US3754918A - Dye bleaching bath for the silver dye bleaching process - Google Patents

Dye bleaching bath for the silver dye bleaching process Download PDF

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Publication number
US3754918A
US3754918A US00166906A US3754918DA US3754918A US 3754918 A US3754918 A US 3754918A US 00166906 A US00166906 A US 00166906A US 3754918D A US3754918D A US 3754918DA US 3754918 A US3754918 A US 3754918A
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Prior art keywords
bath
bleaching
silver
minutes
dye
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Expired - Lifetime
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US00166906A
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English (en)
Inventor
S Hunig
M Heilmann
P Bergthaller
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • 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
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials

Definitions

  • ABSTRACT Color photographic images are produced by the silver dye bleaching process in which the bleaching is accelerated with a bleaching bath containing substituted 1 ,5- diazanaphthalenes as defined below.
  • the present invention relates to a dye bleaching bath for the silver dye bleaching process, which bath contains derivatives of 1,5-diazanapthalene as bleaching catalysts.
  • a photographic material comprising light-sensitive silver halide emulsion layers which contain azo dyes is exposed to light and then developed and fixed in the usual manner.
  • a negative silver image of the original is obtained in the emulsion layers.
  • the photographic material is then treated with a dye bleaching bath and, as the last stage of processing, with a silver bleaching bath or bleach fixing bath.
  • a positive color image of the original is obtained.
  • the process is based on the bleaching of organic dyes, especially azo dyes, with finely divided silver, in this case the photographically produced image silver, the extent of bleaching depending on the quantity of silver present.
  • the known baths which contain as their main components an inorganic or organic acid and substances which form silver salts or silver complexes, generally bleach too slowly, so that it is necessary to use bleaching catalysts at the same time.
  • Heterocyclic nitrogen compounds are suitable for this purpose, e.g., quinoline, isoquinoline or derivatives thereof, quinoxalines and azines such as phenazine or naphthazine.
  • quinoline isoquinoline or derivatives thereof
  • quinoxalines and azines such as phenazine or naphthazine.
  • a bleaching bath for the silver dye bleaching process which bath contains inorganic or organic acids, a substance which forms silver salts or silver complex salts, and a heterocyclic nitrogen compound as bleaching catalyst, said compound being a derivative of 1,5-diazanaphthalene of the following formula:
  • n 0,1 or 2.
  • the bleaching catalysts to be used according to the invention are very highly active even in relatively small concentrations. They are, therefore, considerably superior for this purpose to the known unsubstituted l,5- diazanaphthalene.
  • the compounds which are to be used according to the invention are prepared by known methods.
  • the simplest method is to start from unsubstituted 1,5- diazanaphthalene and react this with a powerful alkylating agent, e.g., with dimethyl sulfate, diethyl sulfate or alkyloxonium borofluorides or sultones.
  • the bleaching catalysts according to the invention are added to the bleach bath in amounts of between 0.005 and 0.200 g/l.
  • the effect of the bath according to the invention is substantially independent of the nature of the azo dye insofar as any given azo dye is bleached much more rapidly than with conventional baths.
  • the bath according to the invention may, therefore, be used quite generally for the silver dye bleaching process regardless of the nature of the dye used. 5
  • the materials which are to be processed in the baths according to the invention are prepared in a known manner.
  • the azo dyes in the silver halide emulsion layers may be e.g., those described in the following patent specifications:
  • the dye bleaching baths according to the invention have a pH of at the most 2 and preferably between and 1.
  • the required pH range is adjusted by the addition of inorganic or organic acids, e.g., sulfuric acid, hydrohalic acids such as hydrochloric acid or hydrobromic acid, phosphoric acid, nitric acid, toluene sulfonic acid or naphthylene disulfonic acid.
  • the silver salt forming agents used may be potassium halides or other alkali metal halides, preferably iodides such as potassiumiodide.
  • thiosemicarbazide or preferably thiourea or its derivatives.
  • the silver salt forming agents are advantageously used in quantities of between 10 and 50 g/l and the complex forming agents in quantities of from 10 to 200 EXAMPLE 1
  • a light-sensitive photographic material for the silver dye bleaching process consisting substantially of a redsensitive silver bromide gelatin emulsion layer containing a cyan azo dye and mounted on a support, a greensensitive silver bromide gelatin emulsion layer containing a magenta azo dye, a yellow filter layer and an uppermost blue-sensitive silver bromide gelatin emulsion layer containing a yellow azo dye, is exposed to white light behind a grey step wedge.
  • Six samples arethen processed as follows:
  • the developed and hardened material is then treated in the following stages, each sample being bleached in a different one of bleaching baths 1 to 6 as described below;
  • the various bleaching baths contain per litre:
  • the temperature of the dye bleaching bath is 30C
  • a light-sensitive photographic material for the silver dye bleaching process consisting substantially of a supported red-sensitive silver bromide gelatin emulsion which contains a cyan azo dye, a green-sensitive silver bromide gelatin emulsion layer containing a magenta azo dye, a yellow filterlayer and an uppermost bluesensitive silver bromide emulsion layer containing a yellow azo dye, is exposed to white light behind a grey step wedge. Eight samples are then processed as follows: 1. Development 5 minutes in a bath of:
  • Bleaching baths (7) and (8) contain, per litre:
  • EXAMPLE 3 The procedure is the same as described in Example 2 but using dye bleaching baths (7) and (9). Bleaching bath (9) differs from bleach bath (8) only by its smaller quantity (0.075 g) of compound (l).
  • the results of the comparison tests are represented in the figure.
  • the curves show the y-value of the cyan part of the image as modified by the action of the dye bleaching baths.
  • the ordinate represents the density and the abscissa the log 1.! value.
  • the broken line curves 1, 2, 3 and 4 show the efficiency of dye bleaching bath (7) acting for 2 5, 7 and 10 minutes, respectively.
  • the continuous line curves 1' to 4 represent the results obtained after the same time with bleaching bath (9).
  • R and R each represents a saturated or olefinically unsaturated aliphatic group having up to five carbons, which may be substituted with halogen, hydroxyl, alkoxy, carboxyl, sulfo or sulfato; and R and R combined may contain n acid groups X represents any photographically inert anion; and
  • n 0, l or 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US00166906A 1970-07-31 1971-07-28 Dye bleaching bath for the silver dye bleaching process Expired - Lifetime US3754918A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702038008 DE2038008A1 (de) 1970-07-31 1970-07-31 Farbbleichbad für das Silber farbbleichverfahren

