EP0588408B1 - Développateur du type acide ascorbique avec une composition déterminé - Google Patents

Développateur du type acide ascorbique avec une composition déterminé Download PDF

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Publication number
EP0588408B1
EP0588408B1 EP19930202545 EP93202545A EP0588408B1 EP 0588408 B1 EP0588408 B1 EP 0588408B1 EP 19930202545 EP19930202545 EP 19930202545 EP 93202545 A EP93202545 A EP 93202545A EP 0588408 B1 EP0588408 B1 EP 0588408B1
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EP
European Patent Office
Prior art keywords
pyrazolidone
phenyl
ascorbic acid
developing
methyl
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
EP19930202545
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German (de)
English (en)
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EP0588408A1 (fr
Inventor
Andriessen C/O Agfa-Gevaert N.V. Hieronymus
Lingier c/o Agfa-Gevaert N.V. Stefaan
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Agfa Gevaert NV
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Agfa Gevaert NV
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Publication date
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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
    • G03C5/30—Developers

Definitions

  • the present invention relates to the field of photographic developing solutions and more particularly to a photographic developing solution having a particular combination of developing agents.
  • aqueous alkaline developer compositions containing a developing agent usually of the dihydroxybenzene type such as hydroquinone.
  • US 2,688,549 discloses the combination of a 3-pyrazolidone developing agent and of an ascorbic acid derivative.
  • GB 1,266,533 describes the combination of an p-hydroxybenzene developing agent, an ascorbic acid and sulphite ions.
  • An equally good developing activity for both surface and internal latent images is claimed in US 3,826,654 which discloses a combination of a 3-pyrazolidone, an ascorbic acid, a heterocyclic thione or thiol and an alkali iodide at a pH of at least 12.
  • the use of particular mixtures of two Phenidone type auxiliary developing agents in combination with an ascorbic acid type main developing agent caused substantially less sensitometric deterioration, namely sensitivity and gradation loss, due to pH decrease, than when only one Phenidone type auxiliary developing agent was present.
  • the ascorbic acid type developing agent is l-ascorbic acid or iso-ascorbic acid, or a salt thereof
  • the mixture of the at least two Phenidone type agents consists of a mixture 1-phenyl-3-pyrazolidone (P) and 1-phenyl-4-methyl-3-pyrazolidone (MP).
  • Preferred ascorbic acid type developing agents according to general formula (I) for use in accordance with the present invention are l-ascorbic acid and iso-ascorbic acid.
  • Other useful compounds include imino-l-ascorbic acid, 6-desoxy-l-ascorbic acid, l-rhamnoascorbic acid, l-fucoascorbic acid, d-glucoheptoascorbic acid, d-glucoascorbic acid, l-erythroascorbic acid, and their stereoisomers.
  • the developing agents can be incorporated in the developing solution in the free acid form or as a salt, preferably an alkali salt.
  • the ascorbic acid type developing agent is incorporated in the developer in a concentration ranging preferably between 0.1 and 0.6 mole/liter, corresponding to a range between 25 and 100 g/l for ascorbic acid.
  • the at least two 3-pyrazolidone type auxiliary agents are chosen from the group consisting of (a) 1-phenyl-3-pyrazolidone ("Phenidone", P), (b) 1-phenyl-4-methyl-3-pyrazolidone ("methyl-Phenidone", MP), (c) 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone("methyl-hydroxymethyl-Phenidone", MHMP), (d) 1-phenyl-4,4'-dimethyl-3-pyrazolidone ("dimethyl-Phenidone", DMP).
  • a mixture of two is chosen and the most preferred choice consists of a mixture of 1-phenyl-3-pyrazolidone ("Phenidone", P) and 1-phenyl-4-methyl-3-pyrazolidone ("methyl-Phenidone", MP) as will become clear from the examples.
  • P 1-phenyl-3-pyrazolidone
  • methyl-Phenidone MP
  • the preferred concentration of 1-phenyl-3-pyrazolidone ranges from 0.1 to 2.0 g/l
  • the preferred concentration of 1-phenyl-4-methyl-3-pyrazolidone ranges from 0.1 to 5.5 g/l.
  • the developing solution can further contain an anti-fogging agent.
