US3619188A - Bleach-fix processing - Google Patents

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US3619188A
US3619188A US843183A US3619188DA US3619188A US 3619188 A US3619188 A US 3619188A US 843183 A US843183 A US 843183A US 3619188D A US3619188D A US 3619188DA US 3619188 A US3619188 A US 3619188A
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bleach
fix
bath
selenourea
water
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David Gerald Alcock
Enzo Piccotti
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Ilford Imaging UK Ltd
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    • 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
    • G03C5/38—Fixing; Developing-fixing; Hardening-fixing
    • 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
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/42—Bleach-fixing or agents therefor ; Desilvering processes
    • G03C7/421—Additives other than bleaching or fixing agents

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  • BLEACH-FIX PROCESSING This invention relates to color photography and more particularly to the processing of photographic material comprising silver halide emulsion layers and adapted for processing to yield color images, (hereinafter referred to simply as "color photographic material").
  • a developable silver salt image is developed with an aromatic primary amino developing agent of the paraphenylene diamine type (a so-called color developer") in the presence of a compound (a so-called color coupler") which will combine with the oxidation products of the color developer to form an azomethine or quinone-imine dye.
  • the dye is thus formed in situ with the developed silver image. SUbsequently the product must be treated with a bleach bath and a fixing bath or a combined bleach-fix bath thereby to remove silver and any residual silver halide or other silver salt, leaving in the product only the dye image.
  • a bleach-fix bath comprises a mild oxidizing agent for example a ferric-chelate complex, a cupric complex salt or a cobalt (Ill) complex together with a silver halide solvent or fixing agent for example a water-soluble thiosulfate or a water-soluble thiocyanate.
  • a mild oxidizing agent for example a ferric-chelate complex, a cupric complex salt or a cobalt (Ill) complex
  • a silver halide solvent or fixing agent for example a water-soluble thiosulfate or a water-soluble thiocyanate.
  • Stable bleach-fix solutions comprising ferric chelate complexes and sodium thiosulfate may be obtained but because of the weak oxidizing power of the ferric chelate complex such bleach-fix baths can only be used commercially for the processing of photographic materials with a fairly low silver content.
  • lt is the object of the present invention to provide a bleachfix step which can be used in the processing of color photographic material which have a relatively high-silver content, for example color negative material and color reversal material.
  • a bleach fix catalyst which is a water-soluble selenocyanate salt, a selenourea of the general formula I:
  • R, R and R are hydrogen atoms or alkyl groups, at least one of them being a hydrogen atom or a selenouracil of the general formula ll:
  • R, and R are a lower alkyl group and the other a hydrogen atom or both represent hydrogen atoms, and simultaneously or subsequently treating the photographic material in a bleach-fix bath which comprises an aqueous solution comprising an oxidizing agent which is either a ferric chelate or a diaquo-tetrammine-cobalt (lll) complex, and a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate.
  • a bleach-fix bath which comprises an aqueous solution comprising an oxidizing agent which is either a ferric chelate or a diaquo-tetrammine-cobalt (lll) complex, and a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate.
  • lower alkyl group is meant an alkyl group which comprises from one to six carbon atoms.
  • ferric chelate complex is meant a coordination compound of the ferric ion and a compound which comprises nitrogen and/or oxygen-containing coordinating groups.
  • the most important coordinating groups are amino, nitrogen heterocyclo, carboxyl and carbonyl groups.
  • the preferred ferric chelate complex for use in the bleachfix step of the present invention is a ferric ethylenediaminetetraacetic acid complex. It is to be understood that this compound may be used as such in the preparation of a bleach-fix bath or it may be formed in situ in a bleach-fix bath by ethylenediaminetetraacetic acid reacting with a ferric salt e.g. ferric chloride. in the examples which follow the ferric ethylenediaminetetraacetic acid complex has been formed in situ.
  • ferric chelate complexes which may be used in the present invention are for example pyridine-2:6-dicarboxylatoferrate (lll) complex, iminodiacetatoferrate (lll) complex and'nitrilo-triacetateferrate (lll) complex.
  • the preferred bleach-fix catalysts for use in the process of the present invention is a selenourea of the general formula III:
  • R is a lower alkyl group.
  • the bleach-fix catalysts of use in the present invention are preferably added to the bleach-fix bath but they may be present during the bleach-fixing treatment adsorbed to or absorbed in the color photographic material.
