US2627461A - Indophenazines as catalysts in dye bleach baths for color photography - Google Patents

Indophenazines as catalysts in dye bleach baths for color photography Download PDF

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Publication number
US2627461A
US2627461A US175467A US17546750A US2627461A US 2627461 A US2627461 A US 2627461A US 175467 A US175467 A US 175467A US 17546750 A US17546750 A US 17546750A US 2627461 A US2627461 A US 2627461A
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United States
Prior art keywords
dye
silver
image
acid
indophenazines
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Expired - Lifetime
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US175467A
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English (en)
Inventor
Joseph S Friedman
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GAF Chemicals Corp
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General Aniline and Film Corp
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Filing date
Publication date
Priority to BE504761D priority Critical patent/BE504761A/xx
Application filed by General Aniline and Film Corp filed Critical General Aniline and Film Corp
Priority to US175467A priority patent/US2627461A/en
Priority to GB16817/51A priority patent/GB687768A/en
Priority to CH302938D priority patent/CH302938A/de
Priority to DEG6603A priority patent/DE902220C/de
Priority to FR1048365D priority patent/FR1048365A/fr
Application granted granted Critical
Publication of US2627461A publication Critical patent/US2627461A/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
    • 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

  • This invention relates to a method of processing photographic color pictures and particularly to pyrrolinophenazines and in dophenazines as accelerators for dye bleach baths used in the production of dyestufi images from dyed silver images.
  • the metallic silver is converted into a silver compound which may be removed subsequently by fixation in a solution of hypo, or dissolved in the dye bleach solution, such'as a strong alkali iodide or an alkali thiocyanate solution.
  • the bleach baths employed in this process, have relatively low pHs and consist of an aqueous solution of a hydrohalic acid, such as hydrochloric, hydrobromic ,acid,.etc., containing an alkali halide, such as potassium iodide, ammonium chloride, or both.
  • a hydrohalic acid such as hydrochloric, hydrobromic ,acid,.etc.
  • an alkali halide such as potassium iodide, ammonium chloride, or both.
  • Such baths require a relatively long treatment time so as to destroy the dyestuii present in situ with the silver image.
  • Long treatment in bleaching solutions of high acidity has the tendency to soften the gelatin of the photographic emulsion containing a silver image and a bleachable dye.
  • various organic compounds have been proposed as catalysts which, when added to the bleach bath, accelerate the action of saidbath and materially reduce thecbleaching time.
  • phenazine such as phenazine, 2:3-diaminophenazine, and the like.
  • phenazine and its substituted products are efiective as accelerators, they are highly colored substances and are substantive to gelatin, i. e., leave a stain in the gelatin layer Which is difficult to remove, and, which seriously aliects the quality or" the final image.
  • substituted phenazines are due to the presence of polar substituents, such as OH, NHz, 3031-1, and COOH. This is an undesirable feature when dye masks are prepared in monopack film containing dye images of the azomethine or quinonimine type.
  • substituted phenazines can only be used in dye bleach baths containing mineral acids because if the concentration of the phenazine accelerator is increased above the prescribed amounts, a heavier stain in the gelatin layer is obtained. 1
  • pyrrolinophenazines and indophenazines which include benzoindophenazines and naphthoindophenazines, although colored substances ranging from reddish-orange to yellow in color, are not substantive to gelatin, do not stain the gelatin layer, and do not afiect the quality of the final dye image.
  • the pyrrolinophenazines and indophenazines because of the absence of polar substituents, have no afiinity for gelatin, can be readily washed out of the treated film and hence much stronger concentrations can be used, with a concomitant reduction of acid concentration, and increase in pH.
  • indophenazines pyrrolinophenazines, indophenazines, benzoindophenazines, and naphthophenazines, which for sake of simplicity will be referred to hereafter as indophenazines, are characterized by the following general formulae:
  • indophenazines are generally prepared by the condensation of substituted or unsubstituted isatin with o-phenylenediamine or homologs thereof by following the procedures described in Beilstein, vol. 26, 4th ed., 1937, pages 88-118.
  • indophenazines exert a very strong catalytic action upon dye destruction in situ with metallic silver and may be employed not only in relatively weak water-soluble acids, such as acetic, propionic, tartaric, citric, boric, or aryl sulfonic acid, e. g., benzene disulfonic or naphthalene trisulfonic acid, but also in mineral acid bleach baths, such as, for example, hydrochloric, hydrobromic, hydroiodic, sulfuric, sulfamic or phosphoric acid with or without the presence of alkali halide, such as sodium or potassium bromide or iodide, sodium chloride, ammonium chloride, and the like.
  • relatively weak water-soluble acids such as acetic, propionic, tartaric, citric, boric, or aryl sulfonic acid, e. g., benzene disulfonic or naphthalene trisulfonic acid
  • the concentration of the mineral acid to be employed is dependent upon the character of the gelatin constituting the photographic color emulsion layer or layers used for color film containing azo dyes.
  • the concentration of the acid may range from 5 to 100 cc. per liter of dye bleach solution.
  • the concentration of hydrohalic acid or acetic acid may range from 25 to 100 cc. per liter of dye bleach solution, and the pH of these solutions must be sumciently high to avoid the destruction of the azomethine and quinonimine dye images.
  • a pH range from 2.0 to 4.0 is preferred.