  • an anti-fogging agent Many known compounds can be added as fog-inhibiting agent or stabilizer to a processing solution. Suitable examples are e.g. the heterocyclic nitrogen-containing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles (preferably 5-methyl-benzotriazole), nitrobenzotriazoles, mercaptopyrimidines, mercaptotriazines, benzothiazoline-2-thione and oxazoline-thione.
  • benzothiazolium salts such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles
  • triazolopyrimidines such as those described in GB 1,203,757, GB 1,209,146, JA-Appl. 75-39537, and GB 1,500,278 and other compounds such as benzenethiosulphonic acid, benzenethiosulphinic acid and benzenethiosulphonic acid amide compounds.
  • a preferred compound for use in accordance with the present invention is 1-phenyl-5-mercaptotetrazole.
  • the developing solution according to the present invention preferably further contains a compound providing halide ions as development rate regulator, most preferably sodium or potassium bromide in a concentration between 0.01 and 0.2 mole/liter.
  • a compound providing halide ions as development rate regulator, most preferably sodium or potassium bromide in a concentration between 0.01 and 0.2 mole/liter.
  • Further sulphite ions can be present as antioxidant preferably as an alkali sulphite in a concentration between 0.1 and 0.8 mole/liter.
  • the alkali agent for establishing the start pH of the developer is preferably sodium or potassium hydroxide.
  • the developing solution can further contain buffering agents.
  • buffering agents include carbonate buffer, phosphate buffer, metaborate buffer, etc.
  • concentration of these buffering agents is preferably about 0.4 mole/liter.
  • the scope of the present invention further comprises a method for developing an image-wise exposed photographic material by means of the described developing solution.
  • the method of the present invention is especially useful when no replenisher solution is present for compensating the pH drop during exhaustive continuous processing.
  • a conventional fixing step washing step and drying step are performed.
  • an automatically driven processing apparatus is used.
  • the silver halide photographic materials which can be processed by the method of the present invention include all kinds of black-and-white materials, e.g. films and papers for amateur photography, films for cinematography, materials for radiographic recording and materials for graphic arts.
  • the silver halide emulsions present as photosensitive element in those photographic materials can be of any known halide composition, e.g. bromide, chloride, iodobromide, chlorobromide or chloroiodobromide emulsions.
  • the best results with the present invention are however obtained with materials containing emulsions rich in bromide, and more particularly with emulsions containing at least 70 mole % of bromide.
  • a silver halide material for microfilm application having a silver halide coverage equivalent to 3.6 g of silver nitrate per sq.m. and containing a 100% silver bromide emulsion with an average grain size of 0.3 ⁇ m was processed in a automatic processor, having a tank solution of 1 liter.
  • the decrease in development activity due to the pH decrease on exhaustive processing was simulated by comparing the sensitometry in two solutions, one adjusted to pH 10.5, the other to pH 9.9.
  • the development time applied was 20 s and the temperature was kept constant at 38 °C.
  • the basic composition of these developer solutions was : Water 600 ml K2SO3 65 g K2CO3 61 g KBr 15 g Ascorbic acid sodium salt 50 g KOH 8.5 g (pH 9.90) or KOH 16.5 g (pH 10.50) Water to make 1 l.
  • the goal of the tests described in this example was to optimize the ratio of the amounts of P and MP, which proved to be the best combination according to example 1.
  • the microfilm material used was similar as the one used in example 1.
  • the basic composition of the developing solutions was the same as the composition of example 1. Table 2 shows the results of using different ratio's of P and MP.
  • Table 2 shows that several ratio's of P and MP gave good results, namely low decrease of sensitivity and toe gradation for a change of pH from 10.50 to 9.90.
  • Table 5 shows the effects of these compounds and of their combinations on the change in sensitivity (DSENS, measured at density 1.1 + Dmin), on the change of gradation in the toe of the sensitometric curve (DGRAD t , measured between densities 0.1 + Dmin and 1.1 + Dmin) and on the change of gradation (DGRAD, measured between densities 0.5 + Dmin and 1.5 + Dmin) when changing the pH from 10.5 to 9.9.

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

Claims (8)