  • the bleach-fix catalysts of use in the present invention and in particular the bleach-fix catalysts of fonnula lll may be present in any treat ment bath or wash bath which is used in the color development process between the development step and the bleachfix step.
  • Exemplary of such baths are stop baths and stop-fix baths.
  • selenocyanate these compounds cannot be used in an acid bath because they decompose yielding a highly toxic gas.
  • the bleach-fix catalysts cannot be present, however, in the developing solution as they interfere with the development of the color material. For the same reason the bleach-fix catalysts of use in the present invention can not be present initially in the photographic material.
  • a bleach-fix bath which comprises an aqueous solution of an oxidizing agent which is either a ferric chelate complex or a diaquo-tetrammine-cobalt (Ill) complex, a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate and a bleach-fix catalyst which is a water-soluble selenocyanate salt, a selenourea of the formula I as hereinbefore set forth, or a selenouracil of fonnula ll as hereinbefore set forth.
  • an oxidizing agent which is either a ferric chelate complex or a diaquo-tetrammine-cobalt (Ill) complex
  • a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate
  • a bleach-fix catalyst which is a water-soluble selenocyanate salt
  • the concentration of water-soluble selenocyanate salt in the bleach-fix bath is from 0.l to 200 g. per liter of solution and most preferably approximately 5 g. per liter of solution.
  • the concentration of selenourea of formula l or of the selenouracil of formula II present in the bleach-fix bath is from 0.5 to 1.5 g. per liter of the solution and most preferably 0.1 g. per liter of solution.
  • the temperature of the bleach-fix bath is approximately 24 C.
  • the concentration of the selenourea of formula I or of the selenouracil of formula ll present in a stop bath or a stop-fix bath or in a wash bath is from 0.5 mg. to 3.0 g. per liter of the solution and most preferably 0.3 g. per liter of solution.
  • a sample of the same photographic material was instead satisfactorily processed by using the same processing sequence, but bleach-fixing it for only 6 minutes, when 300 mg. of selenourea were added to the stop-fix bath described above.
  • a color negative tripack as in example I was given a neutral wedge exposure and processed, the processing sequence being as in example 1, except for the stop-fix stage which was carried out in this example by treating the material for 4 minutes in the following stop-fix bath.
  • a color negative tripack material as in example i was given a neutral wedge exposure and processed, the processing sequence being as in example 1, except for the stop-fix stage which was carried out by treating the material for 6 minutes in a stop-fix bath of the following composition.
  • a color negative tripack as in example I was given a neutral wedge exposure and satisfactorily processed by using a processing sequence similar to that described in example i, except that instead of the stop-fix bath a stop bath of the following composition was used.
  • the bleach-fix bath used in this test has a composition similar to that of the bleach-fix bath described in example 1, except that its sodium thiosulfate pentahydrate content was raised to g.
  • Thebleach-fixing time was 6 minutes.
  • a sample of the same photographic material as used in example l was given a neutral wedge exposure and color processed using the same processing sequence and processing 5 solutions as set forth in example I except that 100 mg. of selenourea were present in the bleachix bath.
  • the bleach-fix time required was only 6 minutes and the material was found to be satisfactorily bleached in the high-exposure areas.
  • a color negative tripack material as in example I was given a neutral wedge exposure and satisfactorily processed, the processing sequence being as in example I except for the bleach-fix stage, which was carried out by treating the material for 8 minutes in the following bath.
  • R,, R and R are hydrogen atoms or alkyl groups, at least one of them being a hydrogen atom or a selenouracil of the general formula:
  • a bleach-fix bath which comprises an aqueous solution comprising an oxidizing agent which is either a ferric chelate or a diaquo-tetrammine-cobalt (lll) complex, and a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate.
  • bleach-fix catalyst is a selenourea of the general formula:
  • R, R, and R are hydrogen atoms or alkyl groups, at least one of them being a hydrogen atom or a selenouracil of the general formula:
  • R, and R are a lower alkyl group and the other a hydrogen atom or both represent hydrogen atoms.
  • bleach-fix catalyst is a selenourea of the general formula:
  • R is a lower alkyl group.

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

Abstract

This application describes a bleach-fix process which comprises bleach-fixing photographic silver halide color material, after development of the silver image, in the presence of a watersoluble selenocyanate salt, selenourea, substituted selenourea or substituted selenouracil.