Publications (1)

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US3754918A true US3754918A (en) 1973-08-28

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US00166906A Expired - Lifetime US3754918A (en) 1970-07-31 1971-07-28 Dye bleaching bath for the silver dye bleaching process

Country Status (6)

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US (1) US3754918A (enrdf_load_stackoverflow)
BE (1) BE769599A (enrdf_load_stackoverflow)
CH (1) CH569991A5 (enrdf_load_stackoverflow)
DE (1) DE2038008A1 (enrdf_load_stackoverflow)
FR (1) FR2099403A5 (enrdf_load_stackoverflow)
GB (1) GB1341575A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4186008A (en) * 1977-03-23 1980-01-29 Ciba-Geigy Aktiengesellschaft Method for processing silver dye-bleach materials
US4266011A (en) * 1978-09-29 1981-05-05 Ciba-Geigy Ag Process for the production of colored photographic images by the silver dye-bleach process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4186008A (en) * 1977-03-23 1980-01-29 Ciba-Geigy Aktiengesellschaft Method for processing silver dye-bleach materials
US4266011A (en) * 1978-09-29 1981-05-05 Ciba-Geigy Ag Process for the production of colored photographic images by the silver dye-bleach process

Also Published As

Publication number Publication date
FR2099403A5 (enrdf_load_stackoverflow) 1972-03-10
GB1341575A (enrdf_load_stackoverflow) 1973-12-25
BE769599A (nl) 1972-01-07
DE2038008A1 (de) 1972-02-10
CH569991A5 (enrdf_load_stackoverflow) 1975-11-28

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