  • the amount employed as catalysts is not at all critical. The higher the amount within practical limits, the greater the catalytic activity. An amount as small as 0.005 gram per liter of bleach solution will have an appreciable bleaching action on silver bearing images. For practical purposes, amounts ranging from 0.005 to 1 gram per liter to saturated solutions may be employed.
  • a film dyed uniformly with an azo dye containing a negative silver image will upon treatment with adye bleach solution containing as little as 0.005 gram of an indophenazine be acted on at those places where silver images are present.
  • the action is destruction of the dye in accordance with the concentration of silver present. At a point where considerable silver exists, 1. e., in the shadows, the dye destruction will be complete. In the highlights where little or no silver is present, little or no dye will be destroyed.
  • the destruction will be partial and to the extent of silver density.
  • a dye image which is a negative rela tive to the silver image is formed. If a silver image is a negative, then the dye image will be a negative of a negative or a positive.
  • a multicolor film containing color formers for the production of azomethine and quinonimine dye images is bleached and destroyed by strong mineral acids, such as those used in silver dye bleach processing.
  • strong mineral acids such as those used in silver dye bleach processing.
  • the concentration of the indophenazine catalyst to approximately 0.5 gram per liter of dye bleach solution containing from 25 to 100 cc. of a weak acid, such as acetic acid, the pH of such a bath can be adjusted so that it is no longer sufliciently low to destroy the azomethine dye irreversibly.
  • a dye bleach bath therefore, utilizing a weak acid instead of a strong acid, such as hydrochloric acid, can serve to yield a dye mask in a monopack film processed by dye coupling procedures.
  • a red-sensitive silver halide emulsion containing Direct Sky Blue (C. I. #520) was coated on a film base, dried, exposed, developed and fixed by 6 the usual processing baths.
  • the fixed film was treated for 10 to 15 minutes in a dye bleach bath of the following composition:
  • Example II A green-sensitive silver halide emulsion containing Fast Acid Magenta (C. I. #30) was coated on a film base, dried, exposed, developed, and fixed by the usual processing baths. The fixed film was treated for 10 to 15 minutes in a dye bleach bath of the following composition:
  • Example III A blue-sensitive silver halide emulsion containing diphenylbiguanide hydrochloride and Dianil Yellow (C. I. #630) was coated on a film base, dried, exposed, developed, and fixed by the usual processing baths. The fixed film was treated for 10 to 15 minutes in a dye bleach bath of the following composition:
  • Example IV A green-sensitive silver halide emulsion. containing diphenylbiguanide hydrochloride and Cotton Red (Schultz #448) was coated on a. glass plate, dried, sensitometrically exposed, developed and fixed by the usual processing baths. The fixed film was treated for 10 to 15 minutes in a dye bleach bath of the following composition:
  • Example V acid -3-stearyl-5 pyrazolone as a color former for the magenta image
  • Benzo Fast Yellow C. 1., 1st ed., #349A
  • diphenylbiguanide hydrochloride as a precipitating agent for the azo dye is coated on top of the cyan layer. After drying, this layer has a density of 1.5 at maximum absorption.
  • the magenta layer is followed by a yellow filter layer and a blue-sensitive silver halide emulsion layer containing 5 (4 stearylaminobenzoylacetamino) terephthalic acid as a non-diffusing color former for the yellow dye image.
  • the film contains yellow dye plus silver negative images in the top layer, magenta dye plus silver negative images and a uniform yellow azo dye in the magenta layer, and cyan plus silver negative images plus a uniform reddish azo dye in the cyan layer.
  • the excess developer is washed from the film and the film subjected to the action of a dye bleach bath of the following composition:
  • the length of time the film is treated in the bleach bath is determined by the time required to bleach the azo dyes and generally will not be sufficient to convert all of the silver into silver salts. Therefore, a treatment with ferricyanide or copper chloride or bromide bleach bath is needed to convert the unused silver to a silver salt soluble in hypo. Following the latter bleaching treatment, the film is fixed and washed in the usual manner.
  • Example Vl Example V was repeated with the exception that the Brilliant Purpurine 10B in the red-sensitive layer was replaced b Orange TA (C. I. #374) and the Benzo Fast Yellow in the greensensitive layer was replaced by Light Fast Yellow (C. I. #640).
  • the negative obtained after processing differs from that obtained in Example V by having in the bottom layer an orange positive masking image instead of a reddish one.
  • a dye bleach bath for producing a colored image in a photographic emulsion layer containing a bleachable azo dye and a silver image comprising an aqueous solution of an alkali halide selected from the class consistin of alkali metal and ammonium bromides, chlorides, and iodides, and an acid selected from the class consisting of mineral and water-soluble organic acids and an accelerating amount of an indophenazine selected from the class consisting of those of the following formulae:
  • R represents a monocyclic aryl hydrocarbon radical and Z and Z represent the atoms necessary to complete a carbocyclic aromatic ring system of the benzene, naphthalene, and anthracene series.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US175467A 1950-07-22 1950-07-22 Indophenazines as catalysts in dye bleach baths for color photography Expired - Lifetime US2627461A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BE504761D BE504761A (en)) 1950-07-22
US175467A US2627461A (en) 1950-07-22 1950-07-22 Indophenazines as catalysts in dye bleach baths for color photography
GB16817/51A GB687768A (en) 1950-07-22 1951-07-16 Indophenazines as catalysts in dye bleach baths for color photography
CH302938D CH302938A (de) 1950-07-22 1951-07-21 Verfahren zur Herstellung von Farbbildern in photographischen Schichten.
DEG6603A DE902220C (de) 1950-07-22 1951-07-22 Farbbleichbad fuer die Farbenphotographie
FR1048365D FR1048365A (fr) 1950-07-22 1951-07-23 Indophénazines catalysantes pour bains de dépouillement de couleurs dans la photographie en couleur