Description

United States Patent Priorities David Gerald Alcock;
Enzo Plccotti, both 01 "ford. England 843,183
July 18, I969 Nov. 9, I971 lllord Limited Iliord. England July 24, 1968 Great Britain Apr. 14, 1969, Great Britain, No. 18,934/69 BLEACH-FIX PROCESSING 9 Claims, No Drawings US. Cl
96/52. 96/60. 96/22 Int. Cl G036 5/32, G03c 7/00, G03c 5/26 [50] Field of Search 96/60, 60 BF,
Primary Examiner- Norman 0. Torchin Assn/an! Examiner-Mary F. Kelley Almrney-Cushman, Darby & Cushman ABSTRACT: This application describes a bleach-fix process which comprises bleach-fixing photographic silver halide color material. after development of the silver image. in the presence of a water-soluble selenocyanate salt. selenourea. substituted selenourea or substituted selenouracil.
BLEACH-FIX PROCESSING This invention relates to color photography and more particularly to the processing of photographic material comprising silver halide emulsion layers and adapted for processing to yield color images, (hereinafter referred to simply as "color photographic material").
In the conventional processing of such color photographic material a developable silver salt image is developed with an aromatic primary amino developing agent of the paraphenylene diamine type (a so-called color developer") in the presence of a compound (a so-called color coupler") which will combine with the oxidation products of the color developer to form an azomethine or quinone-imine dye. The dye is thus formed in situ with the developed silver image. SUbsequently the product must be treated with a bleach bath and a fixing bath or a combined bleach-fix bath thereby to remove silver and any residual silver halide or other silver salt, leaving in the product only the dye image.
The use of a combined bleach-fix bath is preferable because it results in a reduction of the processing time and of the processing equipment required. Normally a bleach-fix bath comprises a mild oxidizing agent for example a ferric-chelate complex, a cupric complex salt or a cobalt (Ill) complex together with a silver halide solvent or fixing agent for example a water-soluble thiosulfate or a water-soluble thiocyanate.
Stable bleach-fix solutions comprising ferric chelate complexes and sodium thiosulfate may be obtained but because of the weak oxidizing power of the ferric chelate complex such bleach-fix baths can only be used commercially for the processing of photographic materials with a fairly low silver content.
lt is the object of the present invention to provide a bleachfix step which can be used in the processing of color photographic material which have a relatively high-silver content, for example color negative material and color reversal material.
According to the present invention in a color development process for the production of the colored image in exposed color silver halide photographic material there is provided after the development step, the step of treating the photographic material with an aqueous solution of a bleach fix catalyst which is a water-soluble selenocyanate salt, a selenourea of the general formula I:
Re I
wherein R,, R and R, are hydrogen atoms or alkyl groups, at least one of them being a hydrogen atom or a selenouracil of the general formula ll:
wherein one of R, and R is a lower alkyl group and the other a hydrogen atom or both represent hydrogen atoms, and simultaneously or subsequently treating the photographic material in a bleach-fix bath which comprises an aqueous solution comprising an oxidizing agent which is either a ferric chelate or a diaquo-tetrammine-cobalt (lll) complex, and a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate.
By lower alkyl group is meant an alkyl group which comprises from one to six carbon atoms.
By ferric chelate complex is meant a coordination compound of the ferric ion and a compound which comprises nitrogen and/or oxygen-containing coordinating groups. The most important coordinating groups are amino, nitrogen heterocyclo, carboxyl and carbonyl groups.
The preferred ferric chelate complex for use in the bleachfix step of the present invention is a ferric ethylenediaminetetraacetic acid complex. It is to be understood that this compound may be used as such in the preparation of a bleach-fix bath or it may be formed in situ in a bleach-fix bath by ethylenediaminetetraacetic acid reacting with a ferric salt e.g. ferric chloride. in the examples which follow the ferric ethylenediaminetetraacetic acid complex has been formed in situ.
Other ferric chelate complexes which may be used in the present invention are for example pyridine-2:6-dicarboxylatoferrate (lll) complex, iminodiacetatoferrate (lll) complex and'nitrilo-triacetateferrate (lll) complex.
The preferred bleach-fix catalysts for use in the process of the present invention is a selenourea of the general formula III:
III
wherein R is a lower alkyl group.