  1. Solution de développement photographique comprenant
    (1) un développateur du type acide ascorbique correspondant à la formule générale (I), ou un de ses sels: dans laquelle:
    X représente un atome d'oxygène ou un groupe imino, et
    n représente un nombre entier de 1 à 4, et
    R représente un groupe hydroxy quand n est 1, et R représente un groupe hydroxy ou un atome d'hydrogène quand n est 2 à 4.
    (2) un mélange d'au moins deux développateurs du type 3-pyrazolidone choisis du groupe composé de:
    (a) 1-phényl-3-pyrazolidone,
    (b) 1-phényl-4-méthyl-3-pyrazolidone,
    (c) 1-phényl-4-méthyl-4'-hydroxyméthyl-3-pyrazolidone,
    (d) 1-phényl-4,4'-diméthyl-3-pyrazolidone.
  2. Une solution de développement selon la revendication 1, caractérisée en ce que le développateur du type acide ascorbique est l'acide 1-ascorbique ou l'acide iso-ascorbique ou un sel de ceux-ci.
  3. Solution de développement selon la revendication 1 ou 2, caractérisée en ce que le développateur du type ascorbique est présent dans une concentration entre 0,1 et 0,6 moles/l.
  4. Solution de développement selon l'une quelconque des revendications 1 à 3, caractérisée en ce que le mélange d'au moins développateurs du type 3-pyrazolidone est un mélange de l-phényl-3-pyrazolidone et de 1-phényl-4-méthyl-3-pyrazolidone.
  5. Solution de développement selon la revendication 4, caractérisée en ce que la 1-phényl-3-pyrazolidone est présente dans une concentration entre 0,1 and 2,0 g/l, et que la 1-phényl-4-méthyl-3-pyrazolidone est présente dans une concentration entre 0,1 et 5,5 g/l.
  6. Procédé pour déveloper un matériau photographique exposé sous forme d'image, comprenant un support et une couche d'émulsion à l'halogénure d'argent, au moyen d'une solution de développement selon l'une quelconque des revendications 1 à 5.
  7. Procédé selon la revendication 6, caractérisé en ce qu'il n'y a pas de solution régénératrice pour la solution de développement.
  8. Procédé selon l'une quelconque des revendications 6 ou 7, caractérisé en ce que l'émulsion à l'halogénure d'argent, présente dans la couche à l'halogénure d'argent, contient au moins 70 moles % de bromure.
EP19930202545 1992-09-15 1993-08-31 Développateur du type acide ascorbique avec une composition déterminé Expired - Lifetime EP0588408B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92202809 1992-09-15
EP92202809 1992-09-15

Publications (2)

Publication Number Publication Date
EP0588408A1 EP0588408A1 (fr) 1994-03-23
EP0588408B1 true EP0588408B1 (fr) 1998-05-13

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EP19930202545 Expired - Lifetime EP0588408B1 (fr) 1992-09-15 1993-08-31 Développateur du type acide ascorbique avec une composition déterminé

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EP (1) EP0588408B1 (fr)
DE (1) DE69318498T2 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3078431B2 (ja) * 1993-09-27 2000-08-21 富士写真フイルム株式会社 黒白ハロゲン化銀写真感光材料の現像方法
GB2292813B (en) * 1994-08-27 1999-02-03 Ilford Ltd Photographic silver halide developing solution
EP0736802A1 (fr) * 1995-04-04 1996-10-09 Minnesota Mining And Manufacturing Company Développateur et méthode de développement de matériaux photographique à l'halogénure d'argent
US5942379A (en) * 1995-08-10 1999-08-24 Eastman Kodak Company 3-pyrazolidone compounds and photographic developer solutions containing same
US5589323A (en) * 1996-01-23 1996-12-31 Sun Chemical Corporation Chemically stable ascorbate-based photographic developer and imaging process
US5702875A (en) * 1996-06-28 1997-12-30 Eastman Kodak Company Weakly alkaline ascorbic acid developing composition, processing kit and method using same
US5866309A (en) * 1997-10-22 1999-02-02 Fitterman; Alan S. Method for processing roomlight handleable photographic elements
US5871890A (en) * 1997-11-14 1999-02-16 Eastman Kodak Company Method for processing roomlight handleable radiographic films using two-stage development
US5932398A (en) * 1997-11-14 1999-08-03 Eastman Kodak Company Kit for roomlight processing of black-and-white photographic elements
JP4865664B2 (ja) 2007-09-28 2012-02-01 富士フイルム株式会社 多孔性担体内で２以上の液を混合する方法
EP2065706B1 (fr) 2007-11-29 2012-11-07 FUJIFILM Corporation Procédé immunochromatographique

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE530885A (fr) * 1953-08-03
GB2011103B (en) * 1977-12-15 1982-05-19 Agfa Gevaert Nv Photographic material for continuous tone reproduction
JPH02304555A (ja) * 1989-05-19 1990-12-18 Konica Corp ハロゲン化銀写真感光材料の処理方法
US5098819A (en) * 1990-01-31 1992-03-24 Knapp Audenried W Non-toxic photographic developer composition

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Publication number Publication date
DE69318498D1 (de) 1998-06-18
EP0588408A1 (fr) 1994-03-23
DE69318498T2 (de) 1998-11-12

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