Applications Claiming Priority (1)

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US175467A US2627461A (en) 1950-07-22 1950-07-22 Indophenazines as catalysts in dye bleach baths for color photography

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US2627461A true US2627461A (en) 1953-02-03

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US (1) US2627461A (en))
BE (1) BE504761A (en))
CH (1) CH302938A (en))
DE (1) DE902220C (en))
FR (1) FR1048365A (en))
GB (1) GB687768A (en))

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3259497A (en) * 1961-09-06 1966-07-05 Ciba Ltd Photographic color reversal process
US3318700A (en) * 1962-09-14 1967-05-09 Ciba Ltd Application of dyestuff bleaching catalysts in the silver dyestuff bleaching process
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
US4393208A (en) * 1982-03-29 1983-07-12 Norwich Eaton Pharmaceuticals, Inc. 5-Methyl-2-trifluoromethylindolo[2,3-b]quinoxaline
US5597921A (en) * 1993-04-22 1997-01-28 Taisho Pharmaceutical Co., Ltd. Indolo[2,3-b]quinoxaline derivatives

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3259497A (en) * 1961-09-06 1966-07-05 Ciba Ltd Photographic color reversal process
US3318700A (en) * 1962-09-14 1967-05-09 Ciba Ltd Application of dyestuff bleaching catalysts in the silver dyestuff bleaching process
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
US4393208A (en) * 1982-03-29 1983-07-12 Norwich Eaton Pharmaceuticals, Inc. 5-Methyl-2-trifluoromethylindolo[2,3-b]quinoxaline
US5597921A (en) * 1993-04-22 1997-01-28 Taisho Pharmaceutical Co., Ltd. Indolo[2,3-b]quinoxaline derivatives

Also Published As

Publication number Publication date
GB687768A (en) 1953-02-18
DE902220C (de) 1954-01-21
FR1048365A (fr) 1953-12-22
BE504761A (en))
CH302938A (de) 1954-11-15

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