/Liter, ein Alkalimetallsulfit in einer Menge von 80 bis 200 g/Liter, ein Gemisch aus Benzotriazol und 1 - Phenyl - 5 - mercaptotetrazol als Antischleiermittel in einer Menge von 0,8 bis 6 g/Liter, ausreichend anorganische alkalische Stoffe um einen pH-Wert von mindestens 11 zu ergeben, und ausreichend Wasser, um 1 Liter zu erreichen, dadurch gekennzeichnet, daß sie einschließt:
(a) ein Alkanolamin in einer Menge von 20 bis 120 g/Liter,
(b) ein sequestrierendes Agens aus der Gruppe Diäthylentriaminpentaessigsäure, 1,3 - Diamino - 2 - propanoltetraessigsäure und 1 - Hydroxyäthyliden - 1,1' - diphosphonsäure in einer Menge von 20 bis 150 g/Liter,
(c) eine Verbindung aus der Gruppe Polyphosphate, Phosphorsäure, Essigsäure, Milchsäure und Citronensäure in einer Menge von 50 bis 150 g/Liter.
EP84110559A 1983-09-20 1984-09-05 Entwicklerzusammensetzungen für photographische Silberhalogenidmaterialien Expired EP0136582B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT65213/83A IT1175017B (it) 1983-09-20 1983-09-20 Composizioni di sviluppo per materiali fotografici agli alogenuri d'argento
IT6521383 1983-09-20

Publications (3)

Publication Number Publication Date
EP0136582A2 EP0136582A2 (de) 1985-04-10
EP0136582A3 EP0136582A3 (en) 1987-09-23
EP0136582B1 true EP0136582B1 (de) 1989-07-19

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EP84110559A Expired EP0136582B1 (de) 1983-09-20 1984-09-05 Entwicklerzusammensetzungen für photographische Silberhalogenidmaterialien

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EP (1) EP0136582B1 (de)
AR (1) AR244894A1 (de)
CA (1) CA1264976A (de)
DE (1) DE3479063D1 (de)
IT (1) IT1175017B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0223883B1 (de) * 1985-11-26 1989-02-22 Agfa-Gevaert N.V. Verfahren zur Entwicklung eines belichteten photographischen Silberhalogenidemulsionsmaterials
IT1215423B (it) * 1987-04-13 1990-02-08 Minnesota Mining & Mfg Composizioni di sviluppo per materiali fotografici agli alogenuri d'argento.
IT1229224B (it) * 1989-04-03 1991-07-26 Minnesota Mining & Mfg Composizione concentrata di sviluppo fotografico e metodo per prepararla.
IT1240596B (it) * 1990-03-12 1993-12-17 Minnesota Mining & Mfg Sviluppatore fotografico alcalino in bianco e nero
EP0518627A1 (de) * 1991-06-10 1992-12-16 International Paper Company Verringerung des Silberschlammes bei der photographischen Verarbeitung
JP2824717B2 (ja) 1992-07-10 1998-11-18 富士写真フイルム株式会社 ハロゲン化銀写真感光材料の処理方法
DE69329173T2 (de) 1992-09-24 2001-01-11 Fuji Photo Film Co Ltd Verarbeitungsverfahren für lichtempfindliches silberhalogenidenthaltendes Schwarzweissmaterial
EP0654705B1 (de) 1993-11-24 2000-06-21 Fuji Photo Film Co., Ltd. Photographische Verarbeitungszusammensetzung und Verarbeitungsverfahren
EP0736807B1 (de) * 1995-03-21 1996-10-16 Agfa-Gevaert N.V. Satz zur Herstellung einer Verarbeitungsflüssigkeit zur Verwendung zum Herstellen einer lithographischen Druckplatte nach dem Silbersalz-Diffusionübertragungsverfahren
US20020146652A1 (en) * 2001-01-24 2002-10-10 Eastman Kodak Company Black-and-white developing compositions and methods of use

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1216854A (en) * 1967-05-05 1970-12-23 Kodak Ltd Photographic developer composition
US3576633A (en) * 1967-06-27 1971-04-27 Eastman Kodak Co Photographic process and compositions
GB1376600A (en) * 1971-02-15 1974-12-04 Agfa Gevaert Photographic developer compositions
US4172728A (en) * 1977-12-16 1979-10-30 E. I. Du Pont De Nemours And Company High contrast continuous tone developer and process of use
GB2027920B (en) * 1978-08-11 1983-02-02 Kodak Ltd Photographic silver halide developer composition

Also Published As

Publication number Publication date
AR244894A1 (es) 1993-11-30
IT8365213A0 (it) 1983-09-20
EP0136582A3 (en) 1987-09-23
DE3479063D1 (en) 1989-08-24
CA1264976A (en) 1990-01-30
EP0136582A2 (de) 1985-04-10
IT1175017B (it) 1987-07-01

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