The bleach-fix catalysts of use in the present invention are preferably added to the bleach-fix bath but they may be present during the bleach-fixing treatment adsorbed to or absorbed in the color photographic material. Thus the bleach-fix catalysts of use in the present invention, and in particular the bleach-fix catalysts of fonnula lll may be present in any treat ment bath or wash bath which is used in the color development process between the development step and the bleachfix step. Exemplary of such baths are stop baths and stop-fix baths. However in the case of selenocyanate these compounds cannot be used in an acid bath because they decompose yielding a highly toxic gas.
The bleach-fix catalysts cannot be present, however, in the developing solution as they interfere with the development of the color material. For the same reason the bleach-fix catalysts of use in the present invention can not be present initially in the photographic material.
According to another embodiment of the present invention there is provided a bleach-fix bath which comprises an aqueous solution of an oxidizing agent which is either a ferric chelate complex or a diaquo-tetrammine-cobalt (Ill) complex, a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate and a bleach-fix catalyst which is a water-soluble selenocyanate salt, a selenourea of the formula I as hereinbefore set forth, or a selenouracil of fonnula ll as hereinbefore set forth.
It is preferred that the concentration of water-soluble selenocyanate salt in the bleach-fix bath is from 0.l to 200 g. per liter of solution and most preferably approximately 5 g. per liter of solution.
It is preferred that the concentration of selenourea of formula l or of the selenouracil of formula II present in the bleach-fix bath is from 0.5 to 1.5 g. per liter of the solution and most preferably 0.1 g. per liter of solution.
It is preferred that in use the temperature of the bleach-fix bath is approximately 24 C.
It is preferred that the concentration of the selenourea of formula I or of the selenouracil of formula ll present in a stop bath or a stop-fix bath or in a wash bath is from 0.5 mg. to 3.0 g. per liter of the solution and most preferably 0.3 g. per liter of solution.
The following Examples with serve to illustrate the invention.
EXAMPLE I A negative tripack color material comprising a silver halide emulsion containing color couplers, was given a neutral wedge exposure and color processed, the processing sequence being as follows.
Color development 6 minutes Sodium metaborate 53.3 g. Sodium hydroxide 2.0 g. Sodium sulfite anhydrous 3.9 g. Potassium bromide 0.70 g. Hydroxylamine sulfate 2.34 g. Sodium sulfate anhydrous 7.8 g. 4-Amino-N-ethyl-N-(4-hydroxybutyl)- aniline sulfate 6.0 g. Water to liter Stop fix 4 minutes Sodium thiosulfate pentahydrate l7l.0 g. Sodium acetate anhydrous 3|.4 g. Sodium sulfite anhydrous 4.3 g. Acetic acid (glacial) 35 ml. Potassium alum l7.0 g. Ammonium chloride 43.0 g. Water 1 liter Wash 4 minutes Bleach-fix 25 minutes Disodium tctraborate decahydrate l2.5 g. Boric acid 22.5 g. Sodium hydroxide 10.0 g. Ethylenediaminetetraacetic acid 16.2 g. Disodium salt of ethylenediaminetetraacetic acid dihydrate 3.5 g. Ferric chloride (60% WIV soln.) l mlv Sodium thiosulfate pentahydrate 95.0 g. Sodium sulfite anhydrous 4.0 g. Water to 1 liter Wash 4 minutes Conditioner 4 minutes Disodium salt of ethylenediaminetetraacetic acid dihydrate 0.50 g. Sodium carbonate anhydrous 4.5 g. Formaldehyde (40% W/V loln.) l0 ml. Lissapol (8% soln.) l.7 ml. Water to 1 liter Walit 4 minutes Dry The processed material was bleached in the low-exposure areas, but unsatisfactorily bleached in the parts at high-exposure.
A sample of the same photographic material was instead satisfactorily processed by using the same processing sequence, but bleach-fixing it for only 6 minutes, when 300 mg. of selenourea were added to the stop-fix bath described above.
EXAMPLE 2.
A color negative tripack as in example I, was given a neutral wedge exposure and processed, the processing sequence being as in example 1, except for the stop-fix stage which was carried out in this example by treating the material for 4 minutes in the following stop-fix bath.
Sodium thiosulfate pentahydrate |7t.0 g. Sodium acetate anhydrous 3L4 g. Sodium sulfate anhydrous 4.3 g. Acetic acid (glacial) 35 ml. Potassium ulum l7.0 g. Ammonium chloride 43.0 g. N-methyl-selenourea 300 mg. Water to l liter The sample was found to be satisfactorily processed.
EXAMPLE 3.
A color negative tripack material as in example i, was given a neutral wedge exposure and processed, the processing sequence being as in example 1, except for the stop-fix stage which was carried out by treating the material for 6 minutes in a stop-fix bath of the following composition.
Sodium thiosulfatc pentuhydratc l7l.0 g. Sodium acetate anhydrous 31.4 g. Sodium sulfite anhydrous 4.3 g. Acetic acid (glacial) 35 ml. Potassium alum 17.0 g. Ammonium chloride 43.0 g. N,N-dimethyl-selenourea 200 mg. Water to l liter The bleach-fixing time was 9 minutes and the sample was found to be satisfactorily processed.
EXAMPLE 4.
The tests described in the examples 1, 2 and 3 were re; peated, but the 4 minutes wash between the stop-fix and the bleach-fix stage was omitted.
The neutral wedge exposed photographic material was again satisfactorily processed.
EXAMPLE 5.
EXAMPLE 6.
A color negative tripack as in example I was given a neutral wedge exposure and satisfactorily processed by using a processing sequence similar to that described in example i, except that instead of the stop-fix bath a stop bath of the following composition was used.
Sodium acctate 9.0 g, Acetic acid (glacial) 5.2 ml. Sodium metalsulfite 5.0 g. Selenourea 300 mg. Water to 1 liter The bleach-fix bath used in this test has a composition similar to that of the bleach-fix bath described in example 1, except that its sodium thiosulfate pentahydrate content was raised to g.
Thebleach-fixing time was 6 minutes.
EXAMPLE 7.
A sample of the same photographic material as used in example l was given a neutral wedge exposure and color processed using the same processing sequence and processing 5 solutions as set forth in example I except that 100 mg. of selenourea were present in the bleachix bath. The bleach-fix time required was only 6 minutes and the material was found to be satisfactorily bleached in the high-exposure areas.
EXAMPLE 8.
A color negative tripack material as in example I, was given a neutral wedge exposure and satisfactorily processed, the processing sequence being as in example I except for the bleach-fix stage, which was carried out by treating the material for 8 minutes in the following bath.
a neutral wedge exposure and satisfactorily processed, the processing sequence being as in example l, except for the bleach fix stage which was carried out for 6 minutes in a bath having the following composition.
Bleach-Fix Disodium tetraborate decahydrate 12.5 g. 45 Boric acid 22.5 g.
Sodium hydroxide 100 g. Ethylenediaminetetraacetic acid 16.2 g.
Disodium salt of ethylenediaminetetraacetic acid dihydrate 3.5 g.
Ferric chloride (60% W/V soln.) l5 ml.
Sodium thiosulfatec pentahydrate 95.0 g. Sodium sulfite anhydrous 4.0 g. Potassium selenocyanate 5.0 g. Water to 1 liter pH 7.l
55 EXAMPLE 10.
Bleach-Fix 5 Diaquo-tetrummine cohalt (Ill) sulfate monohydrute 30.0 g.
Sodium thiosulphate pentahydrute l40.0 g.
selenourea 360 mg.
Water to l liter The same negative material was largely unbleached when processed for the same time in a similar bleach fix bath but from which the selenourea had been omitted. 7
Although the examples given are based on the results obtained for a typical color negative material, similar improvements are obtained when color reversal material is bleachfixed with the exemplified compositions.
The pHs of the solutions quoted are not a limiting factor for the catalytic activity of the compounds disclosed, although soluble selenocyanates are unstable in acid solutions and tend to decompose with evolution of toxic gases.
We claim as our invention:
1. In a color development process for the production of a colored image in exposed color silver halide photographic material. after the development step, the step of treating the photographic material with an aqueous solution ofa bleach-fix catalyst which is a water-soluble selenocyanate salt. a selenourea of the general formula:
It- .40 ll;
wherein R,, R and R are hydrogen atoms or alkyl groups, at least one of them being a hydrogen atom or a selenouracil of the general formula:
50 IT; N H
l ('r: (j r R5 (I) wherein one of R and R is a lower alkyl group and the other a hydrogen atom or both represent hydrogen atoms, and simultaneously or subsequently treating the photographic material in a bleach-fix bath which comprises an aqueous solution comprising an oxidizing agent which is either a ferric chelate or a diaquo-tetrammine-cobalt (lll) complex, and a silver halide solvent which is either a water-soluble thiosulfate or a watersoluble thiocyanate.
2. A process according to claim I wherein the bleach-fix catalyst is present in the bleach-fix bath.
3. A process according to claim 1 wherein the bleach-fix catalyst is present in a stop bath or stop-fix bath which is used to treat the photographic material after development and prior to the bleach-fix step.
4. A process according to claim 1 wherein the bleach-fix catalyst is present in a wash bath wherein the photographic material is washed after development and prior to the bleachfix step.
5. A process according to claim 1 wherein the bleach-fix catalyst is a selenourea of the general formula:
ll R1 N(1--N II ll So it wherein R,, R, and R are hydrogen atoms or alkyl groups, at least one of them being a hydrogen atom or a selenouracil of the general formula:
wherein one of R, and R, is a lower alkyl group and the other a hydrogen atom or both represent hydrogen atoms.
7. A bleach-fix bath according to claim 6 wherein the bleach-fix catalyst is a selenourea of the general formula:
wherein R, is a lower alkyl group.
8. A bleach-fix bath according to claim 6 wherein the con- [0 centration of water-soluble selenocyanate salt therein is from 0.1 to 200 g. per liter of solution.

Claims (8)

  1. 2. A process according to claim 1 wherein the bleach-fix catalyst is present in the bleach-fix bath.
  2. 3. A process according to claim 1 wherein the bleach-fix catalyst is present in a stop bath or stop-fix bath which is used to treat the photographic material after developmenT and prior to the bleach-fix step.
  3. 4. A process according to claim 1 wherein the bleach-fix catalyst is present in a wash bath wherein the photographic material is washed after development and prior to the bleach-fix step.
  4. 5. A process according to claim 1 wherein the bleach-fix catalyst is a selenourea of the general formula:
  5. 6. A bleach-fix bath which comprises an aqueous solution of an oxidizing agent which is either a ferric chelate complex or a diaquo-tetrammine-cobalt (III) complex, a silver halide solvent which is either a water soluble thiosulfate or a water-soluble thiocyanate and a bleach-fix catalyst which is a water-soluble selenocyanate salt, a selenourea of the general formula:
  6. 7. A bleach-fix bath according to claim 6 wherein the bleach-fix catalyst is a selenourea of the general formula:
  7. 8. A bleach-fix bath according to claim 6 wherein the concentration of water-soluble selenocyanate salt therein is from 0.1 to 200 g. per liter of solution.
  8. 9. A bleach-fix bath according to claim 6 wherein the concentration of selenourea therein of the formula set forth in claim 6 or of selenouracil therein of the formula set forth in claim 6 is from 0.5 mg. to 1.5 g. per liter of the solution.
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US3767401A (en) * 1971-12-15 1973-10-23 Minnesota Mining & Mfg Regeneration of photographic bleach/fix baths
US3773510A (en) * 1971-06-26 1973-11-20 Minnesota Mining & Mfg Additives to bleach/fix baths
US3775125A (en) * 1970-10-01 1973-11-27 Ilford Ltd Selenium compounds
US5166045A (en) * 1989-06-19 1992-11-24 Eastman Kodak Company Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains

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DE2226770C2 (en) * 1971-06-07 1982-06-24 Eastman Kodak Co., 14650 Rochester, N.Y. Photographic process for the production of pictures

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US3297447A (en) * 1964-07-22 1967-01-10 Eastman Kodak Co Stabilization of synergistically sensitized photographic systems

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3297447A (en) * 1964-07-22 1967-01-10 Eastman Kodak Co Stabilization of synergistically sensitized photographic systems

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3775125A (en) * 1970-10-01 1973-11-27 Ilford Ltd Selenium compounds
US3773510A (en) * 1971-06-26 1973-11-20 Minnesota Mining & Mfg Additives to bleach/fix baths
US3767401A (en) * 1971-12-15 1973-10-23 Minnesota Mining & Mfg Regeneration of photographic bleach/fix baths
US5166045A (en) * 1989-06-19 1992-11-24 Eastman Kodak Company Doping of silver halide emulsions with group VIB compounds to form improved photoactive grains

Also Published As

Publication number Publication date
DE1937727C3 (en) 1979-01-18
FR2013616A1 (en) 1970-04-03
DE1937727B2 (en) 1978-05-18
GB1217194A (en) 1970-12-31
CA926184A (en) 1973-05-15
DE1937727A1 (en) 1970-01-29

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